_4、‘ 丨‘ r丨_4, ‘ 丨 ‘ r丨
九、發明說明： L 【發明所屬之技術領域】 本發明與一種固態高分子電解質製造有關，特別是一 種奈米級粒子複合高分子電解質之組成與製造方法。 【先前技術】 第一個研究尚分子電解質起始於1973年Wright等— 人他們利用聚氧化乙烯（polyethylene oxide, PEO)與. KSCN混合，形成具結晶性的錯合物（complex)。接著丨975 年Wdght等人更進一步證明，高溫下（10(TC以上）這些錯 合物具有10-4S/cm以上的導電度。在1〇〇。〇左右pE〇_Sah ^具有像有機電解液的導電度1〇.3s/cm。此後，許多研 究早位便積極投入高分子電解質導電度之研究，希望能夠 改善其至溫下的導電度，以期達到實用階段。所謂固態高 分子電解質，係指驗金屬贱和具有未共用電子對之原子 或官能基的高分子所形成之錯合物（_plexes)，其中鹽類 金屬離子與高分子形成配位鍵。例如（pE〇)n_Licl〇4,並中 η是指PE◦單體和㈣的莫耳比。然而高分子主體和⑽ 子鹽必須分別具高介電常數及低晶格能，以利鋰鹽分解，* 而獲得高Li離子濃度之電解質。 7結晶型PE〇高分子電解質，在室溫下的導電度約為 U) S/cm。由Berthier #人發王見，離子傳導必須在非結晶 相中才發生’因此目前的研究方向多著重於製作低或是低 結晶度的高分子主體。雖然如此’一般仍保留pE〇的美本 化學結構，因為其與鹽類的錯合物形態最為穩定。土 4 1312794· · pV明 ，固態高分子電解質屬離子後具有高度 的導電性質’而此導電性機制多位於pE〇非結晶的區塊 内。但對PEO而言，鐘金屬離子之推合有相當大之限制， 故並非摻合數量愈多，其導電性愈好。事實上過多未解離 之鋰凰則集結成塊並會增加對水的吸收度，#常不利導 電性，造成電解質之缺陷。此外高分子介質的高結晶的特 陡亦對導電度造成負面的影響。總而言之，降低高分子介 質之結晶度，增加導電路徑，提昇高分子之運動性，使古 分子介質在常溫下具導電性能為現今固態高分子 ： 力開發的重要方向。 ，下對本發明闡述之複合固態高分子電 加以說明： 聞巧厅、 (1)固態高分子基材 m2高分子電解f ’基本上^具可撓性的高分子某 材與金屬鹽類混摻所構成，冬 土 基材的無定形區域中，：使;摻後，在高分子 基互相作用德產因與高分子上之官能 錯合物結構。當有電場形成 广:形成 定型區域當中，”一 2 屬離子會在面分子的不 移動，進而完成八穷方向經由南分子鏈段之運動而 解質應用在元^ 傳導過程。若將固態高分子電 以下幾個特性次電池’固態電解質就必須擁有 ⑷好的可撓性。ν子導電度，（b)具有好的成膜性質， 一般而言’高分子基材的本質大部分是屬於結晶性材 5 1312794* · :於[爾 3 ；早 ο π f *' ' ' * .... _ f 料例如.聚氧化乙烯（polyef研祝而.器（PE0))，聚偏氟 乙烯（P〇lyvinylldene fluoride (PVdF))，聚甲基丙締酸甲= (P〇ly (methyl methaCrylate (PMMA))等。在具有柔軟鍵广日 的高分子和驗金屬鹽類所組成的固態高分子電解質薄膜: 室溫下的導電率約在1〇-5〜1〇-6s/cm左右，並不符合商業上 的需求。但隨著高分子薄膜操作溫度增加至溶點以上時 ("ο— temperatUre，L約在45〜6(TC時）高分子當中之社 晶區域均被破壞成不定型區域，使得轉子在該電解質薄° 膜當中藉由高分子擾動與使得傳導速率增加而得到較佳的 離子導電率，約在1G.M(r4S/cm左右。不同組成之電解質 有不同的溫度改變行為。近年來有諸多開發出用來改盖高 分子電解質中離子導電度的聚合材料：如高分子包含四烧 基銨鹽基結構（美國專利第5,643,49〇號），或是 P〇lybenzimidazole 摻雜以 h3P〇3 (美國專利第 5 688 613 號）。更有建議加入大量的可塑劑（如碳酸乙酯Ethyi Carbonate，EC、碳酸丙烯 Propylene Carb〇nate, %、碳酸 二甲醋Dimethyl carbonate, DMC等）到高分子電解質當 中，形成“膠態電解質”（如美國專利^ 5,581,394;5,705,084;5,645,960;5,731,104；5,6095974;5,586, 0 01號所示）。使用可塑劑於固態電解質中雖然改善室溫下 導電度不佳的情形’但如此作法除了會大幅的降低機械性 質。、若想要同時保持良好的導電度及機械性並將高分子用 於成膜加工方面，膠態高分子並不是理想的選擇。 (2 )金屬鹽類 1312794. * Γ 1 …… ............ I」，' .· ί ‘.，：，.， 使用鐘金屬作為二次電泥（如高能量密度電池）的方 已被廣泛的研九，其中以具有較尚機械性質之固態電解 質為目前最為迫切的需求。到目前為止，對於一方面想要 改善固態電㈣薄膜的離子導電度另—方面又希望能維持 其較佳的機械性質，仍然是有一定的困難度。一般而言鹽 類需具有易移動之陽離子，如Li, Na，K，Mg，等 子之選擇上可包含BF4、SCN、s〇3CF3、AsF6、pF=、 N—(CF3S03)2¥。較大的陰離子基團且具有較高的未定域電 荷（delocalized charge)，所以易解離形成離子狀態。 (3 )奈米粒子改質劑 改質劑的種類不限定於何種材料，主要的目的是希望 藉由改質劑的加入，使原本高分子系統上的物性缺失獲得 改善，達到增強其機械性與加工性的目的。本發明當中所 採用的即是具有良好半導體性質的二氧化鈦粒子做：改質 劑。在以往的研究當中二氧化鈦通常被用來當做觸媒處理 污水或是做為分解有機物質之用。原理是利用半導體物質 在受到臨界波長以下的光線照射後，皆會激發而產生電子 矛電洞對的機制，進而產生自由基（free radical)解離分解有 機物質。但近年來由於科技的進步，有些學者嘗試研究其 粒子的特性並將其應用到光電材料，電發光裝置及電化學 研九上更有些疋將一氧化鈦混摻著金屬藉以增加其機械 性質。在光電化學的領域當中更有將不同的染料加入系統 中期望增加其導電性。但令人該異的是上述奈米級粒子因 具有高的表面電位與上述金屬鹽類形成良好的電雙層結 1312794 * iTviff' 構。有助於金屬鹽解離，並與分子基材形成良好的 相容性。 (4)高溫高壓處理 非球狀對稱的奈米♦立子在電場冑導下能產i順向的排 2其週遭的高分子在加溫的狀況下，周圍介電場方向與 奈米t子界電場呈反方向的排序。故在施加電場與提昇溫 度的％境中，高分子電解質之介電常數會逐漸提高。但由 於離子導電度和介質中介電常數成比例關係 場與溫度的情況下，導電度能大幅提昇。而能造成此j 象之則提是奈米粒子必須具有非球狀對稱形狀，且具有極 強，介電場方向異性性質。能具有此一性質之奈米粒子並 不多見。本發明即針對以上奈米、級粒子之特性，使高分子 電解質展現優異的導電和機械性能而提出。 【發明内容】 此發明的主要目的是：製備一種新的複合固態高分子 電解質薄膜材質具有優良的離子導電度 性與加工性質。此奈米粒子複合材料固態高分子電解=械 可作為凡件組裝之局能量鐘二次電池及應用在其他電化學 疋件：如超高電容器，感應器等使用。 本發明係關於奈米級粒子複合高分子電解質之組成與 。上述奈米級粒子複合高分子電解質之組成，包含. 2材高分子，其中高分子主鏈或侧鏈上包含有一路易士 鹼S能基’且其熔點或某溫度區間内具有不定型區塊.一 可離子化之金屬鹽類，其包含有金屬陽離子與陰離子’，其 1312794 · 中金屬鹽類可以藉由與 月1j述之尚分子形成錯合物的結構， 使金屬陽離子與陰離子右客公晳由陆日丄，IX. Description of the invention: L [Technical field to which the invention pertains] The present invention relates to the manufacture of a solid polymer electrolyte, and more particularly to a composition and a manufacturing method of a nano-sized particle hybrid polymer electrolyte. [Prior Art] The first study of molecular electrolytes began in 1973 by Wright et al. - They used polyethylene oxide (PEO) and KSCN to form a crystalline complex. Then, in 975, Wdght et al. further proved that at high temperatures (10 (above TC), these complexes have a conductivity of 10-4 S/cm or more. At 1 〇〇. 〇 around pE〇_Sah ^ has organic electrolysis The conductivity of the liquid is 1〇3s/cm. Since then, many studies have been actively investing in the conductivity of polymer electrolytes, hoping to improve the conductivity to the temperature, in order to reach a practical stage. So-called solid polymer electrolytes, Refers to a complex (_plexes) formed by a metal ruthenium and a polymer having atoms or functional groups that do not share an electron pair, wherein the salt metal ion forms a coordinate bond with the polymer. For example, (pE〇)n_Licl〇4 And η refers to the monomer ratio of PE◦ and (4). However, the polymer host and the (10) salt must have high dielectric constant and low lattice energy, respectively, to facilitate decomposition of the lithium salt, and obtain high Li ions. The electrolyte of the concentration. 7 Crystalline PE〇 polymer electrolyte, the conductivity at room temperature is about U) S / cm. By Berthier #人发王见, ion conduction must occur in the amorphous phase. Therefore, the current research direction focuses on the production of low or low crystallinity polymer bodies. Even so, the chemical structure of pE〇 is generally retained because its complex form with salts is the most stable. Soil 4 1312794 · · pV Ming, the solid polymer electrolyte has a high degree of electrical conductivity after the ion' and this conductivity mechanism is mostly located in the non-crystalline block of pE〇. However, for PEO, the push of the metal ion has a considerable limitation, so the more the blending quantity, the better the conductivity. In fact, too many undissociated lithium phoenix aggregates into blocks and increases the absorption of water. #常不负导性, causing electrolyte defects. In addition, the high crystallinity of the polymer medium also has a negative effect on the conductivity. All in all, reducing the crystallinity of the polymer medium, increasing the conductive path, and improving the mobility of the polymer, so that the ancient molecular medium has electrical conductivity at room temperature is an important direction of today's solid polymer: force development. The following description of the composite solid polymer electric power described in the present invention: Wen Qiao Hall, (1) solid polymer substrate m2 polymer electrolysis f 'basically ^ flexible polymer material and metal salt mixed In the amorphous region of the winter soil substrate, after the blending, the polymer matrix interacts with the polymer and the functional complex structure on the polymer. When there is a wide electric field formation: in the formation of the shaped region, "a 2 genus ion will not move in the surface molecule, and then complete the eight-poor direction through the movement of the southern molecular segment and the solution is applied to the meta-conduction process. If the solid state is high Molecular power The following characteristics of the secondary battery 