物理所鈉電池

鈉離子電池電解質(zhì)材料研究進(jìn)展及挑戰(zhàn)一切新電池體系的確立從電解液開始十十電解液：鹽+溶劑Arrhenius電解液：鹽+溶劑Arrhenius提出電解液離子導(dǎo)電理論，獲得1903年諾貝爾化學(xué)獎不同的電池體系需要不同的電解液提出高鹽濃度電解液提出雙功能性金屬鋰基超高鹽濃度電解質(zhì)同時解決多硫離子溶解和鋰負(fù)極高鋰離子濃度：高粘度：DDb0Mi0("cycleaumber/s"CoulombicemciencyM溶解反應(yīng)平衡Li?S(4<x<8)<→2Li++Sx2-同離子效應(yīng)coulomblcsinckens)*%CarbonLit“Salt-in-Solvent”[salt]<[solvent]complexcomplexOLi?Liz+Liz+mSn(8≤n≤4,m>0)提出高鹽濃度電解液概念(打破定式)1.Lithiumionconductor2.Lil/Al?O3"Polymer-in-Salt"([salt]>[polymer])Plasticcrystalelectrolyte([salt]<[polymer])electrolytesLiquid-basedelectroSolvent-in-Salt'([salt]>[solvent]fig.1b)SoggysandelectrolyteTraditionalnon-aqueonselectrolytes([salt]<[10“Solvent-in-Salt“Solvent-in-Salt”Solvent-in-Salt”C“Solvont-in-Salt”L.M.Suo,Y.-S.Hu*etal.,NatureCommun.2013,4,1481.引用1531次高鹽濃度電解液拓展到其他電池體系 w wfmboumdldMs-MterlliYmcmEnhancedCyclingStabilityofRechargeableLi-O?BatteriesUsingHigh-ConcentrationElectrolytesBinLiu,WuXu,*PengfeiYan,XiuliangSun,MarkE.Bowden,JefreyRead,JiangfengQian,DonghaiMei,Chong-MinWangandji-CuangZhang*美國PNNL國家實驗室水系鋰離子電池(2015年)“Water-in-salt”electrolyteenableshigh-voltageaqueousLJumlnSuo,'OlegBorodln,'TaoGao,'MarcoOlguln,2JanetIlo,2XIullnFan!'ChaoLao,'ChunshengWang."KangXu2美國馬里蘭大學(xué)，美國陸軍實驗室高安鈉離子電池(2017年)ARTICLES功ARTICLES功000Fire-extinguishingorganicelectrolytesforsafebatteriesianhulWange:YuKIYamadaP,KeltaroSodoyama,ErikoWatanabo,klTakdalYoshitakaTateyamal"andAtuoYomada.日本東京大學(xué)Solvent-in-Salt引用總次數(shù)在NatureCommun.創(chuàng)刊以來41944篇)中排名131位鋅離子電池(2018年)ARTICLESmaterialsARTICLESHighlyreversiblezincmetalanodeforaqueousbatteriesFlWane.Ogberdn',TGo,XNinfon,Walsun,IwsongHn',Antonslren'.kouchADun'KngX"dOmsWa~美國馬里蘭大學(xué)高安全鋰離子電池(2018年)ZiaiZeng':VjayakumarMurugesan2,KeeSungHan',XIlaoyuJlang',YuliangCao'",LifenXiao',XinpingA',HanslYang',Ji-GuangZhang',MarlaLSushko2andJunLlu3