杭州電解液報告課件

1、The Current Status and Development ofElectrolyte Additives For Lithium IonBatteriesOutlineResearch background12Adjusting solution structureFluoranated additivesS-based electrolyte additivesConclusion3451. Background2017國內(nèi)鋰離子電池電解液市場近200億元，添加劑市場超15億元電動汽車的發(fā)展將帶動鋰離子迅速發(fā)展和電解液技術的巨大進步, 更多新型配方和添加劑投入實際應用高電壓、高能

2、量密度鋰離子電池、功率型電池、 高低溫電池、高安全電池等The importance of battery electrolyte縱觀電池的發(fā)展歷史，電解液的革新對電池科學發(fā)展的貢獻絕不亞于任何一種電極材料，例如鋅錳電池自誕生以來經(jīng)歷了三次革命，其中兩次革命源于電解液組成的變化，分別是從第二代NH Cl為主的電解液到第三代的4ZnCl 為主的電解液，再到第四代的KOH溶2液為主的堿錳電池，由于電解液組成的變化，電池的反應機理和成流機制也發(fā)生了明顯的變化。Zn+2MnO + 2NH Cl 2MnOOH + Zn(NH ) Cl2243 24Zn+8MnO +9H O+ZnCl 8MnOOH+Zn

3、Cl 4ZnO5H O22222KOHZn+2MnO +2H O 2MnOOH+Zn(OH)222The development andrevolution of LIB electrolyte 類似地，鋰離子電池的電解液技術也已經(jīng)經(jīng)歷了3次變革，電解質(zhì)的多樣性也為鋰離子電池多樣化做出了實質(zhì)性的貢獻，人們常根據(jù)電解質(zhì)的類型把鋰離子電池分為液體鋰離子電池、聚合物鋰離子電池和全固態(tài)鋰離子電池，并用以滿足不同的生產(chǎn)和生活實踐。當然，由于液體電解質(zhì)特殊的優(yōu)勢，在未來相當長的一個時期，液體鋰離子電池仍將主導鋰離子電池市場。PC+DME PC+DMCPC+DECEC+DMC EC+DMC function

4、alEC+DEC EC+EMC additiveslithiumbatterybased on based on COKEanode)Li metallithium ion battery(1st generationlithium ion battery(2nd generationwith graphiteanode)當然，由于液體電解質(zhì)特殊的優(yōu)勢，在未來相當長的一個時期，液體鋰離子電池仍將主導鋰離子電池市場。Confifential MaterialsThe role of electrolytes in lithium ion batteriesElectrolyte is the b

5、ridge connecting cathode and anode,the media for Li transportation, the place where sidereaction occursl Cycle lifel Safetyl Operating temperaturel Shelf lifel Rate capabilityl Reversible capacityl Self-discharge properties1. BackgroundObjective for electrolyte development Performance, calendar-life

6、, and safety characteristics ofLi-ion cells are dictated by the nature and stability ofthe electrolyte and the electrode-electrolyte interfaces. The goal is to develop novel electrolytes with the followingcharacteristics: Wide electrochemical stability window, 0 to 5 V Wide temperature stability ran

7、ge, -30 to +80 C Non-reactivity with other cell components Excellent ionic conductivity to enable rapid ion transport Stability for over 5000 deep-discharge cycles Stability over the 10yrs battery life1. BackgroundElectrolyte additives play a crucial role for organicelectrolyte systems1 Adjusting so

8、lution structureThe line on the right of the negative charges represents the innerHelmholtz plane (IHP). The dashed lines depicts the outerHelmholtz plane (OHP) and the dotted line illustrates the plane ofelectrokinetic charge, or the shear plane (SP).陰離子競爭性溶劑化改變?nèi)軇┗Y(jié)構pure PC solventLiTFSI/PCLiTFSI/P

9、C:NMA(2.5:1)EC:PC(1:1 )EC:PC(1:1)+NMA(5%)2.01.61.20.80.40.080006000400020000Li+-PC interactionelectrolyte decomposition7607407207006800100200300400500600700-1Specific capacity/mAh gWave number/cm-13210PC:NMA (2.5:1)DMC:NMA(1:1)PC1000200030004000Wave number/cm-1陽離子競爭性溶劑化對電解液性能的調(diào)控Li ionPC moleculecomp

10、etation ion1.301.251.201.151.101.051.000.950.900.850.800.752.01.51.00.50.0ionic liquidregulation0.054006008001000 1200 1400 1600 1800 20000100200300400500600Wave Number/ cm-1Capacity/ (mAh/g)電解液中納米團簇結(jié)構取向和溶劑化數(shù)調(diào)整AB2. Fluoranated additives fluoro solvents is less flammable Solvent with a F to H ratio 4

11、 appears to have improvedthermal properties. In the wick test the electrolytecontaining the fluoro solvent didnt catch fire. Fluoro solvents in conjunction with cycliccarbonates should exhibit improved thermalproperties Low temperature performance may suffer Fluoro-EC may be an alternative Fluoro et