'solid electrolyte must have (4) good flexibility. ν sub-conductivity, (b) has good film-forming properties, in general, the nature of the polymer substrate is mostly Crystalline material 5 1312794* · : [ [ 3 ; early ο π f * ' ' ' * .... _ f material such as polyethylene oxide (polyef research (PE0)), polyvinylidene fluoride (P〇lyvinylldene fluoride (PVdF)), polymethyl methacrylate A (P〇ly (methyl methaCrylate (PMMA)), etc.. Solid in high solids and metal salts with soft bonds Molecular electrolyte membrane: The conductivity at room temperature is about 1〇-5~1〇-6s/cm, which is not in line with commercial requirements. However, as the operating temperature of the polymer film increases above the melting point (" Ο— temperatUre, L is about 45~6 (TC), the crystal region of the polymer is destroyed The amorphous region causes the rotor to have better ionic conductivity in the electrolyte thin film by polymer perturbation and increasing the conduction rate, which is about 1 G.M (r4 S/cm. The electrolytes of different compositions are different). Temperature change behavior. In recent years, there have been many polymeric materials developed to modify the ionic conductivity of polymer electrolytes: for example, a polymer containing a tetraalkylammonium salt-based structure (U.S. Patent No. 5,643,49), or P 〇lybenzimidazole is doped with h3P〇3 (US Patent No. 5 688 613). It is recommended to add a large amount of plasticizer (such as ethyl carbonate Ethyi Carbonate, EC, propylene carbonate Propylene Carb〇nate, %, dimethyl acesulfate Dimethyl Carbonate, DMC, etc.) to form a "colloidal electrolyte" in a polymer electrolyte (as shown in U.S. Patent Nos. 5,581,394; 5,705,084; 5,645,960; 5,731,104; 5,6095974; 5,586, 0 01). Using a plasticizer in a solid electrolyte Although it improves the case of poor electrical conductivity at room temperature, it does not greatly reduce the mechanical properties, but if you want to maintain good electrical conductivity and mechanical properties. Colloidal polymers are not an ideal choice for the use of polymers for film formation. (2) Metal salts 1312794. * Γ 1 ...... ............ I",' . · ί '.,:,., The use of clock metal as a secondary electrolyte (such as high energy density batteries) has been extensively studied. Among them, solid electrolytes with more mechanical properties are currently the most urgent needs. So far, there is still some difficulty in trying to improve the ionic conductivity of the solid-state (four) film on the one hand and to maintain its better mechanical properties. Generally, the salt needs to have a movable cation such as Li, Na, K, Mg, and the selection may include BF4, SCN, s〇3CF3, AsF6, pF=, N-(CF3S03)2¥. Larger anionic groups and have a higher delocalized charge, so they are easily dissociated to form an ionic state. (3) The type of nanoparticle modifier is not limited to which material. The main purpose is to improve the physical properties of the original polymer system by adding the modifier. The purpose of sex and processing. In the present invention, titanium dioxide particles having good semiconductor properties are used as modifiers. In previous studies, titanium dioxide was often used as a catalyst to treat sewage or as a decomposition of organic matter. The principle is that after the semiconductor material is irradiated with light below the critical wavelength, it will excite the mechanism of the electron spear hole pair, and then generate free radicals to dissociate and decompose the organic matter. However, in recent years, due to the advancement of science and technology, some scholars have tried to study the characteristics of their particles and apply them to photovoltaic materials. Electroluminescence devices and electrochemical research have added some titanium oxide to metal to increase its mechanical properties. In the field of photoelectrochemistry, it is more desirable to add different dyes to the system in order to increase its conductivity. However, it is quite the case that the above-mentioned nano-sized particles have a good electric double-layered structure 1312794 * iTviff' structure due to a high surface potential and the above-mentioned metal salt. It helps to dissociate the metal salt and form good compatibility with the molecular substrate. (4) High-temperature and high-pressure treatment of non-spherical symmetrical nano ♦ 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立The boundary electric field is ordered in the opposite direction. Therefore, in the case where the electric field is applied and the temperature is raised, the dielectric constant of the polymer electrolyte is gradually increased. However, since the ionic conductivity is proportional to the dielectric constant of the medium, the conductivity can be greatly improved in the case of field and temperature. What can be caused by this j-image is that the nanoparticles must have a non-spherical symmetrical shape and have a strong, dielectric-field directional nature. Nanoparticles capable of having this property are rare. The present invention has been made in view of the characteristics of the above nanoparticles and graded particles, and the polymer electrolyte exhibits excellent electrical and mechanical properties. SUMMARY OF THE INVENTION The main object of the invention is to prepare a novel composite solid polymer electrolyte membrane material having excellent ionic conductivity and processing properties. This nanoparticle composite material solid polymer electrolysis = mechanical can be used as a unit of energy for the assembly of energy secondary batteries and applications in other electrochemical components: such as ultra-high capacitors, sensors and so on. The present invention relates to the composition and composition of a nano-sized particle hybrid polymer electrolyte. The composition of the above-mentioned nano-sized particle composite polymer electrolyte comprises a 2-material polymer in which a polymer backbone or a side chain contains a Lewis base S-energy group and has an amorphous block in a melting point or a temperature range thereof. An ionizable metal salt comprising a metal cation and an anion, wherein the metal salt of 1312794 can be formed by a structure which is complex with the molecule described in the month 1j, and the metal cation and the anion right The publicity is by Lu Rizhen,
