聚丙烯腈基聚合物電解質(zhì)的研究進(jìn)展.doc

1、聚丙烯腈基聚合物電解質(zhì)的研究進(jìn)展化學(xué)化工學(xué)院班級：2009131144周明香學(xué)號:2009131144專業(yè)：化學(xué)任課教師:王麗萍2011年12月19日聚丙烯腈基聚合物電解質(zhì)的研究進(jìn)展摘要：詳細(xì)介紹了鋰離子電池用PAN(聚丙烯腈)基聚合物電解質(zhì)的發(fā)展過程，提出了PAN基凝膠型聚合物電解質(zhì)所存在的主要問題,介紹了PAN的改性方法.關(guān)鍵詞：凝膠、聚合物、電解質(zhì)、聚丙烯腈隨著便攜式電子器件的不斷小型化，二次電池也要向質(zhì)量輕超薄的方向發(fā)展。而聚合物鋰離子電池具有比能量高，無電解液泄漏問題、安全性能好、設(shè)計(jì)靈活、易于大規(guī)模生產(chǎn)等特點(diǎn)。因此倍受市場的青睞。聚合物電解質(zhì)是聚合物鋰離子電池的核心部分，它需要具有

2、較高的電導(dǎo)率和電化學(xué)穩(wěn)定性，良好的機(jī)械性能以及與電極的相容性，目前所開發(fā)出的聚合物電解質(zhì)體系主要有PEO14、PMMA56、PVDF710、PVC11、PAN12幾大類，還有許多新體系的電解質(zhì)也在嘗試之中.但能應(yīng)用于生產(chǎn)的卻不多,這是因?yàn)榇蠖鄶?shù)聚合物電解質(zhì)體系難以同時具有較高的電導(dǎo)率和良好的機(jī)械強(qiáng)度。1. 研究進(jìn)展1975年Feuillade和Perche13首次研究制備出PAN-PCNH4ClO4三元凝膠聚合物電解質(zhì)，后來Abraham14等作了深入研究，這類聚合物電解質(zhì)是通過在聚合物基質(zhì)中固化大量的液態(tài)電解質(zhì)溶液而制成的,其電導(dǎo)率已達(dá)到1X103S/cm數(shù)量級。近年來對凝膠型聚合物電解質(zhì)的

3、研究發(fā)展很快,并取得了較大的成就。PAN是一種穩(wěn)定性好、耐熱性強(qiáng)且阻燃性好的聚合物，較為適合用作基質(zhì)材料,采用有機(jī)電解液對其進(jìn)行增塑后，可形成凝膠電解質(zhì)。隨著對微觀結(jié)構(gòu)、界面性質(zhì)以及導(dǎo)電機(jī)理研究的深入，其性能有了較大的提高。Watanabe15等在PAN-LiClO4聚合物體系中加入EC（碳酸乙烯酯)、PC（碳酸丙烯酯）、DMF（二甲基甲酰胺）等塑化劑，結(jié)果發(fā)現(xiàn)電導(dǎo)率隨著塑化劑與LiClO4摩爾比率的增加而增加,最大電導(dǎo)率在25時可達(dá)10410-5S/cm,Appetecchi16等研究了一種組成為PAN-EC-DMCLiPF6（16-60-204摩爾比)+A12O3(6wt。%,w/o)的新

4、型凝膠電解質(zhì)，在25時離子電導(dǎo)率可達(dá)3 X 10-3S/CM，而且電化學(xué)穩(wěn)定窗口很寬,與鋰離子界面穩(wěn)定性也較好。但是因?yàn)檫@些研究中各種合成、制備工藝較為復(fù)雜，而且條件高，不能達(dá)到聚合物鋰離子動力電池的技術(shù)指標(biāo)，因此難用于實(shí)際生產(chǎn).Megahed17等人用復(fù)合增塑劑對PAN進(jìn)行改性,室溫離子傳導(dǎo)率達(dá)4×103S/cm,鋰離子遷移數(shù)也大大提高到0.60.7之間。Kim D18等用乳液聚合法合成了ANMMA-LiClO4EC/PC聚合物電解質(zhì)，在室溫下的離子電導(dǎo)率達(dá)1。9×103S。cm1,而且保液性好，放電容量為130mAhg-1.Jayathilaka等19制備了PAN/EC

