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Ceaseless development of electronics leads to a point where all systems previously heavy and stationary can be produced as light and portable. This creates a new need ¨C the need for a source of energy, compatible with the designed device. For the moment such a source could be lithium ion battery. Its advantages can be found both in the high volumetric and gravimetric energy density in comparison with other electrochemical systems [1]. However, there are some issues that can effectively hinder their development. They are related to such properties of the cell like reversible capacity, cycle life or power density. To increase specific capacity of the econdary lithium cell, one can use lithium as an ultimate negative electrode material. The problem with lithium consists in so-called dendritic growth of lithium. This problem appearing during operation of the battery limits the number of cycles that battery can deliver during its lifetime because of low Faradaic efficiency of lithium deposition¨Cdissolution process. Much more important is that it can be also dangerous, because lithium dendrites growing inside the cell can create a short circuit between negative and positive electrode causing cell failure and possibly thermal runaway. For many years dendritic growth problem was passed round, by exchange of lithium metal with other materials that served as a host for lithium ions like different types of carbon, low potential transition metal oxides or lithium alloys. Nevertheless, these materials have low gravimetric and volumetric specific capacity (in comparison with lithium metal). Other attempts consisted in exchange of liquid electrolyte, by dry solid polymer electrolyte, but this idea is limited to temperatures slightly lower than water boiling point because of their low conductivity at ambient temperatures. Nevertheless, the problem of dendritic growth of lithium has not been solved yet and a practical use of secondary lithium metal cells depends on the solution of this problem [2,3]. The success of practical application of a new technology to the industry depends not only on the advantages of implemented battery, but also on its manufacturing similarity with batteries that are already on the market. State of the art lithium battery technology is PLiON® [3]. The idea of this technology relays on so-called hybrid polymer electrolyte. The advantages of this technology are for example simple and cheap production and easy storage of both electrodes and electrolytes. Moreover, cells can be produced in a variety of shapes and forms. Nevertheless, up to now this technology can not be used with metallic lithium, due to the degradation of PVdF-HFP poly(vinylidene fluoride-co-hexafluoropropylene) polymer in contact with lithium metal and creation of porous lithium (lithium moss), unusable in lithium batteries [4,5]. Solution of the latter problem can be related