月|J述之高分子鹽類錯合物形成路易斯酸 進一步的，本發明乃有關於奈米粒子之製作。—般而 吕，奈米粒子表面殘留由合成遺下的介面活性劑、氧化物 或水份不純物等所造成。使用燒結方法將殘留有碳里不易 除去’而影響奈米粒子之功能。 … 更進一步的，本發明之特點在於該複合高分子電解中 所包含之奈米級粒子因特殊製備方式形成非球形對稱形 狀。配合在混摻時實施超音波照射達到高度分散之效果。 該非球形對稱奈米級粒子在固態高分子電解f巾和鹽類及 基質高分子路易斯鹼基形成一錯化合物結構，一則促進基 質高分子之非定型區比例並且也促進金屬鹽類之陽離子二 陰離子解離程度，進而提昇該高分子電解質之離子導電 性。更進一步因該複合高分子電解質包含非球形對稱奈米 粒其介電常數達到183,經加溫處理或在充放電循環電場 誘導下非球狀對稱的奈米粒子在能產生順向的排列，使高 分子電解質之介電常數逐漸提高，進而使導電度經加熱^ 理後大幅提昇-至二個級數。提昇之導電度有助於減低元 件内阻，抗提昇元件之低溫放電物性，及延長元件壽命。 【實施方式】 可叩 1312794 丨The formation of a Lewis acid by a polymer salt complex as described in JP; Further, the present invention relates to the production of nanoparticle. In general, the residual surface of the nanoparticles is caused by synthetic surfactants, oxides or water impurities. The use of a sintering method leaves the carbon in the residue, which is difficult to remove, and affects the function of the nanoparticles. Further, the present invention is characterized in that the nano-sized particles contained in the electrolysis of the composite polymer are formed into a non-spherical symmetrical shape by a special preparation method. In combination with supersonic irradiation during mixing, the effect of high dispersion is achieved. The non-spherical symmetric nano-sized particles form a wrong compound structure in the solid polymer electrolysis f towel and the salt and the matrix polymer Lewis base, and one promotes the ratio of the amorphous region of the matrix polymer and also promotes the cationic dianion of the metal salt. The degree of dissociation further enhances the ionic conductivity of the polymer electrolyte. Further, since the hybrid polymeric electrolyte comprises non-spherical symmetric nanoparticles, the dielectric constant thereof reaches 183, and the non-spherical symmetrical nanoparticles are heated in the heating process or induced by the electric field of the charge and discharge cycle to produce a forward alignment. The dielectric constant of the polymer electrolyte is gradually increased, and the conductivity is greatly increased by heating to two stages. The improved conductivity helps to reduce the internal resistance of the component, resists the low temperature discharge properties of the lifting element, and extends the life of the component. [Embodiment] 叩 1312794 丨
' I 本發明之複合高分子電解質中包含有高分子基材， 屬鹽類及選擇性的奈米級結晶粒子改質劑。 > 在所有的應用當中就屬以摻合成複合材料的方式最為 廣泛。本發明中所選擇的即是採用奈米二氧化欽㈣做爲 向分子電解質複合材之改質劑。 ‘、、' 本發明所揭露之高分子具有優良可撓性的本質，且擁 ^良好的機械性質，所以在加工的過程當中能製成可挽的 合=又由於在固態高分子電解質當中的離子錯合物結構 會、時和電極產生離子交換效應，使得在應用於電化學裂 置士具有提升的效益。此固態高分子電解質材料特別適^ 於咼能量密度的二次電池。 本發明所揭露的11〇2奈米級粒子由於Ti結 使粒子呈現極大的介電常數方向異性，在結晶粒 ί的過程中’加錢誘導之使成長成條狀的奈米粒子， 八士其方向異性的性f。經與高分子介質形成奈米粒子複 電解質後’經過電場及熱處理，展現出更加優越 =離2導電性質。此材料之組成和形狀正是本發明之複合 呵刀子電解質展現優異導電度之原因。 離子：鹼ΐ屬鹽可以離子化於高分子基材的不定型區，且 著子的配位原子互相作用的影響之下會使離子順 向在高分子當中擴散，而完成離子導電功能。 ?聚乳化乙烯和驗金屬鹽的組成為例，鹼金屬離子 了以和^刀子主鏈上的醚基的氧有 較高的介電常數，同時告利用知^乍用心刀子有 u f田利用加熱的方式使高分子的不定 乎月日_LC JinjLi 1312794 j___/tm <,f 1 里區有足夠的分子鏈段運動，如此即可表現出離子導電 性。有幾種南分子可以適用於作為高分子電解質的基材， 如聚氧化乙烯（PEO )、在伽鍅古 甲基丙稀酸高分子等 鏈有咖結構的聚丙婦酸或 其他適合作為高分子基材的包括：含氣化烧基、氣化 伸烧基、碳酸酯基、氰基等官能基的高分子，這些官該 有如㈣上的氧原子—般扮演著路易士驗的角色，可和^ 屬鹽類的離子產生交互作用促進鹽類解離。這些高分子均 可以由合成的方式或是從商業上得到。本發明的固態複合 南分子電解質因為加入奈米級二氧化鈦粒子於電解質當 中，故具有-良好的機械及加工性質，尤其是，在室溫; 當好的導電度的。此一特性是在於二氧化鈦粒子 與金屬鹽類形成一路易斯酸檢對交互作用力，增加了金屬 =在南分子當中的解離程度，使鋰離子能藉由高分子鏈 奴的運動而移動，進而得到高離子導電度The composite polymer electrolyte of the present invention comprises a polymer substrate, which is a salt and a selective nano-crystal particle modifier. > In all applications, it is the most widely used method of incorporating composite materials. What is selected in the present invention is the use of nano-dioxide (4) as a modifier for the molecular electrolyte composite. ',,' The polymer disclosed in the present invention has an excellent flexibility and possesses good mechanical properties, so that it can be made in a process of processing and can be made in a solid polymer electrolyte. The ion complex structure has an ion exchange effect on the time, and the electrode, which has an improved benefit in application to electrochemical crackers. This solid polymer electrolyte material is particularly suitable for a secondary battery of 咼 energy density. The 11〇2 nanometer particle disclosed in the present invention causes the particle to exhibit a great dielectric constant anisotropy due to the Ti junction, and in the process of crystal grain ί, the nanoparticle which grows into a strip shape is induced by the addition of money. The nature of the opposite sex f. After forming the nanoparticle complex electrolyte with the polymer medium, the electric field and heat treatment show superiority. The composition and shape of this material is the reason why the composite knife electrolyte of the present invention exhibits excellent electrical conductivity. Ion: The alkali bismuth salt can be ionized in the amorphous region of the polymer substrate, and the interaction of the ligand's coordination atoms causes the ions to diffuse in the polymer to complete the ion conduction function. For example, the composition of the polyemulsified ethylene and the metal salt is high, and the alkali metal ion has a higher dielectric constant with the oxygen of the ether group on the main chain of the knife, and at the same time, the use of the knives is used to heat the uf field. The way to make the polymer uncertain is _LC JinjLi 1312794 j___ / tm <, f 1 inner zone has enough molecular segment movement, so that it can show ionic conductivity. There are several kinds of southern molecules that can be used as a substrate for polymer electrolytes, such as polyethylene oxide (PEO), polyglycolic acid in a chain structure such as gamma-glycolic acid, or other suitable polymer. The substrate includes: a polymer containing a functional group such as a gasification base, a gasification extension group, a carbonate group, a cyano group, etc., and these officials have the role of a Lewis test in the oxygen atom of (4). Interaction with ions of the genus Salts promotes salt dissociation. These polymers can be obtained synthetically or commercially. The solid composite south molecular electrolyte of the present invention has good mechanical and processing properties because of the addition of nano-sized titanium dioxide particles to the electrolyte, especially at room temperature; when good conductivity. This property is characterized in that the titanium dioxide particles form a Lewis acid detection interaction with the metal salt, increasing the degree of dissociation of the metal = in the south molecule, so that the lithium ion can be moved by the movement of the polymer chain slave, thereby obtaining High ionic conductivity
