200408154 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種鋰聚合物電池及其製造方法。更詳而 言之，本發明係關於一種在高結晶性石墨粉末的表面附著 低結晶性碳材料之石墨材料粉末二種以上所構成的複合碳 材料粉末，使用此粉末作為活性物質之負極的鋰聚合物電 池及其製造方法。 兒 【先前技術】 近年，已開發出利用鋰離子之吸附-釋放過程的碳材料或 導電性高分子等的基質材料，以取代利用金屬鋰或其合金 成為負極。藉此，利用金屬鋰或其合金時所產生之傳導光 的生成在原理上不會發生，致電池内部之短路問題急劇減 >。尤其，碳材料係比其他的材料在鋰的吸附_釋出電位近 似於鋰的析出-溶解電位還接近乃為已知。其中，石墨材材 係理淪上對於碳原子6個以鋰原子丨個的比率在其結晶格子 中杈入鋰。因此，石墨材料係每單位重量及單位體積具有 咼容量之碳材料。進而，石墨材料係鋰之插入_脫離的電位 很平坦且化學上安定，故使用其，可得到回收性良好的良 好電池。 例如在 J· Electfochem· Soc·，Vol· 137, 2009 (1990)、特開平 4 1 15457唬公報、特開平4-1 15458號公報、特開平4_237971 號a報中，係使用石墨系碳材料於負極活性物質之電池， 又“在特開平4-368778號公報、特開平5-28996號公報、特 開平5 1 14421號公報等中係使用已表面處理之石墨系碳材 87955 200408154 料於負極活性物質之電池。 石墨系碳材料係藉由以碳酸乙晞酯（EC)作為主體之有機 電解液，而得到略近似理論容量之放電容量。又，其充放 電之電位略比鋰之溶解_析出的電位還高，且非常平坦。因 此，使用石墨系碳材料於負極活性物質而製作電池時，可 貫現问谷f且電池電壓之平坦性高的二次電池，可達成電 池之高容量化。 但’石材料因結晶性高、仍會引起有機電解液之 分解的問題點。例如，有機電解液用溶劑即碳酸丙職㈣ 係其電位範圍寬、凝固點低（_7〇〇c)及化學安定性高，故廣 之使用來作為鋰二次電池用之電解液的溶劑。但，使用石 墨系碳材料於負極活性物f時，^之分解反應會很顯著， 正α ίο/。之pc存在於電解液，由石墨系碳材料所構成之負 極無法充放電已報告於L Eleetn)ehem SGe，趾142，⑽ (1995)。 ’ 、其解決對策已提出有：⑴在電解液中加人如碳酸乙烯醋 《⑽劑，在負極活性物質即石墨系碳材料上積極地形成 皮膜，藉其皮膜抑制其後之電解液的分解之方法、或、⑺ 以低結晶性碳材料覆蓋高結晶性石墨系碳材料之表面的方 法。後者之万法’係可得到一複合石墨材料，其係兼備： 高結晶性石墨系碳材料擁有之合 ' 卞禪回谷ϊ的特徵、與、低結晶 性碳材料之特徵即無電解液之選擇性。 近年，以使用液體之電解液的電池之耐漏液性、高安定 性、提高長期保存性4目L彳f具有高離子傳導性之 87955 200408154 離子傳導性聚合物的各種研究。離子傳導性聚合物目前已 提出以環氧乙燒作為基本單元之均聚合物或共聚合物的直 鍵狀高分子、網狀交聯高分子或梳型高分子等差不多已被 實用化。 有關使用上述離子傳導性聚合物之電池，已被廣泛記載 糸專利文獻等。例如：Armand等人之美國專利第4,303,748 號或North之美國專利第4,589，197號及11〇〇1)^等人之美國 專利第4,547,440號等之專利文獻所記載的電池。 可舉例作為此等電池之特徵者乃於具有聚醚構造之高分 子材料中含有已溶解電解質鹽之溶液，使用含有此溶液之 離子傳導性聚合物。此等離子傳導性聚合物因在室溫以下 之離子傳導度低，故特別無法實現攜帶電子機台之驅動用 電源或記憶支授電源用的電池所要求之小型輕量且高能量 密度化。 匕里 疋，杈上述離子傳導性聚合物更進一步謀求提高南 傳導性之方法，已提出··將單體、與由有機溶劑(尤其是 或pc等之高介電率有機溶劑）與電解質鹽所構成的命每 混合、再使單體聚合之方法。藉其方法，而將電解二 於聚合物網絡巾，可得到保持著固體狀態“膠狀p 電解質（以下稱為化學交聯凝膠）。 χ p 化學交聯凝膠係電解液之保持力高， 一 1ππ〇Γ, ^ , 入 ’成為高溫G歹 100C左右)亦不會溶融者，就異常時之液戌漏 ’很有效 '然而，在低溫下之性能差，為交聯W ; 子傳導性聚合物之前驅物的開始劑會人兩 力方 曰' 伃万；電池中， 87955 154 電池性能劣彳p ι 力化寺，尚待解決之課題仍多。 另外，在特表平8-5074〇7號公報 丙烯-¾俋# 促出種使7T氣 丙年-偏氣乙晞之共聚合物物氧 膠電解该r α . 1禾待私解履足凝 ' 下，稱為物理交聯凝膠）。 此型態之凝膠係形成電池元件後，注入電解液 先、而暫時燦融，藉a σ 液體之^、、 ㈣成時。因此，擁有可以與使用 :广夜的鋰離子電池的製造方法相 仃製造等的優點。 万忐瓜進 物理交聯凝膠係在言、、w 液触m A 在至/皿下成為凝膠狀’可期待某程度之 说目豆戌漏抑制的效果。但， 西 又又 熔 成為，成為凝膠狀者會 n然法保持凝膠的狀態，故 抑制的藶ρ ϋ 斗、 〆、吊時 < 夜體洩漏 w审」的觀點，並不充分。基於如 的效果可亦八如咎 、又狀，兄，液體洩漏抑制 无刀，、月待且使用化學交聯凝膠的高性 物電池乃很強烈被期待。 牝〈鋰永合 【發明内容】 乂1:::目的在於提供-種高性能鐘聚合物電池，其係 *吊時，即使在電池之溫度會上昇之情形τ，亦不备 幻起電解液之液體淺漏，且， ' ^ 具有可匹敵於鋰離子兩士、 負荷特性、溫度特性、能量密度者。 " 如此一來，若依本發明，可提供 係具備正極、含有由碳材料η合物電池’其 ^, 冓成足負極活性物質之 負極、使用化學交聯凝膠之電 κ 、人丄 卿貝，石反材料粉末係包各： 万;南結晶性石墨粉末之表面附著低結晶性碳 。 互異之物性值的至少2種麵以> 、，且具有 以上《複合石墨材料粉末的混 87955 200408154 合物。 進步右依本發明，提供一種鋰聚合物電池之製造方 法：、係匕括如下步驟：於負極係含有-於高結晶性石墨 ^末〈表面附著低結晶性碳材料且具有互異之物性值的至 種類以上〈複合石墨材料粉末以作為負極活性物質之 “才料•刀末’而使化學交聯之前驅物含浸於負極之步，驟； 使前驅物凝膠化而得到電解質之步驟。 發明之實施形態 久口石土材料&末作為負極活性物質很優異，但，藉表 面之低結晶性碳材料，古么士曰 ” 十冋、、、口日曰性石墨粉末（以下亦稱為石墨 》）原本具有之潤滑性會被阻礙。因此，有時充殖性声， ί法得到高密度之負極。有關此充填性，本發明之發明人200408154 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a lithium polymer battery and a method for manufacturing the same. More specifically, the present invention relates to a composite carbon material powder composed of two or more graphite material powders having a low-crystalline carbon material adhered to the surface of a highly crystalline graphite powder, and the powder is used as lithium for the negative electrode of an active material. Polymer battery and manufacturing method thereof. [Prior art] In recent years, carbon materials or conductive polymers