to the lithium transference number. Elimination of these problems would play a meaningful role in the development of secondary lithium metal battery [6,7]. By adding some chemicals to solid electrolytes, lithium transference number [8¨C12] can be increased. Similar additive can be applied in liquid and gel electrolytes. Generally the motivation for this work was the exploration of possibilities of using inorganic additives as a means of enhancing the properties of gel electrolytes that are lower cost than boro-organic structures [13]. The latter are soluble in the electrolyte. Another approach consists of the application of hybrid inorganic¨Corganic structures that are widely studied in many different areas of science, including battery electrolytes [14]. One of the driving forces to use this kind of materials is to take advantage of Lewis acid¨Cbase interactions between acidic aluminum and basic anion centers [15¨C19]. In this project we tested one soluble (AlBr3) and several insoluble ones (Al2O3 modified to a different extent with H2SO4). µç×Ó²úÆ·µÄ²»¶Ï·¢Õ¹Ê¹ÔÀ´±¿ÖØÇҹ̶¨µÄϵͳ¿ÉÒÔ±»ÖÆÔì³É¼òµ¥±ãЯʽµÄ¡£Õâ²úÉúÁËÒ»¸öÐèÇ󣬼´ÄÜÁ¿À´Ô´ÓëÉ豸¼æÈÝÐÔµÄÐèÇó¡£Ä¿Ç°£¬ÕâÑùµÄÒ»¸öÀ´Ô´¾ÍÊÇï®Àë×Óµç³Ø£¬Í¬ÆäËûµÄµç»¯Ñ§ÏµÍ³Ïà±È£¬Ëü¾ßÓиßÌå»ýºÍÖÊÁ¿ÄÜÁ¿ÃܶȵÄÓÅÊÆ[1]¡£È»¶ø£¬´æÔÚµÄһЩÎÊÌ⣬¼´Ïà¹ØµÄµç³ØµÄÐÔÖÊ£¬ÀýÈç¿ÉÄæÈÝÁ¿£¬Ñ»·ÊÙÃü»ò¹¦ÂÊÃܶȣ¬ÑÏÖØµØÖÆÔ¼×Åï®Àë×Óµç³ØµÄ·¢Õ¹¡£ÎªÁËÔö¼Ó¶þ´Îï®µç³ØµÄ±ÈÈÝÁ¿£¬¿¼ÂÇʹÓýðÊôï®×÷Ϊ×îÖյĸº¼«²ÄÁÏ¡£È»¶ø£¬ï®´æÔÚµÄËùνµÄÖ¦¾§Éú³¤ÎÊÌâ£¨ÖÆÔ¼Á˽ðÊô﮵ÄÓ¦Óã©¡£ µç³ØÊ¹ÓÃÖгöÏֵijÁ»ý¡ªÈܽâ¹ý³ÌÖÐ﮵ĵçÁ÷¸ÐӦЧÂʵ͵ÄÎÊÌâÏÞÖÆÁËµç³ØÊ¹ÓÃÊÙÃüÖеÄÑ»·´ÎÊý¡£¸üÎªÖØÒªµÄÊÇ£¬µç³ØÖÐ﮵ÄÖ¦¾§Éú³¤ÔÚÕý¸º¼«¼ä½¨Á¢ÁËÒ»¸ö»ØÂ·£¬¿ÉÄܵ¼ÖÂµç³ØµÄʧЧºÍÈÈÁ¿µÄɢʧ¶øÒýÆðΣÏÕ¡£¶àÄê¼ä£¬Í¨¹ýʹÓÃÆäËû¿ÉÒÔ×÷Ϊï®Àë×Ó»ùÌåµÄ²ÄÁÏ£¬Ïñ²»Í¬ÀàÐ͵ÄÌ¿¡¢µÍµçλ¹ý¶É½ðÊôÑõ»¯Îï»ò﮺Ͻ𣬴úÌæ½ðÊôï®ÒÔ½â¾ö½ðÊô﮵ÄÖ¦¾§Éú³¤¡£È»¶ø£¬Í¬½ðÊôï®Ïà±È£¬ÕâЩ²ÄÁϵÄÖØÁ¿ºÍÌå»ý±ÈÈÝÁ¿½ÏµÍ¡£ÆäËûµÄ³¢ÊÔ°üÀ¨Ê¹ÓÃÒºÌåµç½âÖÊ£¬¸ÉÔï¹ÌÌå¾ÛºÏÎïµç½âÖÊÌæ´ú£¬µ«ÊÇÓÉÓÚËüÃÇÊÒεĵ絼Âʽϵͣ¬ÕâÖÖ·½·¨ÏÞÖÆÔÚÉÔµÍÓÚË®µÄ·ÐµãµÄζÈÄÚ¡£È»¶ø£¬ï®µÄÖ¦¾§Éú³¤ÎÊÌâÈÔδ½â¾ö²¢ÇÒ¶þ´Î﮽ðÊôµç³ØµÄʵ¼ÊʹÓÃÒÀÀµÓÚÕâ¸öÎÊÌâµÄ½â¾ö·½°¸[2,3]¡£ Ò»Ïîм¼Êõ³É¹¦Ó¦Óõ½Õâ¸öÐÐÒµ²»½öÔÚÓÚʵÏÖµç³ØµÄÓŵ㣬ҲÒÀÀµÓÚÆäÖÆÔìÓëÒѾÔÚÊг¡ÉÏµÄµç³Ø¾ßÓÐÏàËÆÐÔ¡£Ä¿Ç°£¬×îÏȽøµÄï®µç³Ø¼¼ÊõÊÇËÜÁÏï®Àë×Óµç³Ø£¬ÕâÖÖ¼¼Êõ»ùÓÚËùνµÄÔÓ»¯¾ÛºÏÎïµç½âÖÊ£¬ÕâÖÖ¼¼ÊõµÄÓŵãÊÇÖÆÔì¼òµ¥±ãÒË£¬µç¼«ºÍµç½âÖÊÒ×ÓÚ´æ´¢£¬´ËÍ⣬µç³Ø¿ÉÒÔÖÆÔì³É¸÷ÖÖÐÎ×´ºÍ״̬¡£È»¶ø£¬ÓÉÓÚÆ«¶þ·úÒÒÏ©-Áù·ú±ûÏ©¾ÛºÏÎïÔÚÓë½ðÊô﮵ĽӴ¥¹ý³ÌÖлáÍË»¯ºÍ²úÉú²»ÄÜÔÚï®µç³ØÖÐʹÓõĶà¿×ﮣ¨ï®Ì¦£©£¬Òò´ËÕâÖÖ¼¼ÊõÈÔ²»ÄÜÓë½ðÊôï®Ê¹ÓÃ[4,5]£¬ºóÒ»¸öÎÊÌâµÄ½â¾öÓë﮵ÄÇ¨ÒÆÊýÄ¿Ïà¹Ø¡£ÕâЩÎÊÌâµÄÏû³ý¶Ô¶þ´Îï®µç³ØµÄ·¢Õ¹¾ßÓÐÖØÒªµÄÒâÒå[6,7]£¬Í¨¹ýÌí¼ÓijЩ»¯Ñ§Æ·µ½¹ÌÌåµç½âÖÊÖУ¬¿ÉÒÔÔö¼Óï®Ç¨ÒÆÊý[8-12]¡£Ò»°ãÇé¿öÏ£¬ÕâÑù×öµÄ¶¯»úÊÇ̽Ë÷ʹÓÃÎÞ»úÌí¼Ó¼Á×÷ΪÌá¸ßÄý½ºµç½âÖʵÄÌØÐÔµÄÊֶΣ¬ÕâÖÖ·½·¨±ÈʹÓÃÅðµÄÓлú½á¹¹·ÑÓøüµÍ[13]£¬ºóÕß¿ÉÈÜÓÚµç½âÒºÖС£ ÁíÒ»ÖÖ·½·¨ÊÇÔÚ²»Í¬¿ÆÑ§ÁìÓò±»¹ã·ºÑо¿µÄ°üÀ¨µç³Øµç½âÒºÔÚÄÚµÄÎÞ»ú-ÓлúÔÓ»¯½á¹¹µÄÓ¦Óã¬Ê¹ÓÃÕâÖÖ²ÄÁϵÄÒ»¸öÇý¶¯Á¦ÊÇÀûÓÃËáÐÔÂÁºÍ¼îÐÔÒõÀë×ÓÖÐÐÄ[15-19]Ö®¼äµÄ·Ò×˹Ëá¼îÏ໥×÷ÓõÄÓÅÊÆ¡£ ÔÚÕâÏîÑо¿ÖУ¬ÎÒÃDzâÊÔÁËÒ»ÖÖ¿ÉÈÜÐÔ£¨ä廯ÂÁ£©ºÍ¼¸ÖÖ²»ÈÜÐÔµÄÎÞ»ú¡ªÓлú½á¹¹£¨ÁòË᲻ͬ³Ì¶ÈÉϸÄÐÔµÄÑõ»¯ÂÁ£©¡£ |
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