5、/PC/LiTFSI的凝膠聚合物電解質(zhì)，在室溫條件下,當(dāng)PAN（15。4%）/EC(41.0%)/PC（41。0）/LiTFSI（2.6%) (質(zhì)量比) 時，電導(dǎo)率為 2.5×10 3S.cm-1。HyoSik Min20等應(yīng)用倒相法制備PAN膜,將PAN膜浸泡在不同的電解液中:1 M LiClO4-EC-DMC, 1M LiPF6-EC-DMC 和1M LiBF4 ECDMC (體積比為1：1），用掃描電鏡觀察了膜在浸泡前后的變化，測得其電化學(xué)穩(wěn)定壓均在5。0V以上，其中PAN-LiPF6-ECDMC電解質(zhì)在室溫時的離子電導(dǎo)率為2.8×103S/cm.Fang Yuan2

6、1等將不同用量的AN與不同分子量的PEO共聚制備成固體聚合物電解質(zhì)，控制AN的用量,當(dāng)PEO分子量為3000000時其室溫電導(dǎo)率最大可6。79×10-4S。cm-1。個人收集整理，勿做商業(yè)用途本文為互聯(lián)網(wǎng)收集，請勿用作商業(yè)用途2。存在的主要問題CROCE2527等人對PAN基凝膠聚合物電解質(zhì)（GPE）進(jìn)行了系統(tǒng)的研究，選擇不同的溶劑、不同的鋰鹽，以不同的配比制備出PAN基凝膠聚合物電解質(zhì)，通過比較離子電導(dǎo)率、電化學(xué)窗口、伏安循環(huán)性能、陽離子遷移數(shù)和GPE與電極的相容性，發(fā)現(xiàn)PAN基GPE的室溫離子電導(dǎo)率一般在10-3S/cm數(shù)量級，最高可達(dá)到5。9 × 103S/cm(Li

7、PF6/EC/DMC/PAN），研究發(fā)現(xiàn)：由于PAN鏈上含有強(qiáng)極性基團(tuán)CN，與金屬鋰電極相容性差，凝膠聚合物電解質(zhì)膜與鋰電極界面鈍化現(xiàn)象嚴(yán)重，隨著時間的延長，電池內(nèi)阻會不斷增大。此外PAN的結(jié)晶性強(qiáng)，當(dāng)溫度上升時，電解液容易發(fā)生析出,從而又轉(zhuǎn)化為液體電解質(zhì)，導(dǎo)致漏液問題嚴(yán)重。這些問題限制了PAN體系GPE在鋰離子二次電池中的應(yīng)用.從實(shí)用化角度來看PAN基聚合物電解質(zhì)還存在一些問題需要解決，主要體現(xiàn)在熱力學(xué)穩(wěn)定性和機(jī)械強(qiáng)度較差，電極界面穩(wěn)定性欠佳。機(jī)械強(qiáng)度差是凝膠型聚合物電解質(zhì)普遍存在的問題。為了提高電導(dǎo)率，就需要在 PAN 基質(zhì)中固化較多的增塑劑，而增塑劑含量的增加又會使其機(jī)械性能下降。因此，

8、在保持較高電導(dǎo)率的情況下提高其機(jī)械強(qiáng)度是研制凝膠型 PAN 基聚合物電解質(zhì)的一個難點(diǎn)。3。PAN基聚合物電解質(zhì)改性為了提高PAN基凝膠型聚合物電解質(zhì)的性能,人們嘗試了多種方法對其進(jìn)行改性，目前改性的辦法一般有共聚、共混、交聯(lián)、添加無機(jī)填料等，這樣不僅可以改善電解質(zhì)與電極的界面穩(wěn)定性，還可以使GPE的機(jī)械性能有較大的提高。 Choi28等人把PAN和PEO共混制備得到PEO/PANLiC104EC/BL組成的凝膠聚合物電解質(zhì)膜，離子電導(dǎo)率為1。2×10-3S/cm， PEO的加入提高了PAN凝膠的機(jī)械強(qiáng)度。Kim y29等把PAN和PANI共混制備得到PANPANIEC/BL-LiCl