using lithium ion adsorption-release processes have been developed to replace the use of metallic lithium or its alloy as the negative electrode. As a result, the generation of the conducted light generated when using lithium metal or its alloy does not occur in principle, and the short circuit problem inside the battery is drastically reduced >. In particular, it is known that carbon materials are closer to the adsorption-release potential of lithium than the precipitation-dissolution potential of lithium than other materials. Among them, the graphite material is based on lithium in the crystal lattice of 6 carbon atoms at a ratio of lithium atoms. Therefore, the graphite material is a carbon material having a plutonium capacity per unit weight and volume. Furthermore, the graphite material-based lithium has a flat insertion and extraction potential and is chemically stable. Therefore, a good battery with good recyclability can be obtained by using it. For example, in J · Electfochem · Soc ·, Vol · 137, 2009 (1990), Japanese Patent Application Laid-Open No. 4 1 15457, Japanese Patent Application Laid-Open No. 4-1 15458, Japanese Patent Application Laid-Open No. 4_237971a, graphite-based carbon materials are used in A negative electrode active material battery is also a surface-treated graphite-based carbon material used in Japanese Unexamined Patent Publication No. 4-368778, Japanese Unexamined Patent Publication No. 5-28996, and Japanese Unexamined Patent Publication No. 5 1 14421. 87055 200408154 Material batteries. Graphite-based carbon materials use an organic electrolyte with ethyl acetate (EC) as the main body to obtain a discharge capacity that is approximately the theoretical capacity. In addition, its charge and discharge potential is slightly more than that of lithium. The potential is high and very flat. Therefore, when a graphite-based carbon material is used as a negative electrode active material to make a battery, a secondary battery with a high flatness of the battery voltage can be realized, and a high capacity of the battery can be achieved. However, due to the high crystallinity of the stone material, the problem of decomposition of the organic electrolyte is still caused. For example, the solvent for organic electrolytes, namely propyl carbonate, has a wide potential range, a low freezing point (_700), and It has high stability, so it is widely used as a solvent for the electrolyte of lithium secondary batteries. However, when a graphite-based carbon material is used for the negative electrode active material f, the decomposition reaction of ^ will be significant, positive α ίο /. PC exists in the electrolyte, and the negative electrode composed of graphite-based carbon materials cannot be charged and discharged. It has been reported in L Eleetn) ehem SGe, Toe 142, ⑽ (1995). ', the solution has been proposed: ⑴ in the electrolyte For example, a method such as ethylene carbonate vinegar, a method of actively forming a film on the negative electrode active material, that is, a graphite-based carbon material, and using the film to suppress the subsequent decomposition of the electrolytic solution, or ⑺ cover the high crystal with a low-crystalline carbon material Method for the surface of carbonaceous graphite-based carbon materials. The latter method can obtain a composite graphite material, which has both: a combination of highly crystalline graphite-based carbon materials' characteristics, and low crystallinity The characteristic of non-volatile carbon materials is that it has no electrolyte selectivity. In recent years, batteries using liquid electrolytes have leak resistance, high stability, and improved long-term storage properties. 