LiC104、BF4、SCN、SO γρ … 3、 6、N(CF3S〇3)2 等鹽類， 口 “較大的陰離子基團且具有較高的去定域電荷 (如㈣’所以易解離形成離子狀態。其可解離 ^鐘金屬鹽類的含量與離子導電度之間成—比例之關係。 ^明人相信本發明的高離子導電性之複合固態高分子電解 買(composite solid p〇lVmPr , yte，以下簡稱CSPE) 二it入的改如：二氧化鈦），是解離金屬鹽類 關鍵之一。其解離後之鐘離子進入基材高分子的晶 格之中形成-類似錯合物形式’一方面降低其結晶度，另 11 1312794 I 修 一方面也增加CSPE的自兩個現象增加了不定 形區域的體積，而有利離子導電性。 在本發明中，被促進的CSPE組合物所形成薄膜的離 子導電度可以高達到1〇_3〜lO^Ohm/cm之間較一般傳統的 SPE薄膜南出1〇1〜1〇2倍。本發明被促進的cspE的離子 導電度’足可以運用在實際的電化學電池。 進一步來講，當本發明的CSPE組合物薄膜被使用在 電化學電池中作為一電解質時，基材高分子和金屬鹽類與 改質劑所組成複合材薄膜可提供電極間之良好的隔離效 果，避免電解質因加熱或其外在因素而導致兩電極面之活 性金屬因化學反應所產生的樹枝狀鋰金屬（dendrimer)接 觸到電極而發生短路的現象而產生爆炸。此外添加改質劑 二^化鈦於SPE當中不僅可以調整其電解質成膜後的機械 性質，還可以增加高分子中金屬鹽類的解離能力，增加電 解質當中鋰離子的導電能力。至於CSPE薄膜製作的方式 可包含喷塗（spraying)、含浸（immersing)、鑄造（casting)等 幾種，其中最被建議使用的是以鑄造的技術做為基準的塗 佈方式。其基材上所殘留的有機溶劑，可藉由熱處理的方 式來移除溶劑，其溫度和壓力應小心地控制，並注意不要 弓丨起任何可能改變該基材高分子結晶的情況發生，也應避 免任何的化學反應發生。 本發明更進一步的揭露了改質劑奈米級二氧化鈦的製 作與製備電解質流程上的改進。一般市售的二氧化鈦顆粒 之粒徑均太大，且合成之過程中均加入分散劑、穩定劑或 12 1312794 j. ' ' · -. i 質使用。-般而言， 氧化欽最:普遍:：:：=一)製備二 ΛΛ^ί〇 .、 為主。在利用Sol-Gel法製備凝膠化溶膠 ^ '合膠之形成與否會受到縮合反應之反應速率及 :T·二取代方式的控制，因此我們在進行Sol_Gel法製 2時特別針對其四丁基鈦酸㈣沉抑4]之反應性做 進一步的修飾與探討。 .二烷氧化物在空氣中是屬於極易反應的物質，且在水 ^ a生成白色沉殿之Ti(〇H)4。為了製備奈米級的二氧 BB粒子懸$液’醇氧化鈦水解反應下所生成的沈殺 砬大小，在整個合成的過程當中扮演著極重要的角色。 :般：藉由調整ΡΗ值，來控制其整體的反應性，並且可 以使得生成的二氧化鈦粒徑達到奈米級的尺寸。pH值的調 整可藉由若酸如冰醋酸來達成用以降低鈦烧氧化物之反應 性。以避免粒子集結產生沉澱。 在本實驗中我們㈣四丁基鈦酸為起始物，並且在反 應的過程中加人適量的醋酸調制粒子之大小。在實驗中我 們發現到醋酸會先行與起始物（四丁基鈦酸）發生反應， 而產生兩種新型式的中間產物，如圖一所示。藉由分析測 4 ( GC Mass, FTIR等）所得到的結果得知，這兩種型式 之中間產物皆存於我們的系統當中。我們將這兩種結構統 稱為螯合（chelating)和架橋（bridging)兩種型式。在本 系統當中，四丁基鈦酸會先行與醋酸進行反應而形成新的 1312794 ‘ 平月日.”； 扭私也& ^ ___桶无丨 (σ物質，廷疋因為醋酸的加入會使得鈦烷氧化物由原本 的四配位演變成更加穩定的六配位的鍵結方式，使得鈦的 2位數達到餘和而產生安定的鈦院氧化物。在我們的系統 田中也發現到，其取代後鈦烧氧化物上的醋酸基 不易被氫氧基（_0H)所取代，因而降低水解後形成凝膠 化之反應速率，且延長其凝膠之時間也可以避免沉澱反應 現象發^。經過這樣的修飾過程後，則達到我們所想要的 奈米二氧化鈦的結晶膠體溶液。且由實驗中也證實了螯合 型式之醋酸基（_0Ac)在進行水解反應的過程中鍵結隨即 被打斷。 由於本發明之製造方法不使用界面活性劑，成品粒子 表面不包覆有機化合物，這對製備純的奈米粒子為重要的 關鍵。 本發明中奈米粒子的製備方法如以下各實施例所述： (1 )奈米級Ti〇2結晶粒子的製備 量取冰醋酸與去離子水以莫耳比為丨：1〇的比例配製 成醋酸水溶液，再將異丙醇加入到四丁基鈦酸（醇氧鈦） 中，緩緩的加入到醋酸水溶液當中，其過程屬於水解反應 且會因反應速率過快而放出大量的熱能故必須要小心，所 以在反應的過程中採用冰浴在〇艺下採用機械攪拌方式進 行。當反應物加入完畢後，改用油浴方式加熱至8〇^讓溶 液反應八個小時之後停止攪拌，將溶液放入高壓反應器 (Autoclave)當中放置在23〇t的烘箱中，利用水熱法 (Hydrothermal)之方式反應，且反應時間宜控制在12個 年LiC104, BF4, SCN, SO γρ ... 3, 6, N (CF3S〇3) 2 and other salts, the mouth "larger anionic group and has a higher delocalized charge (such as (four)' so easy to dissociate to form ions The relationship between the content of the metal salt and the ionic conductivity can be dissociated from the ionic conductivity of the complex organic solid polymer (composite solid p〇lVmPr , yte , hereinafter referred to as CSPE), the change of the second input: titanium dioxide), is one of the key to dissociation of metal salts. After the dissociation, the ions enter into the crystal lattice of the substrate polymer - similar to the complex form Reducing the crystallinity, another 11 1312794 I also increases the volume of the CSPE from the two phenomena, increasing the volume of the amorphous region, and favoring the ionic conductivity. In the present invention, the ions of the film formed by the promoted CSPE composition The conductivity can be as high as 1〇_3~lO^Ohm/cm, which is 1〇1~1〇2 times larger than that of the conventional SPE film. The ionic conductivity of the promoted cspE of the present invention can be used in practice. Electrochemical cell. Further speaking, When the CSPE composition film of the invention is used as an electrolyte in an electrochemical cell, the composite film composed of the substrate polymer and the metal salt and the modifier can provide good isolation between the electrodes and avoid electrolyte heating. Or its external factors cause the active metal on the two electrode faces to explode due to the phenomenon that the dendrimer generated by the chemical reaction contacts the electrode and short-circuited. In addition, the modifier is added to the titanium dioxide in the SPE. It can not only adjust the mechanical properties of the electrolyte after film formation, but also increase the dissociation ability of metal salts in the polymer and increase the conductivity of lithium ions in the electrolyte. As for the way of making CSPE film, it can include spraying and impregnation ( Immersing), casting, etc., the most recommended one is the coating method based on the casting technology. The organic solvent remaining on the substrate can be removed by heat treatment. The temperature and pressure should be carefully controlled, and be careful not to smash any conditions that may change the polymer crystallization of the substrate. The invention also avoids any chemical reaction. The invention further discloses an improvement in the preparation and preparation of the electrolyte for the modification of the titanium dioxide. Generally, the particle size of the commercially available titanium dioxide particles is too large and synthesized. In the process, a dispersant, a stabilizer or 12 1312794 j. ' ' · -. i is used. In general, the oxidation of the chin is the most common::::=1) Preparation of two ΛΛ^ί〇. In the preparation of gelled sol by Sol-Gel method, the formation of the gel will be affected by the reaction rate of the condensation reaction and the control of the T·disubstituted method. Therefore, we specifically target the Sol_Gel process 2 The responsiveness of butyl titanate (4) inhibition 4] was further modified and discussed. Dioxane is a highly reactive substance in air and forms Ti(〇H)4 in the white sink in water. In order to prepare the nanometer-sized dioxo BB particles, the size of the sputum produced by the hydrolyzed reaction of the titanium oxyhydroxide plays a very important role in the whole synthesis process. : General: By adjusting the enthalpy, the overall reactivity is controlled, and the particle size of the produced titanium dioxide can be made to the nanometer size. The pH adjustment can be achieved by reducing the reactivity of the titanium oxide oxide by an acid such as glacial acetic acid. To avoid precipitation of particles. In this experiment, we (tetra) tetrabutyl titanate was used as the starting material, and the amount of acetic acid was adjusted to the size of the particles during the reaction. In the experiment, we found that acetic acid reacted first with the starting material (tetrabutyl titanate) to produce two novel intermediates, as shown in Figure 1. The results obtained by Analytical Measurement 4 (GC Mass, FTIR, etc.) show that the intermediates of these two types are present in our system. We refer to these two structures as chelating and bridging. In this system, tetrabutyl titanic acid will react with acetic acid to form a new 1312794 'Flat Moon Day.'; Twisted also & ^ ___ barrel without flaws (σ substance, Tingyi because of the addition of acetic acid The titanium alkoxide is evolved from the original tetracoordinate to a more stable six-coordinate bonding method, so that the two digits of titanium reach a balance and produce a stable titanium oxide. It is also found in our system field. The substituted acetic acid group on the titanium oxide oxide is not easily replaced by the hydroxyl group (_0H), thereby reducing the reaction rate of gelation after hydrolysis, and prolonging the gelation time can also avoid the precipitation reaction phenomenon. After such a modification process, we have reached the crystalline colloidal solution of nano titanium dioxide that we want. It has also been