9、O4組成的凝膠聚合物電解質(zhì)，離子電導(dǎo)率達(dá)1.9×103S/cm,電化學(xué)穩(wěn)定性能、電極界面的相容性都有所改善，但是其機(jī)械性能差。Kim D3032等人采用丙烯腈-甲基丙烯酸甲酯苯乙烯三元共聚物為基體制備的凝膠電解質(zhì)，與以PAN均聚物為基體的凝膠電解質(zhì)相比，與電極界面的相容性改善很多，組成Li/PAN基GPE/Li電池的界面電阻在10天內(nèi)由224增加到436,但從第10天到第30天，界面電阻變化很小。Lee33等在PAN鏈上引入了甲基丙烯酸鋰鹽(LIMA)制備了P(ANLIMA)離聚物，在LiC104+EC電解質(zhì)中，25時離子電導(dǎo)率為1。9 ×103 S/CM。研究者采用交流阻

10、抗法測試了P（ANLIMA）電解質(zhì)膜與電極間阻抗隨時間的變化情況，從圖1可知,PAN基電解質(zhì)經(jīng)30d后，界面阻抗增加了近3倍，而P(AN-LIMA)電解質(zhì)基本沒有增加，同樣的,他們還發(fā)現(xiàn)經(jīng)過20次循環(huán)伏安后P（AN-LIMA)電解質(zhì)與電極間界面阻抗無明顯增加,但純PAN基電解質(zhì)卻增加了數(shù)倍，他們認(rèn)為，P(AN-LIMA）界面穩(wěn)定性提高的原因是LIMA與EC中氧原子相互作用，從而阻止了增塑劑EC的偏析。此外，向GPE中添加適量的無機(jī)填料也可以改善電解質(zhì)膜/鋰電極的界面穩(wěn)定性。SLane34等用沸石粉末對PAN基凝膠電解質(zhì)進(jìn)行改性，制備了LiAsF6-ECPCPAN沸石復(fù)合聚合物，圖2是不同存放時

11、間后聚合物電解質(zhì)與電極間阻抗隨時間的變化情況,盡管圖2（b）初期界面阻抗較大，但再隨時間增加，其增加量很小，由此可知，沸石粉末的加入可以起到減緩界面阻抗增加，明顯改善了其界面性質(zhì)。 Panero35等人在PAN/LiPF6/PC體系中加入A12O3粉末制成凝膠電解質(zhì)，在25的離子電導(dǎo)率可達(dá)8×10-3S/cm，電化學(xué)化學(xué)穩(wěn)定窗口達(dá)5.5V,特別適用于高電壓可充電鋰離子電池中作為電解質(zhì)隔層。參考文獻(xiàn)1 LaikB,legrandL,ChausseAetal。J。Electrochem.Soc.，1999,146(5）：1672.2 AppetecchiGB,CroceF，PersiLe

12、tal.ElectrochimicaActa,2000，45:1481.3 MunichandraiahN,ShuklaAK,ScanlonLGetal。ElectrochimicaActa，2000,45:1203.4 AndreevYG，BurcePG.ElectrochimicaActa,2000，45：1417.5 TatsumaT,TaguchiM，OyamaN.ElectrochimicaActa，2001,46:1201。6 AgnihotrySA，Pradeep，SekhonSS.ElectrochimicaActa,1999，44：3121。7 SaitoY，Capiglia

13、C,YamamotoH。J.Electrochem.Soc.,2000，147（5）：1645。8 AbrahamKM，KochVR，BlakleyTJ.J.Electrochem.Soc。,2000,147(4）：1251.9 MichotT，NishimotoA,WatanabeM.ElectrochimicaActa，2000,45:1347。10 BoudinF,AndrieuX,JehouletCetal。J。PowerSources，1999,81-82：804。11 RajendranS，UmAT。J.PowerSources,2000，87：218.12 AppetecchiG

14、B,ScrosatiB.ElectrochimicaActa，1998，43（9):1105.13Feuillade G，Perche .Ion-conductive macromolecular gels and membranes for solid lithium cellJ,J Appl Electrochem， 1975，5(1)：63-68.Polyacrylonitrile and the research progress of polymer electrolyteAbstract： introduced the lithium ion battery with PAN (p

15、olyacrylonitrile) and the development process of polymer electrolyte, and put forward the PAN and gel polymer electrolyte type of the existing main problems， this paper introduces the modification methods of PAN。Keywords： gel, polymer， electrolyte， polyacrylonitrileAlong with the continual miniaturi