4 mesh L 彳 f has high ion conductivity 87955 200408154. Various studies of conductive polymers. Ionic conductive polymers have been proposed as straight-chain polymers, network-crosslinked polymers or comb polymers with homopolymers or copolymers based on ethylene oxide. Almost all have been put into practical use. Batteries using the above-mentioned ion-conducting polymers have been widely documented. Patent documents, etc. For example, US Patent No. 4,303,748 by Armand et al. Or US Patent Nos. 4,589,197 and 11 of North. The battery described in U.S. Patent No. 4,547,440 and others. An example of the characteristics of these batteries is a solution containing a dissolved electrolyte salt in a polymer material having a polyether structure, and an ion conductive polymer containing the solution is used. Since these ion conductive polymers have low ionic conductivity below room temperature, it is particularly difficult to achieve the compact, lightweight, and high energy density required for batteries for driving power supplies or memory power supplies for carrying electronic equipment. The above-mentioned ion-conducting polymer further seeks a method for improving the conductivity of the south. A monomer, an organic solvent (especially a high-permittivity organic solvent such as a pc), and an electrolyte salt have been proposed. The method is to mix the monomers and polymerize the monomers. By this method, electrolysis of the polymer network towel can obtain a "gel-like p electrolyte (hereinafter referred to as a chemically crosslinked gel) in a solid state. Χ p chemically crosslinked gel-based electrolyte has a high holding power. ， 1ππ〇Γ, ^, into 'becoming high temperature G 歹 100C) will not melt, the liquid leakage when abnormal,' very effective 'However, the performance at low temperature is poor, it is cross-linked W; The starting agent of the precursors of polymer polymers will be a combination of the two: 伃 ；; in the battery, 87955 154 battery performance is poor 彳 Lihua Temple, there are still many issues to be resolved. In addition, in the special table flat 8- Proclamation No. 5074〇7 Propylene-¾ 俋 # promotes the electrolysis of the oxygen polymer which is a copolymer of 7T gas propane-biased acetam to the r α. Glue). This type of gel system is formed into the battery element, and then the electrolyte is injected first, but temporarily melts, so when a σ liquid is used, it has a lithium ion battery that can be used with: Guangye The manufacturing method is based on the advantages of manufacturing, etc. Wan Zhiquan physical cross-linking gel is described in the above, w liquid contact m A becomes gelatinous under the condition of 'dish'. It can be expected to have a certain degree of effect of suppressing the leakage of the soybeans. However, it will melt again, and those who become gelatinous will keep the gel state, so it will be suppressed. The view of 苈 ρ ϋ 斗 〆, 时, hanging time < night body leak w trial '' is not sufficient. Based on the effects of this, there are many blame, shape, and high-performance batteries that use liquid-crosslinking gels to prevent liquid leakage without a knife. They are also highly expected.