confirmed by experiments that the chelating type of acetic acid group (_0Ac) is bonded during the hydrolysis reaction. Since the manufacturing method of the present invention does not use a surfactant, the surface of the finished particles is not coated with an organic compound, which is an important key for preparing pure nano particles. Preparation of Nanoparticles in the Invention The method is as follows: (1) Preparation amount of nano-Ti〇2 crystal particles: glacial acetic acid and deionized water are prepared in an amount of molar ratio of 丨:1〇 to prepare an aqueous solution of acetic acid, and then different Propyl alcohol is added to tetrabutyl titanate (alcohol titanate) and slowly added to the aqueous acetic acid solution. The process belongs to the hydrolysis reaction and will release a large amount of heat due to the reaction rate being too fast, so care must be taken, so the reaction In the process, the ice bath is used to carry out the mechanical stirring method under the process of the art. When the reactants are added, the oil is heated to 8 〇^, the solution is allowed to react for eight hours, the stirring is stopped, and the solution is placed in the high pressure reactor. (Autoclave) placed in an oven of 23 〇t, reacted by hydrothermal method, and the reaction time should be controlled in 12 years.
1312794 小時至14何之㈣f 小時 緩慢降、、ww、去2：丨1 〜4〇 C的速度 〜皿相熟的目的，並可得到較好的莊曰型離 為白色亀殿之水溶液，此溶液 乳鈦粒子水溶液。由於我們在製備高分子 中必須絕對要求控制其水分的含量，所處的環= 疋屬於無水的狀態，所以對其製備上所需之夺 鈦結曰:曰粒子必須先經過除水之過程。我們將奈:級:氧化 =溶液放置在鐵氟龍的燒杯中’繼續以烘箱在低溫的狀 心下（約50 C)緩慢的將溶劑除去，這是為了避免其水溶 液當:的醇類及其他反應物因高溫反應燒結而形成焦炭，， 而附著在二氧化鈦結晶粒子的表面形成雜質，影響其成八 的純度。發明人嘗試利用8(rc以上的溫度供乾水=並ς 現其二氧化鈦粒子轉變成為褐色粉冑。且若在烘乾的過程 中採用高溫則會使得二氧化鈦之晶形由Anatase轉變成為 Rutile結構（約MKTC以上）。將乾燥後形成塊狀之二氧化 鈦結晶（Anatase)利用瑪瑙研缽研磨成細微的粉末，並將 粉末放置於不透光之樣品瓶當中備用。這是由於奈米二氧 化鈦粒子一經由UV光照射後會有一能帶上的差異而擁^ 半導體之性質，這當中的轉變是我們在製備電解質溶液當 中所希望能避免的。 田 此時高分子電解質液混摻當中所需之二氧化鈦結晶粒 子粉體’並非均勻之奈米級粒子’介面電荷作用力使之集 結成大小不同的區塊（Cluster)。在高分子複合材料的區塊 15 1312794 中出現會降低電性^機械性的改進效能。所以，我們在製 備的過％中將二氧化鈦粒子先與無水之溶劑混合並利用超 =波震盪能將樣品打散至最小分散粒子。並利用具有特定 介電常數之溶劑來加強分散二氧化鈦粒子至奈米等級。不 同的溶劑所得到的分散效果也不盡相同，這是因為二氧化 ，，子與溶劑間所形成的溶劑效應（solvent effect)會隨 著心劑界電常數的不同而有所差異。此外隨著超音波震盪 時間的不同，其粒徑也會有所改變。透過光散射分析儀 (=LS )及穿遂式電子顯微鏡（TEM )觀察粒子在溶劑中 的分散性與粒子之平均粒徑大小的結果發現，隨著超音波 震盛的時間不同其粒徑的分散性及強度亦有其一定程度的 =勢。且二氧化鈦粒子的粒徑大小均介於20〜5〇nm之間。 5如圖二所示：3Qmin震盪後的粒子分佈約可分成兩個 二知、，一為20nm另一區為5〇nm，而震i時間45論後則 p都均勻勿政成50nm大小的顆粒。圖中可看出利用超 =震Μ奴顆粒大小分佈均在5Qnm以下。 的時間增加粒子逐漸分離成單獨的奈米粒子。 利用DLS儀器測量粒徑所得到的結果並非最直接的 ^ ’其最能精準的表達結晶粒子之形狀、顆粒大小盘分 器應屬τεμ。如圖三所示，左圖為將樣品溶液放 圖级5網上’再將溶劑除去後，放大倍率為20Κ的ΤΕΜ 圖巾可清楚的觀察到奈綠子是明的方 ^在由右圖為將樣品以200Κ的倍率放大所得到的而圖 θ可以看到一氧化鈦粒子集結的情形以及顆粒之 16 1312794 大小、構型，由此證^中所製備出來之二氧化產； 子屬於奈米級顆粒，粒徑的分佈範圍在20〜5此茁之卩太粒 且呈現之粒子為非球形對稱（長寬比^”。 間’ (2)複合尚分子電解質液之製備 以下的固態高分子電解質液之製備則使用前述 高分散非球形對稱奈米級的二氧化鈦粒子做為摻和的租 份。以定比例的聚氧化乙烯（PE〇)與鋰鹽⑴加4)為 主體，加入不同比例之奈米級二氧化鈦粒子，觀察二4 : 鈦對於整個電解質㈣統的影響。首先將上述合成好的二 氧化鈦粒子加入適量的溶劑，（在此所使用的溶劑 THF)’利用超音波震m 5_η以上以確保粉體完全均句的 分散在溶劑當中。#與不同重量比例的電解質液 (PE0/LlC104)混摻成複合之固態高分子電解質液，並置 =加熱器加熱㈣到7代並確保其高分子（聚氧化乙稀） 完全溶解並且沒有沈殿物出現。再將所得到高分子電解質 液到入鐵㈣⑽㈣盤當中，然;後將聚摻合物放置於洪箱 中以5(TC的溫度贱將大部分的溶劑除掉，最後將系統置 於真空下將所有的溶劑與水氣通通除去，最後得到本研究 當中所使用的固態高分子電解質薄膜。每一樣品均經過長 時間於80°C下熱處理24小時後使用。 導電度量測乃使用交流阻抗儀器經等效電路分析獲取 導電度質。上述分析方法及步驟為熟悉此項技藝者所習知 之電解％再經過80C咼溫加熱並同時於1〇〇〇v/cm電場 下處理四小時再度量測導電度。以下實施例將顯示添加奈 I i ' .·.· -. 1312794 . 〜默 ... .............. ί ,； Π 米粒子之電解質（+施例8-¾¾¾導電度在高溫及電場處理 之後均大幅度提昇。 以下為七個比較例及九個實例的製備條件和導電度、 結晶度、物性的說明。 〇)比較例1-4:聚氧化乙烯（PE0)與二氧化鈦粒子 (Ti〇2) 將製備好的二氧化鈦粉體加入適量的溶劑（在此採用 )放置在超音波下震蘯4Q分鐘，再將溶液放置在加熱 授拌器加熱到60 C以上同時加入枰好重量之聚氧化乙稀 粉體，攪拌3小時後放置於真空烘箱中除去所有的溶劑與 水氣。並在真空烘箱中放置一天以確保溶劑完全除去。聚 氧化乙烯（PEO)與二氧化鈦粒子（Ti〇2)之重量比及莫爾比 如下表所示： ' 表I，氧化乙烯（PEO)與二氧化鈦粒子（Ti〇2)之重量比 重量（g) Mmole Ti02 PEO LiC104 Ti〇2 PEO LiC104 比較例1 0 0.54 0 0 2.7E-02 〇 比較例2 0.0284 0.54 0 0.36 ------ 2.7E-02 0 比較例3 0.06 0.54 0 0.75 2.7E-02 〇 比較例4 0.095 0.54 0 1.19 ------ 2.7E-02 0 c干又,ί r.”丄」〇 鬲分子電解質之結晶度與外觀的描述如下表所示： 表II聚氧化乙烯（PEO)與二氧化鈦粒子（Ti〇j高分子 電解質結晶度 1河力 18 1312794 結晶度（％) 比較例1 66.27 比較例2 54.79 比較例3 50.91 比較例4 50.9 外觀 透明無色之薄膜，有韌性不 易切割 —------ - —_____ 乳白色不透明之薄膜 乳白色不透明之薄膜 乳白色不透明之薄膜 (2 )比較例5-7氧化乙烯（PE〇)與過氯酸鹽（uci〇4) 將秤好重量之過氣酸鹽與聚氧化乙烯放置在樣品瓶當 中，加入適量的溶劑（在此採用THF)，再將溶液放置在 加熱攪拌器加熱到6 0。(：以上攪拌3小時後放置於真空烘箱 中除去所有的溶劑與水氣。並在真空烘箱中放置一天以確 保，劑完全除去。聚氧化乙烯（PE〇)與過氯酸鹽（Licl〇4)之 重量比及莫爾比如下表所示： ^111聚氧化乙浠（PEO)與過氯酸鹽（LiCl〇4)之重量比 重量（g) mmole ---- Ti02 PEO LiCIO Ti02 PEO LiC104 比較例1 --------i 0 0.54 0 0 0.027 0 比較例5 — 0 0.54 0.0285 0 0.027 0.27 比較例6 ^_ 0 0.54 0.06 0 0.027 0.56 比較例7 ^----- 0 0.54 0.095 0 0.027 0.89 南分子電解質結晶度及外觀的描述如下表所示： 表iv聚氧化乙烯（PE0)與過氣酸鹽（Licl〇4)高分子電 解質導電度與結晶度 19 1312794 . 修正1 —-- —jr-; __ 低i 貪·Ι 室溫導電 度（s/cm) 溫度處理 後導電度 結晶度（％) 外觀 比較例1 7.25E-08 7.63Ε-08 66.27 透明無色薄膜， 有韌性不易切割 比較例5 8.68E-06 8.21Ε-06 54.76 淡黃色薄膜，質 地較柔軟易彎曲 比較例6 —— 3.02E-06 3.51Ε-06 29.95 淡黃色薄膜，質 地柔軟有彈性 比較例7 3.43E-05 2.89Ε-05 7.32 淡黃色薄膜，無 彈性易破裂 (3)實施例8-19聚氧化乙烯（pE〇)過氣酸鹽（Licl〇4) 與二氧化鈦粒子（Ti02) ； -jr-： 將製備好的非球形對稱二氧化鈦（Ti〇2)粉體加入適量 的溶劑（在此採用THF)，並與秤好重量之過氯酸鹽（Licl〇4) 與聚氧化乙烯(PEO)放入已經加入二氧化鈦的樣品瓶當 中，放置在超音波下震盪4〇分鐘，再將溶液放置在加熱攪 拌器加熱至“0〇C以上’攪拌4小時後，確定聚氧化乙烯 (PEO)已輕&全浴解在溶劑當中。再將溶劑到人鐵氣龍盤 當中置於真空、烘箱以除去所有的溶劑與水氣。其溫度控制 在50 C下’並在真空供箱中放置—天以確保溶劑完全除 去。聚氧化乙烯（PEO)過氣酸鹽（⑽⑹與工氧化欽粒子 (Ti〇2)之重量比及莫爾比如下表所示. 表V聚氧化乙婦/過氣酸鹽與二氧化欽粒子間之重量 及莫爾比 20 1312794 ,b “ V.. ;;导 Η1312794 hours to 14 (4) f hours slow down, ww, go 2: 丨 1 ~ 4 〇 C speed ~ the purpose of the dish is cooked, and can get a better Zhuang 曰 type is the aqueous solution of the white , temple, this An aqueous solution of solution titanium hydroxide particles. Since we must absolutely control the moisture content in the preparation of polymers, the ring = 疋 is in an anhydrous state, so the titanium-bearing crucible required for its preparation: the cerium particles must first pass through the process of removing water. We placed the Nai: grade: oxidation = solution in a Teflon beaker 'continue to slowly remove the solvent in the oven at a low temperature (about 50 C), in order to avoid the alcohol as: The other reactants are sintered by high-temperature reaction to form coke, and adhere to the surface of the titanium dioxide crystal particles to form impurities, which affects the purity of the eight. The inventors attempted to use 8 (temperature above rc for dry water = and converted its titanium dioxide particles into brown powder. If high temperature is used during drying, the crystal form of titanium dioxide is converted from Anatase to Rutile structure. MKTC or higher). After drying, the block-shaped titanium dioxide crystals (Anatase) are ground into a fine powder by an agate mortar, and the powder is placed in an opaque sample bottle for use. This is because the nano titanium dioxide particles are passed through the UV. After the light is irradiated, there will be a difference in the bandability of the semiconductor, and the change in this is what we hope to avoid in the preparation of the electrolyte solution. The titanium dioxide crystal particles required for the mixing of the polymer electrolyte solution at this time. The powder 'is not