武漢大學(xué)，美國PNNL國家實驗室鉀離子電池(2019年)storageUwelliangYaiangLuo",ChenglongZhao,UluLu,JienanZhang',QingeiangZhng,XIngShen',JunmelZhao',XlalanYuo',Hongur,XuejieHuang',UqunChen'and中科院物理所高鹽濃度電解液拓展到其他電池體系避免電極材料溶解和擴(kuò)散(庫侖效率)抑制金屬鋰枝晶生長(安全性)調(diào)控SEI界面膜組成及結(jié)構(gòu)(庫侖效率)拓寬電解液電化學(xué)窗口(能量密度)抑制集流體腐蝕(庫侖效率)提高阻燃性而且不揮發(fā)(安全性)鈉鹽…鈉離子電池液體電解質(zhì)材料電解液有機(jī)溶劑…添加劑六氟磷酸鈉、高氯酸鈉亞胺鹽硼酸鹽NaBOB磺酸鹽NaOTF碳酸酯醚類溶劑羧酸酯砜類溶劑TMSEMS氟代溶劑氟醚(D2)成膜添加劑過充添加劑BP、CHB阻燃添加劑磷腈浸潤劑FB目前有機(jī)鈉離子電池體系延用了鋰電池體系；針對鈉離子的特點(diǎn)還需要開發(fā)特定的添加劑鈉離子電池液體電解質(zhì)材料1:1:固有屬性3:鈉鹽熱穩(wěn)定性更高√更小的斯托克斯半徑(低鹽濃度)更低的去溶劑化能(低溫、倍率)六氟磷酸鈉的熱穩(wěn)定性遠(yuǎn)好于六氟磷酸鋰，電解質(zhì)對溫度不敏感(高√更小的斯托克斯半徑(低鹽濃度)更低的去溶劑化能(低溫、倍率)2:2:寬溶劑選擇4:電解液更高的熱穩(wěn)定性√PC與正極的相容性好(高壓)√鈉電電解液的放熱溫對金屬陽離子的溶解性小(循環(huán))系數(shù)√PC凝固點(diǎn)低、低溫性能好(低溫)√PC密度小于EC、吸濕性小于EC(更少的用量)醚類體系與碳負(fù)極和磷酸鹽正極兼容性好60DSC/DSC/mW42——1mol/LNaPF?EC+DEC04-6鈉離子電池液體電解質(zhì)材料——低鹽濃度電解液提出了鈉基低鹽濃度電解液一c(mol/L)CostofsolventTotalcostConcentrated(>1.5M)(<0.8M)ViscosityViscosity(low)(high)去溶劑化能(PC中)0.68A—Anion—Na·—SolventanionsolventsolventSpecialfunctionality■WidevoltagewindowConventionaluse■WideworkingtemperaturerangeEnergyLett.2020,5,1156-1158.鈉離子電池液體電解質(zhì)材料——低鹽濃度電解液電導(dǎo)率8648電導(dǎo)率8648口2-0.00.2C(mol/L)4一25℃00.81.00.00.20.40.60.40.6C(mol/L)200025002500Cyclenumber1C/1C,100%DOD,3000周循環(huán)容量保持率80.3%不同鹽濃度電解液的理化性質(zhì)及在全電池中的驗證心開發(fā)新型鈉鹽NaFSI,設(shè)計高性能電解液Nat.Commun.2013,4,1481必提出鈉離子電池用低鹽濃度電解質(zhì)體系A(chǔ)CSEnergyLett.2020,5,4,1156-1158cites:34心商用鈉離子電池電解液的探索與論證高溫循環(huán)、低溫充放電、高倍率等鈉離子固體電解質(zhì)研發(fā)2016La-dopedNASICONNVP|IL/NASICON|Na,10,000cyclesPEO/NaTFSI/NASICONF-dopedNASICON,CPEMg-dopedNASICONPP@NASICONSeparatorPEO/NaPF?SPE20202017201920202017I⑦8935?