牝 <Lithium Yonghe [Content of the invention] 乂 1 ::: The purpose is to provide a kind of high-performance clock polymer battery, which is designed to suspend even when the temperature of the battery will rise τ, it is not ready to start the electrolyte. The liquid leaks shallowly, and has a load characteristic, temperature characteristic, and energy density that are comparable to lithium ions. " In this way, according to the present invention, it is possible to provide a negative electrode including a positive electrode, a carbon material containing a η-composite of a carbon material, a negative electrode which is a sufficient negative electrode active material, an electric current using a chemically crosslinked gel, and a human Qin Bei, Shi Anti-Material powders include: Wan; South surface of crystalline graphite powder adheres to low crystalline carbon. At least two kinds of mutually different physical property values are > and have the above-mentioned mixture of composite graphite material powder 87955 200408154. According to the present invention, a method for manufacturing a lithium polymer battery is provided. The method includes the following steps: the negative electrode system contains-on the highly crystalline graphite ^ low-crystalline carbon material attached to the surface and has mutually different physical properties. To the above types <the step of impregnating the precursor of chemical cross-linking with the negative electrode active material as the "active material and knife" of the negative electrode active material; the step of gelling the precursor to obtain the electrolyte. The embodiment of the invention The long mouth stone material & is excellent as a negative electrode active material, but by virtue of the surface of the low-crystalline carbon material, Gu Mo Shi said "Shiyao," and "Kouri" graphite powder (hereinafter also referred to as "Graphite") the lubricity originally possessed will be hindered. Therefore, sometimes it is full-featured, and high-density negative electrodes are obtained. Regarding this filling property, the inventor of the present invention
等經洋細研究妹果 I 菩的.§人 果|現料性受被覆比、或芯材之種類 寺勺I δ石墨材料粉末的物性質影響很大。 進而，就上述觀點，本癸明 性佶 、 月乏务明人寺亦發現藉使用物 而#兴以上複合石墨材料粉末作為負極活性物質 。有、學叉聯凝膠之前驅物硬化時，有效率地進行交聯 進行交聯的理由係如下般推測。石墨粉末係在 :、阻:：消耗自起始劑受熱或υν等方法所產的自由基 里Iφ W 、 人何村被覆表面，可抑制石 之自由基的消耗，所產生之自由基可有效率 地使用於聚合反應。 I文+ 在本發明中所謂含有物性值 合石墨材料粉末，係入右s i 種類以上的複 才枓知末係吕有至少作為主活性物質之複合石墨 87955 -10- 200408154 材料知末、與、用以提高其充填性之複合石墨材料粉末的2 種類。藉由含有如此之至少2種類以上之複合石墨材料粉末 的負極，可製作高容量密度、且負荷特性優之高性 、Λτ兩、！ 肥W、』一 /人電池0 複合石墨材料粉末係粉末之集合體，若嚴格言之，要得 到芫全均—之粉末的集合體乃很難，故具有粒子一個一個 之物性值、與作為粒子之集合體的物性值（平均值）。在本笋 明中所謂2種類以上，係作為後者之集合體而互異之物值的 複合石墨材料粉末存在2種類以上。此處，所謂物性值可舉 例：結晶性（面間隔、結晶格大小等）、比表面積、粒度分; 、被覆比、拉曼強度比、真密度、體密度、純度、形狀等。 在本發明中，宜使用被覆比為互異之2種類以上的複合石 墨：料粉末。具體上，所謂被覆比互異係低結晶性碳二料 4里/回結晶性石墨粉末之量+低結晶性碳材料之量）的平 均值（以下稱為被覆比）為相異。藉由使被覆比相異，可製作 更南容量密度且高性能的二次電池。 又’所謂被覆比並非粒子一個一個的值，而是作為複合 石墨材料粉末之集合體的值即平均值。此值係由製造 中之石墨粉末的重量、與最終所得到之複合石墨材料粉末 的重量變化而算出。 77 〜0.3 晶邵 對於 被覆比大者的複合石墨材料粉末之被覆比宜在〇·们 的範圍内，更宜為0.1〜0.25。若被覆比大於〇3，低結 分會過多，充放電容量變低，故不佳。若未達〇，们， 電解液之分解的控制效果會變低，故不佳。 87955 -11- 200408154 又’被覆比小者的複合石墨材料粉末之被覆比宜在〇1以 下’更宜為G.G1〜(Mo，最宜為g.hm，若未達〇別， 雖可抑制上述之聚合的阻礙因素，卻不充分，〖，若大於 0.1之被覆比’因很難得到性能優且高充填密度之負極，^ 不佳。 