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鋰電池電解液阻燃添加劑技術(shù)進(jìn)展 已有1人參與
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鋰電池電解液阻燃添加劑技術(shù)進(jìn)展 限制電動汽車普及的主要因素，主要包括價格、基礎(chǔ)設(shè)施、續(xù)航里程和安全性。事實上，價格、基礎(chǔ)設(shè)施和續(xù)航里程都可以通過其他方式進(jìn)行彌補和改進(jìn)；而安全性，是用戶最關(guān)心的，也是電動汽車和鋰電池生產(chǎn)商必須解決的重要問題。 鋰電池電解液一般采用有機溶劑，在過熱條件下易燃，因此在電解液中加入阻燃添加劑是提高電池安全性最經(jīng)濟有效的方法之一。目前用于鋰離子電池阻燃的物質(zhì)主要包括磷酸酯類、亞磷酸酯類、有機鹵代物類和磷腈類等。 烷基磷酸酯類化合物（如TMP、TEP等）是最早研究用于鋰離子電池的阻燃劑，但其粘度較大、電化學(xué)穩(wěn)定性差，在提高電解液阻燃性的同時會對電解液的離子導(dǎo)電性和電池的循環(huán)可逆性造成負(fù)面影響。利用F元素取代烷基上的H得到氟代烷基磷酸酯（如TFP、BMP、TDP），可以提高化合物的還原穩(wěn)定性及阻燃效果。此外，磷酸甲酚二苯酯（CDP）和磷酸二苯一辛酯(DPOF)等芳香基磷酸酯也具有良好的阻燃效果。 除了磷（V）化合物之外，磷（Ⅲ）化合物也是有效的阻燃添加劑。磷（Ⅲ）化合物與磷（V）化合物比較，更有利于SEI膜的生成，并且前者能使五氟化磷（PF5）失活。在磷（Ⅲ）化合物中，三（2，2，2-三氟乙基）亞磷酸酯（TTFP）不僅能夠降低電解液的可燃性，而且能夠提高鋰離子電池的循環(huán)性能，是一種比較有潛力的阻燃劑。 有機鹵代物阻燃劑主要是指氟代有機物，包括氟代環(huán)狀碳酸酯、氟代鏈狀碳酸酯和烷基-全氟代烷基醚等。氟代有機物具有較高的閃點，同時氟取代氫原子后會降低溶劑分子的含氫量及其可燃性，將其添加到有機電解液中可以提高電解液的安全性。氟代環(huán)狀碳酸酯類化合物，如CH2F-EC、CHF2-EC 和CF3-EC 都具有較好的化學(xué)和物理穩(wěn)定性，較高的閃點和介電常數(shù)，能夠很好的溶解鋰鹽電解質(zhì)并與其它有機溶劑混溶。 磷腈類化合物是指小分子的環(huán)狀或高分子線性磷氮化合物，一些磷腈化合物自身有比較好的離子導(dǎo)電性，可單獨用作鋰離子電池電解液，如含寡居氧化乙烯側(cè)鏈的線性多聚磷腈，離子導(dǎo)電率可達(dá)10-5S/cm。并且，這些聚合物有比較高的分解溫度（約235℃），放熱量適中。如寡聚環(huán)氧乙烯側(cè)鏈的環(huán)狀磷腈三聚體在保持離子導(dǎo)電性的同時具有很好的阻燃性能。 雖然很多種類的電解液添加劑都一定程度上起到了阻燃的效果，但是由于添加劑的物理性質(zhì)（粘度大等）、化學(xué)或電化學(xué)不穩(wěn)定等性質(zhì)，它的加入往往又會對電池的其他方面性能造成負(fù)面影響。因此，在保持電池各方面電化學(xué)性能的同時，開發(fā)具有有效阻燃性能的添加劑是鋰離子電池電解液阻燃添加劑未來發(fā)展的方向。 此外，熱聚合添加劑也是鋰離子電池安全性添加劑研究的一個重要方向。熱聚合添加劑能夠在一定溫度下（如110～150℃）發(fā)生聚合反應(yīng)，從而阻斷電池充放電，阻止電池溫度的上升，避免“熱失控”的發(fā)生。熱聚合的單體需滿足電化學(xué)穩(wěn)定性好、熱穩(wěn)定性好，且不影響鋰離子電池內(nèi)部鋰離子傳導(dǎo)。目前國內(nèi)對該類熱聚合型添加劑的研究尚少，在其實現(xiàn)應(yīng)用之前還需投入大量的研究工作。 2013中國鋰電池電解液研討會將于7月25-26日在上海召開。來自國內(nèi)電解液行業(yè)領(lǐng)軍企業(yè)的專家將做《鋰電池電解液阻燃添加劑技術(shù)進(jìn)展》的主題報告。 Technical Progress of Lithium Battery Electrolyte Flame Retardant Additives The major limits of promotion of electric vehicles (EV) include the price, infrastructure, mileage, and safety. Actually, price, infrastructure, mileage issues can be revamped or improved by other ways; while safety, is the most concerned by customers, also the must be solved problem of EV and lithium battery manufacturers. Lithium battery electrolyte commonly used organic solvents, it is flammable in overheat condition. Therefore, adding flame retardant additives into the electrolyte is one of the most cost-effective ways to improve battery safety. Currently, the LIB flame retardant additives include phosphate ester, phosphite ester, organic halides and phosphazene etc. Alkyl phosphate ester compounds (such as TMP, TEP etc.) are the firstly studied flame retardant additive for lithium ion batteries. But its viscosity is high and electrochemical stability is poor. Although it can improve the electrolyte flame retardance; while at the same time, it may cause negative effects to the electrolyte ionic conductivity and battery cycle reversibility. Use the F element to substitute the H element of the alkyl phosphate ester then get the fluoroalkyl phosphate ester (such as TFP, BMP, TDP) can improve its reduction stability and flame retardant. In addition, cresyl diphenyl phosphate (CDP), diphenyl isooctyl phosphate (DPOF) and other aromatic phosphate ester also has good flame retardant effect. In addition to phosphorus (V) compounds, phosphorus (Ⅲ) compounds are also effective flame retardant additives. Phosphorus (Ⅲ) compounds compared with phosphorus (V) compounds, it is more conducive