uniform nano-particles' interface charge force to form clusters of different sizes. In the polymer composite block 15 1312794, the improved performance of reducing electrical and mechanical properties appears. Therefore, we will mix the titanium dioxide particles with the anhydrous solvent in the % prepared and use the ultra-wave oscillation energy. The product is dispersed to the smallest dispersed particles, and a solvent having a specific dielectric constant is used to strengthen the dispersed titanium dioxide particles to the nanometer level. The dispersion effect obtained by different solvents is also different because of the oxidation, the sub-solvent and the solvent. The solvent effect formed between the two will vary with the electrical constant of the cardiac agent. In addition, the particle size will change with the time of ultrasonic oscillation. Transmitted light scattering analyzer ( =LS) and a transmission electron microscope (TEM) to observe the dispersibility of the particles in the solvent and the average particle size of the particles. It is found that the dispersion and strength of the particle size vary with the time of the ultrasonic vibration. The particle size of the titanium dioxide particles is between 20~5〇nm. 5 as shown in Fig. 2: the particle distribution after 3Qmin oscillation can be divided into two two knowers, one is 20nm The other area is 5〇nm, and after the shock time of 45, the p is evenly sized into 50nm particles. It can be seen that the particle size distribution of the ultra-shock slaves is below 5Qnm. Gradual separation Separate nanoparticles. The results obtained by measuring the particle size using the DLS instrument are not the most direct. The most accurate expression of the shape of the crystal particles and the particle size disc should be τεμ. As shown in Figure 3, the left image In order to put the sample solution on the screen 5 and then remove the solvent, the magnification of 20 Κ can clearly see that the neon is a bright square. In the right picture, the sample is magnified at a magnification of 200 Κ. The obtained graph θ can be seen in the case of the aggregation of titanium oxide particles and the size and configuration of the particles 16 1312794, thereby confirming the production of the dioxide produced by the catalyst; the sub-negative particles, the distribution of the particle size The range is between 20 and 5, and the particles present are non-spherical symmetry (aspect ratio ^". (2) Preparation of composite molecular electrolyte solution The following solid polymer electrolyte solution was prepared by using the above-mentioned highly dispersed non-spherical symmetric nano-sized titanium dioxide particles as a blending rent. Taking a proportion of polyoxyethylene (PE〇) and lithium salt (1) plus 4) as the main body, different proportions of nano-sized titanium dioxide particles were added to observe the influence of titanium on the whole electrolyte (4). First, the above-mentioned synthesized titanium oxide particles are added to an appropriate amount of a solvent (solvent THF used herein) using ultrasonic waves m 5 η or more to ensure dispersion of the powder in a complete solvent. # Mixed with different weight ratio of electrolyte solution (PE0/LlC104) into a composite solid polymer electrolyte solution, juxtaposed = heater heating (four) to 7 generations and ensure that its polymer (polyethylene oxide) is completely dissolved and there is no sediment appear. Then, the obtained polymer electrolyte liquid is poured into the iron (4) (10) (4) tray, and then the poly blend is placed in a water tank to remove most of the solvent at a temperature of TC, and finally the system is placed under vacuum. All the solvents and water vapor were removed, and finally the solid polymer electrolyte film used in the study was obtained. Each sample was used after heat treatment for 24 hours at 80 ° C for a long time. Conductivity measurement was performed using AC impedance. The instrument is subjected to an equivalent circuit analysis to obtain the conductivity. The above analysis methods and steps are known to those skilled in the art to be electrolyzed and then heated by 80 C enthalpy and simultaneously treated under an electric field of 1 〇〇〇 v/cm for four hours. Conductivity is measured. The following examples will show the addition of Nai I i '...-. 1312794 . ~ 默..................... ί ,; +Example 8-3⁄43⁄43⁄4 Conductivity is greatly improved after high temperature and electric field treatment. The following are the preparation conditions and conductivity, crystallinity, and physical properties of seven comparative examples and nine examples. 〇) Comparative Example 1-4 : Polyethylene oxide (PE0) and titanium dioxide particles (Ti〇2) The prepared titanium dioxide powder is added to an appropriate amount of solvent (here used) and placed under ultrasonic waves for 4Q minutes, and then the solution is placed in a heated agitator and heated to 60 C or more while adding a good weight of polyethylene oxide. The powder was stirred for 3 hours, placed in a vacuum oven to remove all solvent and moisture, and placed in a vacuum oven for one day to ensure complete removal of the solvent. Weight ratio of polyethylene oxide (PEO) to titanium dioxide particles (Ti〇2) And Mohr are as shown in the table below: 'Table I, weight ratio of ethylene oxide (PEO) to titanium dioxide particles (Ti〇2) Weight (g) Mmole Ti02 PEO LiC104 Ti〇2 PEO LiC104 Comparative Example 1 0 0.54 0 0 2.7 E-02 〇Comparative Example 2 0.0284 0.54 0 0.36 ------ 2.7E-02 0 Comparative Example 3 0.06 0.54 0 0.75 2.7E-02 〇Comparative Example 4 0.095 0.54 0 1.19 ------ 2.7E- 02 0 c dry, ί r. "丄" 〇鬲 molecular electrolyte crystallinity and appearance are described in the following table: Table II Polyethylene oxide (PEO) and titanium dioxide particles (Ti〇j polymer electrolyte crystallinity 1 river Force 18 1312794 Crystallinity (%) Comparative Example 1 66.27 Comparative Example 2 54.79 Comparative Example 3 50.91 Comparative Example 4 50.9 Transparent and colorless film with toughness and not easy to cut ------- -______ Milky white opaque film Milky white opaque film Milky white opaque film (2) Comparative Example 5-7 oxidation Ethylene (PE〇) and perchlorate (uci〇4) Place the weighed perchlorate and polyethylene oxide in a sample vial, add the appropriate amount of solvent (here THF), and place the solution in Heat the stirrer to heat to 60. (: The above stirring was carried out for 3 hours, then placed in a vacuum oven to remove all solvent and moisture, and placed in a vacuum oven for one day to ensure complete removal of the agent. Polyethylene oxide (PE〇) and perchlorate (Licl〇4 The weight ratio and Mohr are as shown in the table below: ^111 