進而’被覆比小之複合石墨材料粉末的量斜被覆比大之 複合石墨材料粉末的量’就重量，宜為50%以下，更宜 為10〜30%左右。若添加量過多，其材料之性質會支配， 要抑制阻礙聚合的因素之效果無法充分得到，材料本身會 =向’因電解液之渗人會變差等之理由，⑥負荷特性等會 變差。又，若添加之量不足’會產生無法充分得到充填性 提昇之效果的問題。 又，藉改變石墨粉末之種類以取代使被覆比相異，亦可 得到高容量密度且高性能之電池。使用以又射線繞射、拉曼 分光法、真蜜度等所定義之結晶性評估為相異的2種類以I 石T粕末，即使以相同的被覆比被覆低結晶性碳材料時， 依石墨粉末之種類而充填性相異乃很明顯。此係依乂射線繞 射法等之評估方法無法判斷的微細組織、以及、依來自芯 材之形狀的衩合石墨材料粉末形狀、粒徑之均衡等的差異 ’而推論於充填性會產生差別。 石墨粉末相異時之被覆比並無特別限定，但為更提高充 填性，被覆比大之複合石墨材料粉末的被覆比宜為0.03〜 0·3，被覆比小之複合石墨材料粉末的複比宜為〇〇1〜〇1〇 。更佳之後者的被覆比為0 01〜0 05。 87955 -12 - 200408154 被復比小之複合石墨材料粉末的量對被覆比大之複 合石墨材料粉末的量，就重量比，宜為5〇%以下，更宜為 10〜30%左右。若添加量過多，其材料之性質會支配，要 制阻％聚合的因素之效果無法充分得到，材料本身會定 " 因兒解液之滲入會變差等之理由，而負荷特性等會變 ，若添加之量不足，會產生無法充分得到充填性提 昇之效果的問題。 /、 人本务月中，係使用塊狀之人造石墨作為被覆比大之複 费石I材料粉末的石墨粉末，使用天然石墨作粉末作為被 旻匕】之杈合石墨材料粉末的石墨粉末時，可得良好之么士 果。 、、、口 在本秦明中’係足義所謂壓縮比之參數m合石墨 f料‘末〈物性作為表示充填性左右的指標。此處，所謂 蜃縮比係於成為對象之複合石墨材料粉末中加人7·5重量 刀（相對於不旻合石墨材料粉末1〇〇重量份）之下（聚偏氣 乍為黏結劑’與溶劑混合所得到之漿液，再塗布成銅 消[以線壓300 kg/em沖壓時之厚度變化。具體上係以如 壓縮比=沖壓後之塗膜的厚度/沖壓前之塗膜厚度 ^ C v製作’至膜時之塗膜密度亦很重要。亦即，沖屬 R塗膜密度愈高，進—步壓縮比愈小，愈可得到高㈣ 〈負：。壓縮比即使非常小，沖壓前之塗膜密度亦太小日; 古為：到高密度之負極，若進行沖壓，有時易引起石墨老 《疋向，變成負荷特性差之負極。又，即使沖壓前之2 87955 -13 - IΜ 嗅歡度為非常高的材料，若壓縮比 ^ 量密度之負極，故不佳。 ，因無法得到高能 在本1明中’為使沖壓前之 壓縮比為〇.4〜〇.7，_ 版山度為0.7g/⑽3以上，Et al. Carefully studied the young girl fruit I, Bo. §Human fruit | Preservability is greatly affected by the physical properties of the coating ratio, or the type of core material. Furthermore, in view of the above, Bengui Mingxue and Yuewuwu Renren Temple also found that the use of composite materials and xing above composite graphite material powder as a negative electrode active material. When the precursor is hardened, the cross-linking gel is efficiently cross-linked. The reason for the cross-linking is estimated as follows. The graphite powder is consumed in the free radicals produced by methods such as heating of the initiator or υν, and the surface covered by Ren Hecun, which can suppress the consumption of free radicals in the stone. Efficiently used for polymerization. I text + In the present invention, the so-called graphite powder containing physical properties is compounded with more than the right si species. It is known that there are composite graphites that are at least the main active material. 87955 -10- 200408154 Material knowledge, and, 2 types of composite graphite material powder to improve its filling properties. By using such a negative electrode containing at least two types of composite graphite material powder, a high-capacity, high-capacity, Λτ, and two having high capacity density can be produced! Fertilizer W, 一一 / person battery 0 Composite graphite material powder is an aggregate of powders. If strictly speaking, it is difficult to obtain a uniform aggregate of powders. Therefore, it has the physical properties of particles one by one. Physical property value (average value) of the aggregate of particles. In the present invention, there are two or more types of composite graphite material powders having different values as the aggregate of the latter. Here, the so-called physical property values can be exemplified: crystallinity (surface interval, crystal lattice size, etc.), specific surface area, particle size; coating ratio, Raman intensity ratio, true density, bulk density, purity, shape, and the like. In the present invention, it is preferable to use two or more types of composite graphite powders having