12、her: is used as co-solvent to improve oxidationpotential in Hatachi.氟代碳酸酯類添加劑的成膜與鈍化該添加劑對負極表面膜結(jié)構和性能的影響(a)(b)(d)(f)(c)(e)添加劑在整體電池中的作用,發(fā)展具有同時優(yōu)化正極和負極表面的新型添加劑對電池產(chǎn)業(yè)的發(fā)展具有特別重要的意義,特別是發(fā)展高低溫電池和長壽命電池非常重要.3. S-based electrolyte additives環(huán)狀磺酸酯系列OOOOOOS別名：DTD PCS PEGLSTTSSOO外觀：白色固體（部分為液體）含量：99.5%（GC）水分：200PPMOOOOO

13、SSOOO已經(jīng)成為當前成膜添加劑的主流，特別在三元和磷酸鐵鋰電池中具有重要的意義Honghe Zheng et. al.For example Control electrolyte：EC/DMC/EMC(1:1:1) 1.0M LiPF6EC/FEC/DMC/EMC(1:1:3:1) 1.0/1.2M LiPF6 Additives：FEC 5% + VC 5%DTD 1% + MMDS 1%PC 5%LiODFB 5%LiTFSI 5%DTD 1%TFPC 5%BS 1%LiBOB1%+MMDS1%LiPOF21%+DTD1%PST 1%DTD 1%+LiTFSI 5%DTD 1%+LiD

14、OFB 5%VC5%+DTD1%+LiTFSI5%BS 1%+LiDOFB 5%PST 1%+LiDOFB 5%Traditional additive combined with different sulfonate additives includingBS, PST, DTD, MMDS etc.Honghe Zheng et. al.140120100801131-1.01.0-LiODFB5%1.0-LiTFSI5%1.0-DTD1%1.0-BS1%601.0-PST1%401.0-DTD1%-LiTFSI5%1.0-DTD1%-LiODFB5%1.0-BS1%-LiODFB5%1

15、.0-PST1%-LiODFB5%1.0-VC5%-DTD1%-LiTFSI5%200050100Cycle Number150200Honghe Zheng et. al.140120100801131-1.21.2-LiODFB5%1.2-LiTFSI5%1.2-DTD1%1.2-BS1%1.2-PST1%601.2-DTD1%-LiTFSI5%1.2-DTD1%-LiODFB5%1.2-BS1%-LiODFB5%1.2-PST1%-LiODFB5%1.2-VC5%-DTD1%-LiTFSI5%40200050100150200Cycle Number4. Si based electro

16、lyte additive這是一類新的系統(tǒng)，具有新型官能團的硅烷添加劑，在改善硅負極性能方面取得了一些進展硅烷添加劑用于硅負極的研究OSiSiO樣品 C-CD-CFE SE0123453116.4 410076.0 94.3012037.9 271475.0 93.9483140.7 3996.4 78.5 95.0393192.1 4061.7 78.5 9592805.7 369375.9 93.8372048.6 2802.8 73.0 94.519硅烷添加劑用于硅負極的研究OSiOSi引入雙鍵希望增強電極表面的成膜性質(zhì)穩(wěn)定硅表面硅烷添加劑用于硅負極的研究SamplesD-CC-CF-E

17、S-ES003S0031%2131.51974.229702798.42634.33812.376.1774.9477.994.0492.7396.812%3%4%3212.73204.53752.640754033.6467478.8479.4480.2894.8695.5594.655%2435309979.5494.47硅烷添加劑用于硅負極的研究0%1%2%首效：91.71%二次：96.65%首效：90.19%二次：95.93%首效：91.03%二次：95.76%引入氟希望增強電極表面的成膜性質(zhì)3%首效：89.80%二次：96.32%4%首效：89.94%二次：95.47%5%首效：89

18、.34%二次：96.22%穩(wěn)定硅表面硅烷添加劑用于硅負極的研究首次放電 首次充電比容量 比容量（mAh/g） （mAh/g）首次效率（%） 效率（%）第二圈添加劑體積比%電池電池1電池2電池1電池2電池1電池2電池1電池2電池1電池2電池1電池23128.22741.63135.31626.53477.03817.62806.52806.53427.13408.33696.1981.42918.52486.72827.71417.63165.33458.52520.22520.23082.33068.93302.1787.391.7190.7090.1987.1591.0390.5989.8086.7589.9490.0489.3480.2396.6596.2195.9395.2295.7696.0096.3294.7395.4795.8996.2291.560%1%2%3%4%5%這類添加劑在效率和容量方面也沒有表現(xiàn)出明顯的優(yōu)勢硅電極的長期循環(huán)性能有一定提升，但提升效果不顯著硅烷添加劑用于硅負極的研究不同濃度首次放電 首次充電 首次效率四氟硅烷基添加劑比容量3318.81974.32653.43166.12051.52445.5比容量2745.61563.92141.32521.11