Weight ratio of poly(ethylene oxide) (PEO) to perchlorate (LiCl〇4) Weight (g) mmole ---- Ti02 PEO LiCIO Ti02 PEO LiC104 Comparative Example 1 --------i 0 0.54 0 0 0.027 0 Comparative Example 5 - 0 0.54 0.0285 0 0.027 0.27 Comparative Example 6 ^_ 0 0.54 0.06 0 0.027 0.56 Comparative Example 7 ^----- 0 0.54 0.095 0 0.027 0.89 The crystallinity and appearance of the South Molecular Electrolyte are described in the following table: Table iv Polyethylene oxide (PE0) and pervaporate (Licl〇4) polymer electrolyte conductivity and crystallinity 19 1312794 . Amendment 1 — --jr-; __ Low i Greedy Ι Room temperature conductivity (s/cm) Conductivity crystallinity after temperature treatment (%) Appearance comparison example 7.25E-08 7.63Ε-08 66.27 Transparent colorless film, toughness Not easy to cut Comparative Example 5 8.68E-06 8.21Ε-06 54.76 Light yellow film, soft and flexible texture Comparative Example 6 —— 3.02E-06 3.51Ε-06 29.95 Light yellow film, soft and elastic texture Comparative Example 7 3.43E-05 2.89Ε-05 7.32 Light yellow film, non-elastic and easy to break (3) Example 8-19 Polyethylene oxide (pE〇) peroxy acid salt (Licl〇4) and titanium dioxide particles (Ti02); -jr-: The prepared non-spherical symmetrical titanium dioxide (Ti〇2) powder is added with an appropriate amount of solvent (here, THF is used) And with a good weight of perchlorate (Licl〇4) and polyethylene oxide (PEO) into the sample bottle that has been added to the titanium dioxide, placed under ultrasonic waves for 4 minutes, and then placed in the heating stirrer After heating to “0〇C or above” for 4 hours, it is determined that the polyethylene oxide (PEO) has been lightly and completely dissolved in the solvent. The solvent is placed in a human iron pan and placed in a vacuum, oven to remove all Solvent and moisture. The temperature is controlled at 50 C' and placed in a vacuum supply tank - to ensure complete removal of the solvent. Polyethylene oxide (PEO) peroxyacid salt ((10) (6) and Oxidation of the particles (Ti〇2) The weight ratio and Mohr are shown in the table below. Table V Polyoxyethylene / Pervaporate Chin weight ratio between the oxide particle and moire than 20 1312794, b "V .. ;; guide Η
Wt% Wt% 重量比 莫爾比 THF = 75ml Li比 例 Ti比 例 Ti〇2 PEO L1CIO4 Ti〇2 PEO LiC104 實施例 8 5 5 0.0299 0.54 0.0284 1.7 45.9 1 實施例 9 10 5 0.0316 0.54 0.06 0.7 21.8 1 實施例 10 15 5 0.0334 0.54 0.0953 0.5 13.7 1 實施例 11 18 5 0.0365 0.54 0.113 0.4 11.0 1 實施例 12 5 10 0.0632 0.54 0.0284 3 45.9 1 實施例 13 10 10 0.0667 0.54 0.06 1.5 21.8 1 實施例 14 15 10 0.0706 0.54 0.0953 1 13.7 1 實施例 15 18 10 0.0746 0.54 0.113 0.8 11.0 1 實施例 16 5 15 0.1003 0.54 0.0284 4.7 45.9 1 實施例 17 10 15 0.1059 0.54 0.06 2.3 21.8 1 21 1312794 --^— 實施例 V.1 ： 18 15 15 -----1 實施例 19 18 15 0.1121 13.7 1 11.0 1 0.54 高分子電解質結晶度及外觀描述如下- 表VI聚氧化乙烯/過氯酸鹽與二氧化鈦粒:複合高< 子電解質導電度與結晶度 ------ 室溫導 電度 (S/cm2) 處理後 導電度 DSC 結晶度 (% ) — ------ 外觀 ------ 實施例 8 1.37E-5 2.36E-4 — 47.07 樣品質地較硬的乳白色 片狀組合明顯的結晶的 紋路 ____ 實施例 9 5.38E-5 9.23E-4 32.8 樣品表面較平整的白色 薄膜仍可看到些微的結 晶 實施例 10 2.16E-4 4.87E-3 11.6 樣品表面平整的白色薄 膜表面非常光滑 實施例 11 5.58E-4 8.96E-3 5.1 樣品表面平 膜表面非常光滑呈現透 明 實施例 12 1.02E-5 2.21E-4 52.33 樣品平整的 有些微的彈性但仍不了 22 1312794 實施例 13 1.20E-5 3.54E-4 32.22 實施例 14 1.63E-5 5.38E-4 16.25 實施例 15 2.01E-5 8.38E-4 0.0 實施例 16 1.33E-5 3.72E-4 47.8 實施例 17 4.89E-5 7.69E-4 36.2 實施例 18 2.96E-5 3.56E-4 10.6 實施例 19 1.16E-4 5.84E-3 0.0 拉伸 實施例說明 平整的白色薄膜，有彈 性可拉伸 —----------- 有顆粒狀物在樣品表 面，失去彈性，拉伸不 易 有顆粒狀物在樣品表 面，失去彈性，拉伸不 易 膜且膜呈較硬質地的片 狀 樣品表面較平整的白色 薄膜且膜呈柔軟的片狀 地柔軟呈現不透明白色 比較例1-4中的樣品未加入鋰鹽，在此pE〇之結晶度 受到Ti〇2增加而逐漸下降，但仍保有〜5〇%的結晶區塊二 系統當中，也可以說二氧化鈦的加入有可能影響pE〇結晶 區塊的排列，但二者的作用力並不明顯。 比較例5-7中未加入二备 一孔化鈦，在此PEO之結晶度受 23 1312794 · ； 1 - I 二”會 到鹽類增加而快速下降，當含量增加至15%Licl04 時，結晶度只剩下7.32%，而當增加至15%Licl〇4時幾乎 無結晶。其變化較二氧化鈦為鉅大，雖此樣品（比較例乃 至’服導電度為最咼，但其機械性能甚差，不易拉伸並無彈 性且易破裂。且此樣品只有在超過熔點以上導電度才會迅 速上昇。此結果與文獻上觀察之結論相符。 實細*例8 -19則為摻合不同比例之Lic丨％與之結 果導電度和結晶程度係列於表VI中。其變溫導電度由 表VI中可看到5%Ti〇2的樣品（實施例8_u)在變溫下的導 電行為均較未加入Ti〇2的樣品優良，尤其增加鹽類濃度至 15%時（實施例ίο)，室溫導電度可達5xl〇-3s/cm之值，此 樣品表面平整、光滑具良好的機械性質，比含有同樣鹽類 不含一氧化鈦的比較例7要更為優秀。值得注意的是此樣 °°的導電度在超過Tm時並不似比較例5有著快速上升的 趨勢’亦反應了其低級品之特性。 由表IV中可見到i〇〇/〇Ti〇2的樣品（實施例12_15)在變 溫情況下的導電行為’不同鹽含量的差異較不如少量Ti〇2 來的明顯。其結晶度雖亦會隨著鹽類含量的增高而快速降 低但導電度似乎並不較未添加Ti〇2時（比較例6)有大幅 度改進的傾向。這可能是Ti〇2與多量的LiCl〇4形成錯合 物，減低可導電的離子數，在實施例13，及14中更可見到 粒狀物質（析出鹽類）出現表面。 由表1V中可見15%Ti〇2的樣品（實施例16-19)。與前 面兩系列（50/。、i〇〇/〇Ti〇2)最大的不同是導電度在熔點時呈 24 *'·** ·"···· ^ 9. 年 /1 g j 樣品中可以導電的離子 1312794 現快速增高的趨勢 是存在於非a日&二了 1㈣導電的離子 速導電。而:： 中，隨著PE〇結晶層的融解而加 兄等玉。而大部份的鋰離子 體的導電性盥去* I、Tl〇2形成錯合物體。其整 均較差。 人Tl02的1 5%LiC1〇4樣品相比，導電度 會快連~ 添加少量加#5%)時，其導電性能 加’而且保持良好的機械性能。其主要的原因是 類解離料减鈦與鹽類共同的作用導致結晶度降低，鹽 解離&升，進而使導電度明顯的增加。纟4G〜6〇t之門 的快速提升現象為其主要的特點。但超過咖叫時，: 米粒子與鹽類相結合形成錯合體，阻礙可導電的離子數， f剩餘之未錯合的UC1〇4導電機構則與未添加Ti〇2的樣 品相似’皆在非結晶的pE〇中傳導。此組樣 優良，但導電性質不佳。 寶 更明顯的是樣品再經過8〇〇C高溫及1〇〇〇v/cm電場處 理四小時後添加奈米粒子之電解質（實施例8·19)導電度均 較處理之前大幅度提昇，最大可提升15倍（實施例^及 19)。然而在比較例中未加入非球形奈米粒子時則未見如此 顯見之提昇現象。此乃因非球形對稱奈米粒其介電常數達 到183，經加溫處理或在充放電循環電場誘導下非球狀對 稱的奈米粒子在能產生順向的排列，使高分子電解質之介 電常數逐漸提高，進而使導電度大幅提昇一至二個級數。 提昇之導電度有助於減低元件内阻’抗提昇元件之低溫放 電物性，及延長元件壽命。此一具有非球形對稱奈米粒子 25 1312794 /'； * I Ον 之複合高分子雷鮭餅^ .,... 解貝材貝其製備及後續電場下高溫處理 法具有，述之優點具有實用之價值。 万 上，然立肩域技藝者，本發明雖以一較佳實例闕明如 神虛ιί圍内所I以限定本發明精神。在不脫離本發明之精 申言主專之修改與類似的安排，均應包含在下述之 :1耗内’這樣的範圍應該與覆蓋在所有修改與類 :、、’“冓的最寬廣的詮釋一致。因此’闡明如上的本發明一 實幻可用來鑑別不脫離本發明之精神與範圍内所作 之各種改變。 【圖式簡單說明】 圖一所示為顯示本發明存於本系統當中螯人 (cheating )和架# ( bridging )㈣型式中間產物之示二 圖0 。 不為顯不本發明之奈米級粒子粒徑分佈示意 圖三所示為顯示本發明之將樣品溶液放置在銅網上 再將溶劑除去後，不同放大倍率的奈米粒子簡圖譜 【主要元件符號說明】 益 ό、 26Wt% Wt% weight ratio molar ratio THF = 75 ml Li ratio Ti ratio Ti〇2 PEO L1CIO4 Ti〇2 PEO LiC104 Example 8 5 5 0.0299 0.54 0.0284 1.7 45.9 1 Example 9 10 5 0.0316 0.54 0.06 0.7 21.8 1 Example 10 15 5 0.0334 0.54 0.0953 0.5 13.7 1 Example 11 18 5 0.0365 0.54 0.113 0.4 11.0 1 Example 12 5 10 0.0632 0.54 0.0284 3 45.9 1 Example 13 10 10 0.0667 0.54 0.06 1.5 21.8 1 Example 14 15 10 0.0706 0.54 0.0953 1 13.7 1 Example 15 18 10 0.0746 0.54 0.113 0.8 11.0 1 Example 16 5 15 0.1003 0.54 0.0284 4.7 45.9 1 Example 17 10 15 0.1059 0.54 0.06 2.3 21.8 1 21 1312794 --^ - Example V.1 : 18 15 15 -----1 Example 19 18 15 0.1121 13.7 1 11.0 1 0.54 Polymer electrolyte crystallinity and appearance are described as follows - Table VI Polyethylene oxide / perchlorate and titanium dioxide particles: composite high < sub-electrolyte conductivity And crystallinity ------ room temperature conductivity (S / cm2) after treatment DSC crystallinity (%) - ------ appearance ------ Example 8 1.37E-5 2.36 E-4 — 47.07 Sample texture harder milky white tablets Combining Significantly Crystallized Grains ____ Example 9 5.38E-5 9.23E-4 32.8 A slightly white film on the surface of the sample can still see some slight crystallization Example 10 2.16E-4 4.87E-3 11.6 The surface of the sample is flat The white film surface is very smooth. Example 11 5.58E-4 8.96E-3 5.1 The surface of the sample is flat and the surface is very smooth and transparent. Example 12 1.02E-5 2.21E-4 