different coating ratios. Specifically, the average value (hereinafter referred to as the coating ratio) of the so-called coating ratio lower than the dissimilar low-crystalline carbon secondary material / the amount of crystalline graphite powder + the amount of the low-crystalline carbon material (hereinafter referred to as the coating ratio) is different. By varying the coating ratio, it is possible to produce a secondary battery with a higher capacity density and higher performance. The so-called coating ratio is not the value of each particle, but the average value as the value of the aggregate of the composite graphite material powder. This value is calculated from the weight of the graphite powder in production and the weight change of the composite graphite material powder finally obtained. 77 ~ 0.3 Crystal Shao The coating ratio of the composite graphite material powder with a larger coating ratio is preferably within the range of 0.1, more preferably 0.1 to 0.25. If the coverage ratio is greater than 0, the low junction will be excessive, and the charge / discharge capacity will be low, which is not good. If it is less than 0, the effect of controlling the decomposition of the electrolytic solution will be low, which is not good. 87955 -11- 200408154 Also, the coating ratio of the composite graphite material powder with a smaller coating ratio is preferably below 〇1 ', more preferably G.G1 ~ (Mo, most preferably g.hm, if it does not reach 〇, otherwise, although The inhibitory factors that inhibit the above-mentioned polymerization are not sufficient. 〖If the coating ratio is greater than 0.1 ', it is difficult to obtain a negative electrode with excellent performance and high filling density, and it is not good. Furthermore, the amount of the composite graphite material powder with a small coating ratio The amount of composite graphite material powder with a large oblique coating ratio is weight, preferably 50% or less, and more preferably about 10 to 30%. If the amount is too large, the material properties will be dominated. The effect of inhibiting the factors that hinder polymerization If it is not fully available, the material itself will be = 'for reasons such as electrolyte penetration, deterioration, etc., ⑥ load characteristics, etc. will deteriorate. If the amount added is insufficient', the effect of improving filling properties will not be fully obtained. In addition, by changing the type of graphite powder instead of different coating ratios, high-capacity density and high-performance batteries can also be obtained. Crystals defined by ray diffraction, Raman spectrometry, true honey, etc. are used. Sexual assessment as dissimilar 2 types of I stone T powder, even when coating low-crystalline carbon materials with the same coating ratio, it is obvious that the filling properties differ depending on the type of graphite powder. This is not possible with evaluation methods such as the ray diffraction method. It is inferred that there is a difference in filling properties depending on the judged fine structure and the difference in shape and particle size of the graphite material from the shape of the core material. There is no particular limitation on the coating ratio when graphite powders differ. However, in order to further improve the filling property, the coating ratio of the composite graphite material powder with a large coating ratio should preferably be 0.03 ~ 0.3, and the composite ratio of the composite graphite material powder with a small coating ratio should preferably be 0.001 ~ 〇10. The coating ratio of the latter is 0 01 ~ 0 05. 