聚合物基固态电池关键材料开发 2024.docx

目标：高安全.高能量密度电池固态电池体系:(1)不(少)含易燃液体,提高安全锂(合金)负极(>150OmAhg),替代石墨负极(372mAhg),提高能量密度1态聚合物电解质的发展简史K.Shinohara,J.Polym.Sci.Polym.1.ett.Ed.1984,22,659-663.tM.Watanabe.Macromolcculcs.1984,17,2908-2912I.M.Ward.乙MellgPommel；jAppl.Polym.Sci984,25,1600-1602D.HShriver92010,115,2718-2722.W.D.ZhuuChem.Maten4199«,10,2307-2308Adv.Mater.,2019,31,1805574聚硅氧烷g聚(从丙内曲)(PP1.)聚(乙二2)甲基酸丙怵酸酯(PPlGlA)聚环里乙烷(PEO)聚乙二醇丁二酸酯(l,E-2,4)聚磷脂(PP)聚裱酸亚乙烯能聚味酸亚丙诙(PPC(PVc聚拮基丙饪酸能聚草酸酯(POE)聚二叙戊环.聚四氢味喃(PIX)1.,PTIIE)聚丙二酸胺(P1聚三亚甲基碳酸能PfMCP.V.Wright.Polymer,1973,14.5H9M.Watanabe.,Macromolecules,I).F.Shriver.1.m.C'hen.Soc.,1984,106.6854-6855M.J.Smith,SolidStateIonics.2001,140,345-3511984.17,2902-2908K.N1.AbrHham,Elcctrochiin.Acta,199136,773-782W.D.ZhouAdv.EnergyMater.,2020,10.2002416G.1.Cui,CSpl.Mater.Interfaces,2015,7,4720-4727ACSSustainableChemistry&Engineerings2023,11,1253-1277I标：高安全,高能量密度电池生产成本较高离子扩散动力学迟缓界面电化学不稳定聚合物分子结构调控相界面重构固态电解质回收电解质带隙调控电极表面调控聚合物热行为分析一二一0000CF人rRpArR+"阐明聚合物电解质构淡关系拓宽电化学窗口,稳定界面抑制界面副反应电解质热降解与锂盐高效回收聚合物结构调控OOOeq人CrR(O人CrR)O乂CG,1100CFrR(cr<)0YCF30，n0挑战：聚合物电解质的氧化还原窗口较窄策略：（1）双层聚合物/聚合物电解质，高电压SPE接触正极，低电压SPE接触锂金属负极；（2）原位钝化界面全固态电池设计图析（d）固态1.UMO-T1.UMO-2H0M0-1HQMOT2|固态双层电解质扩大窗口液态1.UMO1H0M0-2液态双电解质固态混合电解质VS减少窗口最高占据分子轨道（HOMO）,最低未占据分子轨道（1.UMO）Adv.Mater.,2019,37,1805574,高被引；中国专利授权号：201810768363.8Adv.EnergyMater.2020,2002416储能科学写技术2Q22,H,17881.2同时稳定正负极界面？氟化聚草酸酯目标：设计新的聚合物结构，同时兼容高电压正极和低电压负极策略：聚酯耐受高电压，含F基团可以原位与金属锂形成钝化层，稳定与金属锂的界面。新结构：氟化的聚草酸酯。聚草酸酯类电解质的本征导离子率氟化草酸酯HOMO£*OfJ1.2同时稳定正负极界面？氟化聚草酸酯1.iNMC811全固态电池2w-1FFrc*A4<wMcacycltne-*UCft-POE-F-UMMCail*mcM<y-SHGMAyMCimmoRcy7-»QCS三UanouOMWM50100150200Capacrty(mAhg')(d)BOINt0CyemmbfDcycle100CYCte200cycle100OG5UJMO-kMOINoIWOT(ohmcm,)_>&&o>13聚酯类电解质系统研究(1)揭示分子结构导离子率关系,以聚碳酸酯.聚草酸酯,聚丙二酸酯为例，(2)氟带乙酸酯封端，与锂金属原位形成1.iF基复合S曰，提高与锂金属稳定性。