16、zation of portable electronic devices, secondary battery and to light quality ultrathin direction. And polymer lithium ion battery is better than the high energy， no electrolyte leakage problem， safety performance is good, design flexibility， easy to mass production etc。 Characteristics。 So much mar

17、ket favour. Polymer electrolyte， polymer lithium ion battery core part, it needs to have higher electrical conductivity and electrochemical stability， good mechanical properties and the compatibility and electrode， the creation of polymer electrolyte system mainly PEO 1 4, PMMA 5 6， PVDF (7 10, PVC

18、11， 12 a few kinds big PAN, and many of the new system in electrolyte also trying。 But can be applied to the production of but not much, this is because most polymer electrolyte system has high conductivity to at the same time and good mechanical strength.個人收集整理，勿做商業(yè)用途個人收集整理，勿做商業(yè)用途1. The research pr

19、ogress1975 Feuillade and Perche 13 first study the preparation PAN-PC-NH4ClO4 three yuan gel polymer electrolyte， Abraham later 14 the thorough research, this kind of polymer electrolyte is through in a polymer matrix curing a large amount of liquid electrolyte solution of made the conductivity has

20、reached 1 X10-3 S/cm orders of magnitude。 In recent years to gel type of polymer electrolyte research and development soon， and made great achievements. PAN is a kind of good stability, heat resistance and flame retardancy good strong polymer， a suitable used as a matrix materials, using organic ele

21、ctrolyte to its plasticized， can form a gel electrolyte。 As the core of the micro structure, interface properties and the deepening of the research conductive mechanism, the performance of a large improvement.個人收集整理,勿做商業(yè)用途文檔為個人收集整理,來源于網(wǎng)絡(luò)Watanabe 15， etc in the PANLiClO4 polymer system with EC (ethyl

22、ene carbonate esters, PC (TanSuanBingXi ester）, DMF （DMF） plasticizing agent, and found the conductivity plasticizing agent and with LiClO4 Moore ratio increases with the increase in 25 maximum conductivity can reach up to 104 105 S/cm, Appetecchi 16 of a PANEC-DMCLiPF6 （16-60-204 Moore than） + A12O

23、3 （6 wt。 ， w/o) new gel electrolyte, 25 in when ionic conductivity up to 3 X 103 S/cm， and electrochemical stability window is very wide, and lithium ion interface stability is better also。 But because these studies various synthesis， preparation technology is relatively complex， and conditions high

24、， cannot achieve polymer lithium ion power battery technology index, so difficult for practical production。個人收集整理,勿做商業(yè)用途文檔為個人收集整理，來源于網(wǎng)絡(luò)17 Megahed， using composite plasticizer to PAN on modification, room temperature ionic conduction rate up to 4 x 103 S/cm, lithium ion migration number also greatly

25、improved to 0.6 to 0。7。 18 Kim D by emulsion polymerization synthesized MMA-ANLiClO4EC/PC polymer electrolyte, the ionic conductivity at room temperature of 1.9 x 10-3 S. Cm1， and the liquid sex good, discharge capacity for 130 mAhg1。 Jayathilaka 19 such as prepared PAN/EC/PC/LiTFSI gel polymer elec

26、trolyte, at room temperature, when PAN (15。4） / EC (41。0) / PC （41。0%) / LiTFSI (2.6%） （quality than）， the conductivity of 2。5 x 103 S. Cm-1。 HyoSik Min 20 applications pour in PAN method for film, will be soaked in different PAN film electrolyte： 1 M LiClO4-ECDMC, 1 M LiPF6ECDMC and 1 M LiBF4 EC-DM

27、C (volume ratio of 1：1), with scanning electron microscopy （sem) in the film before and after soaking, the change of the electrochemical stability measured pressure are in the 5.0 V above, including PANLiPF6EC-DMC electrolyte the ionic conductivity at room temperature for 2.8 x 10-3 S/cm。 Fang Yuan

28、21 will be different with different molecular weight of the amount of AN PEO copolymerization of preparation into solid polymer electrolyte， control of AN amount, when PEO molecular weight for 3000000 when the room temperature conductivity can be biggest 6.79 x 104 s。 cm1。個人收集整理,勿做商業(yè)用途本文為互聯(lián)網(wǎng)收集，請勿用作商