⑦89352021全新聚合物電解質(zhì)的設(shè)計EOEO/NaFSI/NASICONPEO/NaFSI/Al?O?2016WaterToothpaste-likeElectrodeNVP|Na-β"-Al?O?INa,10,000cycle~PEO/NaFSI/Na-β"-NASICONMigrationAl?O?CPENASICONAnodePEO/NaFSI/Al?O?HighVoltageSSBNVOPF|CPE|Na鈉離子固體電解質(zhì)研發(fā)2016La-dopedNASICON3.4mScm-1at25℃NVP|IL|NASICON|Na,10,000cycles2017PEO/NaTFSI/NASICON20162017201920162017②②2019F-dopedNASICON,Mg-dopedNASICON3.5mScm-1at25°CPP@NASICONSeparatorPEO/NaPF?SPE2020662021全新聚合物電解質(zhì)的設(shè)計2019PEO2019PEO/NaFSI/Al?O?WaterassolventPEO/NaFSI/NASICONCPE2016Toothpaste-likeElectrodeNVP|Na-β"-Al?O?|Na,10,000cycles2020PEO/NaFSINa-β'"-2019Al?O?CPENASICON20202020NVOPF|CPE|NaCorrelatedNASICONMigrationAnodeInterfaceModification鈉離子固體電解質(zhì)材料——優(yōu)勢與挑戰(zhàn)stackingAnodeSolidelectrolytestackingAnodeSolidelectrolyteCurrentcollectorCathodeaBipolarAnodeCathodeElectrodeegslurryElectrodeegCurrentcollectorCElectrolyteCurrentcollectorCElectrolyteslurryCutandlaminationAnodeelectrolyteSolidSolidelectrolyte優(yōu)勢：安全、能量密度高挑戰(zhàn)：固體電解質(zhì)、界面、生產(chǎn)工藝Y.-S.Hu*,NatureEnergy2016,1,16042鈉離子固體電解質(zhì)材料Li+固體電解質(zhì)GlassLi?S-SiS?-Li?PO?Li?2Gea2sPoS?DopedLi?NLi??GeP?Si2Li?Zn(GeO?)?Lio3sLaoszTiO?96Li-B-AI?O?Al-dopedLi,La?Zr?O?22.02.53.03.54.00Glass-ceramicLi?P?S?1Na+固體電解質(zhì)mixtureofβandβ"phase)Self-formingcompositeNaSICON50Na?S-50SiS?10?Tetragonal-Na?PS?2.62.72.82.93.03.13.23.33.43.5(sinteredbody)94Na?PS,-6Na,SiS.Na,,Sn?PS,22.5低的電子電導(dǎo)率化學(xué)穩(wěn)定性高，與電極材料不反應(yīng)低的電子電導(dǎo)率化學(xué)穩(wěn)定性高，與電極材料不反應(yīng)熱膨脹系數(shù)同電極材料相匹配與電極材料相容性好；寬的電化學(xué)窗口；環(huán)境友好、原料廉價、易制備等鈉離子固體電解質(zhì)材料Na1+xZr?SixP?-xO12:當(dāng)1.8≤x≤2.2時，x=2時離子電導(dǎo)率最高NNaZr?(PO?)?Na1+xZr?SixP3-x012-50℃提高離子電導(dǎo)率的方法：a-50℃1.摻雜改性：((b)提高遷移離子的濃度4.0k4.0k8.0k12.0k(c)4.0k8.0k12.0k2.兩相復(fù)合：例如Lil、Al?O?Z'(Ω)3.自形成復(fù)合電解質(zhì)引進(jìn)一種元素與Na+、陰離子結(jié)合形成第二相鈉離子固體電解質(zhì)材料—NASICON中Na+傳輸機(jī)制重新認(rèn)識：NASICON相中Na+傳輸發(fā)現(xiàn)NASICON中一個新的Na5位置CC需Na5bNa4NaNa4—Na3Na3Na5Na3Na+離子主要通過協(xié)同擴(kuò)散來傳導(dǎo)通過AIMD和MEM分析得到Na?Zr?Si?PO12的Na+離子傳輸通道：Na2-Na3-NaNa2-Na3-Na3-Na2Z.Z.Zhang,…Y.