ThisWorkTypicalSPEsPEO<basedSPEPPC<basedSPEC5-PCEFC5-POE-FC54>ME-FDM-C5-PMEVStaMIixed1.Ianode>/StabilizedUanodHighoxidativetobUltyX1.owionicconductivityUnsUblwith1.fanodHJghoxldt)vatabilrty1.owionicconductivityXStabilUed1.iano«l«y/HighoktetivstabilityGoodIonicconductivityvz,StotMlized1.ianode×Pooroxidauv*stabilityVGoodionicconductivityV*rHighoxldativstability"improvedIonicc(Mtducbvityy/StobiIiMd1.ianody<Highovidtivtab*iity×DecreawdIonkConducttvftySolidclrotylinterpMsolMtatpolymrctrolyt;Udendrite*Angew.Chem.Int.Ed.f2023,e202218229hotpaper1.4聚酯类电解质系统研究聚酯类电解质的本征导离子率100200300400SOO600700800Temperature(eC)第二号M100200300400500600700800Temperature(eC)GO)号medE>luo三sodEO。吕OO51.4s6(db.uns)b号05044srE。S)Temperature(oC)7060504030.93.03.13.23.3341000T(K1)3.0<5.5(EOSK号Temperature()7060504302.8293.03.13.23.33.4100Qrr(KT)-3-3Y-5-5)runebwlTemperature()70605040303.03.13J3.33.4100OZT(K,)碳酸酯Singlecrystal1.iTFSI=(EC)1导离子率升高的原因：(1)聚合物分子链的柔性增加，Tg降低(2)草酸酯,丙二酸酯与锂盐之间形成螯合配位，有利于锂盐的解离草酸酯1.iSinglecrystalSinglecrystal1.iFSk(DMOA)11.iTFSI=(DMOA)2TFSF<Jio含氟基团对界面稳定性的影响（八）o,O150.0100005<0000占0.010三0005t0000O0010OOOS0000SOS.52.53.03.6404.6Voltage(V)060.0>)。6£。>663o31)O.O.O.ADS&3-o>400600Time（三）210120.0.0.4Q<E)wexlnu9.3-1.0-0.50.00.51.01.S2.02.5<E=u£n。-O6.3O.3O.O.O.4皿£)362o>0601002003004005006007008009001000Time（三）-o,4-4，-J01002003004005006007008009001000Time（三）Il406.2E4.4.3.3.Za)£wso>1801501209060300可(q<E)3UedeU1.iC5*PCEF1.VNCM6221»t,3rd-Soth100th200f聚碳酸酯65C306090120150Capacity(mAhg1)聚草酸酯1.VC5OEF-1.UNCMcycling.U/C54»ME#-U4<CMcycling1.VCM>CF1.VNCMefficiency1.VC54>OE-F.1.UNCMefficiency1.MC5PME<F1.UMCMrficiency4080120160Cyclenumber(K)AUUOOE山U2EO3OO406.84.4.3.3Zb)(>)02-o>e)6u4三Aoedeo1.iZCS-POEF4uNCM6221st-100I-SOth100lh200th草酸酯45。C50100150Capacity(mAhg'1)二聚二甲基丙二最醋聚丙二酸酯UM-C5-PMEUMCMcycling1.iC64>M-F4JNCMcycling1.0MCS4>MEF-1.VNCMflcwncy1.iCS4>ME-F-1.VNCMfftcr4080120160CyclenumberKetone-enoltautomeric.40.62.84.4.3.1N>)362o>U/CSPME.F4.UNCM6221st3rd60th丙二酸酯35C50100150200Capacity(mAhg'1)Dd1U。一W98JXUedeO(渣)mu三lu&qEO30。Oooooo198765Trasitionmetalchelate12C2-C10a6r,-C4-vN£S二0加二长发I38”Ml才9卜。ja456CX4P筑一长度/OCb*"、opcr¾I99II-。C5«¥jIi5.1*W!.A-<Jy445cc*A5干.e4cj*/4“H3MBM信用i(.一卫一一五CTV31m-TAV定C，二*J.Am.Chem.Soc.2024,146,5940-595113From全固态to准固态?