52.33 The sample is flat and slightly elastic but still not 22 1312794 Example 13 1.20E-5 3.54E-4 32.22 Example 14 1.63E-5 5.38E-4 16.25 Example 15 2.01E-5 8.38E-4 0.0 Example 16 1.33E-5 3.72E-4 47.8 Example 17 4.89E-5 7.69E-4 36.2 Example 18 2.96E-5 3.56E-4 10.6 Example 19 1.16E-4 5.84E-3 0.0 Tensile Example Description Flat white film, elastically stretchable - ----------- There are particles on the surface of the sample, losing elasticity, stretching is not easy to have particles on the surface of the sample, losing elasticity, stretching is not easy to film and the film is a harder sheet sample A white film with a flat surface and a soft sheet in the form of a soft sheet showing opaque white. Comparative Examples 1-4 The sample is not added with lithium salt. The crystallinity of pE〇 is gradually decreased by the increase of Ti〇2, but still retains ~5〇% of the crystallization block II system. It can also be said that the addition of titanium dioxide may affect the pE〇 crystal. The arrangement of the blocks, but the force of the two is not obvious. In Comparative Example 5-7, the titanium dioxide was not added, and the crystallinity of the PEO was affected by 23 1312794 · ; 1 - I II", which increased rapidly when the salt increased, and crystallized when the content increased to 15% LiCl04. The degree is only 7.32%, and when it is increased to 15% Licl〇4, there is almost no crystal. The change is much larger than that of titanium dioxide. Although the sample (comparative or even the 'electrical conductivity is the most flawed, its mechanical properties are very poor, It is not easy to stretch, is not elastic, and is easily broken. This sample will rise rapidly only when it exceeds the melting point. This result is consistent with the conclusions observed in the literature. Really fine*Example 8-19 is a blend of different ratios of Lic丨% and the resulting conductivity and crystallization degree are listed in Table VI. The temperature-varying conductivity is shown in Table VI. The sample with 5% Ti〇2 (Example 8_u) has a lower conduction behavior at temperatures than those without Ti. The sample of 〇2 is excellent, especially when the salt concentration is increased to 15% (Example ίο), the room temperature conductivity is up to 5xl 〇 -3s/cm, and the surface of the sample is smooth and smooth with good mechanical properties. Comparative Example 7 in which the salt does not contain titanium oxide is more excellent. Note that the conductivity of ° ° ° does not appear to have a tendency to rise rapidly in Comparative Example 5 when it exceeds Tm'. It also reflects the characteristics of its lower grade. It can be seen from Table IV that i〇〇/〇Ti〇2 The conductivity behavior of the sample (Example 12_15) under variable temperature conditions is different from that of a small amount of Ti〇2. The crystallinity of the sample is also rapidly decreased as the salt content increases, but the conductivity seems to be There is no tendency to greatly improve when Ti〇2 is not added (Comparative Example 6). This may be that Ti〇2 forms a complex with a large amount of LiCl〇4, reducing the number of conductive ions, in Example 13, and The surface of the particulate matter (precipitated salt) was more visible in Fig. 14. A sample of 15% Ti〇2 was observed in Table 1V (Examples 16-19). The previous two series (50/., i〇〇/〇) The biggest difference of Ti〇2) is that the conductivity is 24*'·** at the melting point. 9. Year/1 gj The ion that can conduct electricity in the sample 1312794 is now increasing rapidly. a day & two 1 (four) conductive ion velocity conduction. And::, with the melting of PE 〇 crystal layer, brother, etc. Most of the lithium ion conductors have a conductivity of I*I and Tl〇2 to form a complex body. The overall average is poor. Compared with the 15% LiC1〇4 sample of human Tl02, the conductivity will be fast. When a small amount of #5% is added, the conductivity is increased and the mechanical properties are maintained. The main reason is that the decomposed material reduces the combination of titanium and salt, resulting in a decrease in crystallinity, salt dissociation & liter, and thus conductivity. The degree of increase is obviously increased. The rapid lifting phenomenon of 纟4G~6〇t is its main feature. However, when it exceeds the coffee, the rice particles and the salt combine to form a mismatch, which hinders the number of conductive ions, f remaining The uninterrupted UC1〇4 conductive mechanism is similar to the sample without Ti〇2, and both are conducted in the amorphous pE〇. This group is excellent but has poor electrical conductivity. It is more obvious that the conductivity of the sample is increased by 8 〇〇C high temperature and 1 〇〇〇v/cm electric field for four hours. The conductivity of the electrolyte is increased (Example 8·19). Can be increased by 15 times (Examples ^ and 19). However, in the comparative example, when the non-spherical nanoparticles were not added, no such obvious improvement was observed. This is because the non-spherical symmetric nano-particles have a dielectric constant of 183. The non-spherical symmetry of the nanoparticles can be produced in a forward direction by heating or induced by a charge-discharge cycle electric field, so that the dielectric electrolyte is dielectrically charged. The constant is gradually increased, which in turn increases the conductivity by one to two steps. The increased conductivity helps to reduce the internal resistance of the component, the low temperature discharge properties of the lifting component, and the life of the component. The composite polymer scorpion cake with non-spherical symmetrical nano-particles 25 1312794 /'; * I Ον ^,... The preparation of the shellfish and the subsequent high-temperature treatment under the electric field have the practical advantages of the advantages described. . In the present invention, the present invention has a preferred embodiment, such as a singularity, to limit the spirit of the present invention. Modifications and similar arrangements that do not depart from the essence of the invention should be included in the following: 1 consumption within such a range should be covered with the broadest of all modifications and classes:, ' It is to be understood that the present invention may be used to identify various modifications within the spirit and scope of the present invention. [Simplified Schematic] Figure 1 shows the present invention in the present system. Figure 2 shows the particle size distribution of the nano-particles of the present invention. The third embodiment shows the sample solution placed on the copper mesh. Nanoparticles at different magnifications after removal of the solvent. [Main component symbol description] 益ό, 26