29、業(yè)用途2. The main problems of theCROCE 25-27 to PAN the gel polymer electrolyte (GPE） on the system research， choose different solvents， different lithium, with different proportion of preparation and gel polymer electrolyte PAN out, by comparing ionic conductivity, electrochemical window, voltammetric

30、 circulation performance， cationic migration number and GPE with electrodes compatibility, found the room temperature， GPE PAN ionic conductivity in general 10-3 S/cm orders of magnitude, the highest reaches 5。9 x 10-3 S/cm （LiPF6 / EC/DMC/PAN)， the study found： because in the chain of PAN with stro

31、ng polar groupsCN， and lithium metal electrodes compatibility is poor, gel polymer electrolyte membrane and lithium electrode interface passivation phenomenon seriously, with the extension of time, the internal battery will increase。 In addition the crystallization of the PAN with strong sex， when t

32、he temperature rises, electrolyte prone to exhalation, thus and into liquid electrolyte， lead to serious leakage problems。 These problems limits the GPE PAN system in lithiumion secondary battery of application。個人收集整理,勿做商業(yè)用途個人收集整理，勿做商業(yè)用途From the practical Angle and polymer electrolyte PAN also exist

33、 some problems to be solved, mainly reflects in thermodynamic stability and mechanical strength is poorer， electrode interface poor stability。 Mechanical intensity difference is gel type polymer electrolyte common problem. In order to improve conductivity, they need in the PAN in matrix curing more

34、plasticizer， and the increase of the content of plasticizer and will make its mechanical properties fall。 Therefore, in high conductivity of mechanical strength is developed to improve the gel type, the polymer electrolyte PAN a difficulty.本文為互聯(lián)網(wǎng)收集，請勿用作商業(yè)用途個人收集整理，勿做商業(yè)用途3。PAN and polymer electrolyte

35、modification In order to improve the PAN and gel polymer electrolyte type of performance， people tried several methods to its modification, at present the modification to the general copolymerization, blending， crosslinking， adding inorganic materials, such not only can improve the stability of the

36、electrolyte with electrodes interface, still can make GPE mechanical performance is greatly raised。Choi 28 the PAN and PEO people of mixed preparation get PEO/PANLiC104-EC/BL gel polymer electrolyte of membrane， ionic conductivity of 1.2 x 10-3 S/cm, PEO to join improve the PAN gel mechanical streng

37、th。 29 Kim y the PAN and PANI blending preparation PANPANIget EC/BL-LiClO4 composition gel polymer electrolyte, ionic conductivity of 1.9 x 103 S/cm, electrochemical stable performance, electrode interface compatibility are improved, but its mechanical performance is poor。Kim D 30-32 people using ac

38、rylonitrilemethyl methacrylate (mma）-styrene three yuan for the preparation of copolymer matrix gel electrolyte， and to all homopolymers as matrix PAN gel electrolyte compared with electrodes of the interface to improve compatibility many, Li/PAN of the GPE/Li battery interface resistance in 10 days

39、 increased to 436 from 224 , but from the day 10 to 30 days， interface changes very little resistance.and in Lee PAN chain introduced methylacrylic acid lithium (LIMA) preparation the P （AN-LIMA) from homopolymers, in LiC104 + EC electrolyte， 25 to 1。9 when ionic conductivity x 10-3 S/CM。 The resear

40、chers used the method of ac impedance test P (AN-LIMA） electrolyte membrane with electrodes over time between the changes of impedance， from figure 1, it is known that the yankees by 30 d PAN electrolyte， interface impedance increased almost 3 times, and P （ANLIMA) electrolyte basic did not increase

41、, the same, they also found that after 20 times cycle after currentvoltage P (ANLIMA) electrolyte and electrode interface without obvious increase between impedance， but pure PAN and electrolyte actually increased the number of times， they think， P (ANLIMA) interface stability was the reason for the

42、 increase in LIMA and EC oxygen interaction， and so stop plasticizer segregation of EC。 In addition， GPE to the addition of appropriate amount of inorganic packing can also improve electrolyte membrane/lithium electrode interface stability.文檔為個人收集整理，來源于網(wǎng)絡(luò)個人收集整理,勿做商業(yè)用途34 SLane with zeolite powder to the gel electrolyte PAN on modification， the preparation LiAsF6-ECPC-PAN-zeolite composite polymer, figure 2 is different storage time polymer electrolyte and after between electrodes impedance changing with time， although figure 2 (b） initi