-S.Hu*,Adv.EnergyMater.2019,9,1902373鈉離子固體電解質(zhì)材料—NASICON固體電解質(zhì)Na?Zr?Si?PO?2+La→Na?+xZr?Si?+xP?-xO?2+Na?La(PO?)?+La?O?+LaPO?x=0.40x=0.40x=0.35x=0.30x=0.25X=0.20x=0.15x=0.10x=0.05x=01020…人認(rèn)b0fb0axInNa3.LaZr2.Sl?PO12Z.Z.Zhang,…Y.-S.Hu*,Adv.EnergyMater.,2017,7,1601196.鈉離子固體電解質(zhì)材料NASICON固體電解質(zhì)Na?+Zr?-xLa,Si?PO125.0×10-3x=0.059.6×10-47.2×10-3x=0.101.3×10-38.0×10-3x=0.151.5×10-39.3×10-30.1270.3240.2x=0.20x=0.253.2×10-3x=0.303.4×10-3x=0.352.0×10-37.9×10-3x=0.405.8×10-3鈉離子固體電解質(zhì)材料心玻璃-陶瓷NASICON復(fù)合固體電解質(zhì)bbaaNaF的加入同時降低了晶粒和晶界阻抗，其中晶粒電導(dǎo)的提比的提升，材料結(jié)構(gòu)內(nèi)鈉含量的提高使載流子濃度增加；晶界電導(dǎo)的提升歸因于晶界玻璃相的生成。Na?Zr?Si?PO12-0.7NaF室溫下離子電導(dǎo)為1.7×10-3Scm-1(遠(yuǎn)大于Na?Zr?Si?PO?2的4.5×10-?Scm-1),55度下離子電導(dǎo)率為1.9×10-2Scm-1,a;C-5.0Na?Zr?Si?PO??-xNaFb材料的離子導(dǎo)通性能Y.J.Shao,…Y.-S.Hu*,鈉離子固體電解質(zhì)材料NASICON修飾心玻璃-陶瓷NASICON復(fù)合固體電解質(zhì)a當(dāng)x<0.6時，隨著NaF的加入，當(dāng)x<0.6時，隨著NaF的加入，NASICON結(jié)構(gòu)中的P逐漸減少轉(zhuǎn)變?yōu)椴Ａ嘀械腜;當(dāng)x>0.6時，隨著NaF的加入，NASICON中的P繼續(xù)減少，并伴隨著越來越多Na?PO?的出現(xiàn)。x=0.1Na,PO,GlassphasNASICON0"Pshiftfppm)b"Pshiftfppm)x=1.0Na?Zr?Si?PO12-xNaFx=1.0Na?Zr?Si?PO12-xNaF材料的SEM表征鈉離子固體電解質(zhì)材料—NASICON負(fù)極界面心NASICON電解質(zhì)中存在鈉枝晶問題vorh07vorh07叫有以0.3mAcm-250電池拆解，NASICON片局部出現(xiàn)黑線貫穿；>SEM觀測到網(wǎng)狀和錐狀“鈉枝晶”心NASICON電解質(zhì)中鈉枝晶生長NASICON中鈉枝晶生長的原位光學(xué)顯微觀察鈉離子固體電解質(zhì)材料—NASICON負(fù)極界面心界面修飾抑制鈉枝晶：基于上個工作界面引入NaFa·Nonunlformcurrentdistributlon表面處理NASICON與鈉的良好浸潤性dNINZsPjs20.PVDF在NASICON20.SalSalerclinggPvDrsNPNaFACNZSPFACINaNASICON表面后的的SEM和DES表征NASICON陶瓷片中鈉枝晶生長及抑制機(jī)理示意圖鈉離子固體電解質(zhì)材料—NASICON負(fù)極界面必界面轉(zhuǎn)換與性能20CIsCIsFIs0.10-VoltageVoltage/V-0.05--0.10-0.15v心小1v心小144Tlme/NchwN心上1NchwN心上1山八”山八-0.20300400500600Timc/hNaU/.Z-U/.Z-FACNZSPFACNZSPQ.Q.Zhang,…Y.