聚合物基准问题:(1)较低的本征导离子率，在完全无溶剂的条件下，室温的导离子率低于10-4s/cm(2)成本低，有利于规模化应用，100o500元kg,1.iTFSl回收后会进一步降低“全固态”“准固态”聚合物基准固态是一个更加切实的路径(1)室温的导离子率高于103S/Crn(2)电化学窗口宽，界面接触好(3)成本低，有利于规模化应用runS)O号2.93.03.13.23.33.4IO(WTK1Cyclenumber2原位固态化路线选择双键自由基聚合vs.开环聚合(1)两条路线，四种代表性酯类单体，揭示聚合条件单体转化率导离子率关系(2)相同含F链段为锂金属提供相似1.iF基S日保护，揭示残留单体对界面稳定性影响。双键自由基聚合开环聚合（八）DoubleBondRadicalPolymerizationVECTFPMA(b)RingOpeningPolymerization(c)KeyPointsforln-situPolymerizationAngew.Chem.Int.Ed,2023,e202309613催化剂用量2.原位固态化路线选择双键自曲基聚a4=5环聚合开环聚合1SM0t*t%)双键自由基聚合一7C聚合时间双键自由基聚合三,WBG=5eo<n开环聚合241.5eFJ70Jrn%rtu5rclo2M3.13.23SX4100am2.原位固态化路线选择锂盐和碳黑,双键自由基聚合VS.开环聚合界面稳定性2.原位I态化路线选择双键自由基聚合VS,开环聚合VEO1.iTFSIUmUl(IrnV三C-TFPMA-UTFSIUmtal(RT)Ooo叼<£HJa(b)0.002.53.03.54.04.55.05.5Voltage(V)（三）o.30100200.300400500600CO.c3Jno0.00,1.01.52.02.53.03.54.04.55.05.5Voltage(V)2原位固态化路线选择双键自由基聚合vs开环聚合PVECgPV1.基(b)0504.3.3.>)6so>O50100150200Specificcapacity(mAhg1)(d)4.52.5O(6UqE-oEdeoQ.5.04.3.3.(>B6B1O>240-200160-12080*40V-Auuu三w2EO三o3OQoO8642JP(V三C.TFPIIA)IFMP(25*C)50100150SpecificCapacity(mAho.O20406080Cyclenumber(n)0.5。&l3.>)362o>1.IP(V1.-TFP)1.FMP(45).5Q.5.0&4.3.配CT5O>Oooooo4062842211Hv<6f<三-xlpedeo(点)>uco三U2EC3O0OoOoOO18642Oo*.o124k=.，O50100150200Specificcapacity(mAhg“)20406080Cyclenumber(n)SIPrecursor÷U9.OI.Precursor1.iPrecursor÷UMoltensaltc?FSingIe-CrystalAIHighNickelI?.p×ideCathode/W&W力、.7SMteRngdJI.、A三三三三三Adv.EnergyMater.2023,2203188Adv.EnergyMater.,2023,2300378>-aso>55OX3.262o>1060oC-1min250Initialdischargecapacity1.VNiintermixingVl/050100150200250Capacity(mAhg,)ZO0(e)50100150200250CapacityfmAhg，2-1I(MOAC15mln106Qai5min50100150200250Capacity(mAhg')2502001501000oC1020oCI(MooC1060oC-15min15mi11>15min-15min(求)6UM-BWfzjIoi15<6we)edj2皿3750oC1OOOoC1020oC1040oC1060oCm-h1mln-1min1min-1min1201英)Au3o三w750oC-8h75OeC1000C102OoC1040CIOeOOCMOOg级制）备颗粒形貌可调控的高银小单晶:SGNCM90)报告总结聚合物固态电解质体系a）提出了双层聚合物电解质的设计概念，扩大电化学窗口b）制备了含F的聚草酸酯结构，同时稳定金属锂和高电压的正极。c）揭示了聚合物结构与导离子率性能之间的构效关系。低成本生产单晶高锲正极材料a）无熔盐脉冲高温法制备八面体单晶b）晶粒生长抑制剂存在下的三段烧结，制备高分散立方体单晶