to the formation of SEI membrane and it can make the phosphorus pentafluoride (PF5) loss of activity. In phosphorus (Ⅲ) compounds, Tris(2,2,2-trifluoroethyl) phosphite ester (TTFP) can not only reduce the flammability of the electrolyte, but also improve the cycle performance of lithium-ion batteries, it is a potential flame retardant additive. The organic halide flame retardant additive mainly refers to organic fluorine compounds, includes the fluorinated cyclic carbonate ester, fluorinated chain carbonate ester and alkyl - perfluoroalkyl ether etc. Fluorinated organic compounds have a high flash point and a fluorine atom substituted for a hydrogen atom will reduce the hydrogen content and flammability of the solvent molecules. Adding it to the organic electrolyte can improve its safety. Fluorinated cyclic carbonate ester compounds such as CH2F-EC, CHF2-EC and CF3-EC have high chemical and physical stability, high flash point and permittivity. They are capable of dissolving lithium salt well and miscible with other organic solvents. Phosphazene compounds refer to small molecule cyclic or macromolecule linear phosphorus-nitrogen compounds. Some phosphazene compounds have good ionic conductivity, can be used alone as a lithium-ion battery electrolyte. For example, the ionic conductivity of the linear multi polyphosphazene with widowed ethylene oxide side chain can reach 10-5S/cm. Moreover, these polymers have relatively high decomposition temperature (about 235 ℃) and moderate heat release. For instance, cyclic phosphazene trimer with oligomeric oxirene side chains has excellent flame retardant while keeping good ionic conductivity. Although many kinds of electrolyte additives have played a certain extent of flame retardant effect, but they may bring negative effects to the other performance of battery due to their peculiar physical properties (such as high viscosity etc.), chemical or electrochemical instability and other characteristics. So to develop an effective flame retardant additive and maintaining all the electrochemical performances of the battery is the future direction. In addition, the thermal polymerization additive is also an important research direction of lithium-ion battery safety additives. Thermal polymerization additives can produce polymerization reaction at a certain temperature (such as 110 ~ 150 ℃), thus blocking the battery charge and discharge, prevent the battery temperature rise and avoid thermal runaway. The monomer that used for thermal polymerization must be with high electrochemical stability, thermal stability, and does not influence the internal lithium ion conductive of the lithium ion battery. At present, the domestic study on the thermal polymerization additive are very few, we need to invest a lot of research work to make it become applied. 2013 China LIB Electrolytes Conference will be held on 25-26 July in Shanghai, China. In the upcoming conference, expert from LIB Electrolytes industry leading company will deliver a speech on “Technical Progress of Lithium Battery Electrolyte Flame Retardant Additives” Probably, ASIACHEM's email is seen as spam by your mail system, please regularly check the spam box, and add ASIACHEM's EMAIL to the whitelist, to make sure you can receive the industrial newsletter. 2013-07-01 -------------------------------------------------------------------------------- |
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