-S.Hu*,EnergyMaterialAdvances,2021,2021.North-Holland,NewYork,1979,pp.131-136.CHEMELECTROCHEMCHEMELECTROCHEM★ChemPubSocEuropeDOl:10.1002/celc.201600221SodiumBis(fluorosulfonyl)imide/Poly(ethyleneoxide)XuejieHuang,alandLiquanChenathesepointsintoconslderation,sodlum-lonbatterles(SIBs)havethesepointsintoconslderation,sodlum-lonbatterles(SIBs)havebeenahotresearcharea,becauseoftheabundanceofoffunction,withLIBs."ThealreadymatureIndustrialtech-niquesforLIBscanbeadopnum,whichfurthercontalnsthecostofSIBsystems!"lyte-basedSIBs.Here,wedescribeanSPEcomposedofsodiumABESABES5鈉離子固體電解質(zhì)材料PEO-PEO-NaFSI80C480C4.1×10-4Scm-1有待進(jìn)一步提高Temperature/℃Temperature/℃Capacity(mAhg)Capacity(mAhg)Cawiy(mAhg)2002.52.0-Cathode:NasNiMnsO?0.5Capacity(mAh/g)全電池問題有待解決X.G.Qi,…Y.-S.Hu*,CylenumttCyclenumberCycleCylenumttCyclenumberCycle鈉離子固體電解質(zhì)材料—水系加工PEO基聚合物aaCNaFSI+H?OHF+R-SO?H(1)HF+Al?O?+H?O—→AlF3·xH?O{2)6FNaTFSI工溶劑，安全、環(huán)保、價格低廉、操作方便。…水加工過程中產(chǎn)生的分解產(chǎn)物有利于中和正極材料表面的弱堿性，輔助形成生成AlF?,提升了電池界面的穩(wěn)定性?！礟EO基聚合物固體電解質(zhì)膜的制備及鈉鹽的結(jié)構(gòu)示意圖L.L.Liu,…Y.-S.Hu*,ACSEnergyLett.2019,4,1650-1657鈉離子固體電解質(zhì)材料—水系加工PEO基聚合物交電化學(xué)性能aa%Uo80°℃時電導(dǎo)率可達(dá)9.52×10+Scm-180°℃時電導(dǎo)率可達(dá)9.52×10+Scm-1鈉負(fù)極界面兼容性良好長循環(huán)性能優(yōu)良，1C倍率下循環(huán)2000周容量保持率達(dá)到92.8%鈉離子固體電解質(zhì)材料—PEONa/C電極抑制枝晶a基于NASICON工作發(fā)現(xiàn)碳一定a基于NASICON工作發(fā)現(xiàn)碳一定程度可以抑制枝晶，因此我們直古b豆0.110鈉離子固體電解質(zhì)材料—PEO基聚合物負(fù)極界面必性能分析20-■-Na||PEO,。NaFSI|INa,V,(PO),●-Na/C|IPEONaFSI|INa,V?(PO),a—Na||a—Na||PEOzNaFSI||Na?V?(PO——Na/C|IPEO。NaFSIINa,V?(PO),2.0Cpeoy(mAho"406020406020Capacity(mAhC1.1Na/C|IPEO?oNaFSI||Na?V?(PONa/C|IPEO?oNaFSI||Na?V?(PO)?Na||PEO?NaFSI||Na,V?(PO)?CyclenumberNa/C負(fù)極與常規(guī)Na負(fù)極的PEO金屬半電池對比Na/C負(fù)極與PEO基聚合物固體電解質(zhì)之間優(yōu)異的接觸性能，接觸面積顯著增大，且鍵合，實現(xiàn)穩(wěn)定的界面。C.L.Zhao,…Y.-S.Hu*,Angew.Chem.C.L.Zhao,…Y.-S.Hu*,Angew.Chem.鈉離子固體電解質(zhì)材料—無機(jī)有機(jī)復(fù)合電