87955 -12-200408154 The amount of composite graphite material powder with a small coating ratio to the amount of composite graphite material powder with a large coating ratio is preferably 50% or less in terms of weight ratio. It is more suitable to be about 10% to 30%. If the amount is too large, the properties of the material will be dominated. The effect of the factors that hinder the% polymerization cannot be fully obtained, and the material itself will become worse due to the infiltration of the solution. And other reasons, and The load characteristics and the like will change, and if the amount added is insufficient, the problem of the filling effect cannot be fully obtained. Powder graphite powder, using natural graphite as the powder as the graphite powder of the graphite material powder, can obtain good Mo Shiguo. ",", In the Qin Ming's is the meaning of the so-called compression ratio parameter The physical properties of the m-graphite f material are used as an indicator of the filling property. Here, the so-called shrinkage ratio is obtained by adding a 7.5 weight knife to the target composite graphite material powder (compared to the non-graphite graphite material powder). 100 parts by weight) (Polyvinylidene is a binder 'mixed with a solvent, and the slurry is coated with copper to eliminate the thickness change during stamping at a linear pressure of 300 kg / em. Specifically, the compression ratio = the thickness of the coating film after punching / the thickness of the coating film before punching ^ C v ′ to the film thickness at the time of film production are also important. That is, the higher the density of the R-coated R coating film, the smaller the step-to-step compression ratio, the more high ㈣ <negative :. Even if the compression ratio is very small, the density of the coating film before stamping is too small; the ancient is: to high-density anodes, if stamped, sometimes it will easily cause graphite to become "negative" and become a negative electrode with poor load characteristics. In addition, even if 2 87955 -13 -IM before embossing is a very high olfactory material, it is not good if the compression ratio is the negative electrode of the volume density. ， Because high energy cannot be obtained In the present invention, in order to make the compression ratio before stamping be 0.4 ~ 0.7, _ version mountain degree is 0.7g / ⑽3 or more,
、曰人 後又®膜密度為1.5 g/cm3w L 混合2種以上之複合石墨 g/⑽以上’宜 古八^ / ^各末。右冲壓後為塗膜宓厣人 …恩可得到高容量的負極。但 “度恩 壓縮比小時，所得到々古‘、 Τ 土則乏堂腠货度低， ,44 ^ 迭、度的負極係藉材料等之定Θ等 負诗特性會變差， 疋向寺 、 。又，沖壓後之塗膜宓y#永^ 1·8 g/cm3左六甘、 腺山度抑制至 v 、、、 以上很高時，負極中之空隙會不亦 分，故負極中之電解質^ Ί 、 一… 4貝的里會不足，有時無法得到充分自 何特性寺之電池特性。 /、 在本發明中之複合石墨材料粉末係藉氣相法、液相法、 固相法等之方法’如圖1所示般，於高結晶性石墨粉末r 表面附著低結晶性碳材料2而得到。 使用於芯材〈石墨粉末係可使用天然石墨、粒子狀（鱗片 狀乃至塊狀、纖維狀、晶鬚狀、球狀、破碎狀等）之人造石 墨、或中間碳微粒、中間相歷青粉末、等方性歷青粉末等 之石墨化品的1種或2種以上。 此處，成為芯材之石墨粉末更佳係以χ射線廣角繞射法之 (002)面的平均面間隔（d〇〇2)為〇·335〜0.340 nm、（002)面方 向之結晶格厚度（Lc)為1〇 nm以上（更佳係4〇 nm以上）、（丨1〇) 面方向之結晶格厚度（La)為1〇 nm以上（更佳係5〇 ηιη以上） 、以氟雷射拉曼宜在1360 cm-1附近之譜學強度比對1580 cm—1 附近< i晋峰強度比（以後記為r值）為〇·5以下（更宜為〇·4以 87955 -14- 200408154 於〇.340賊時，或Lc、La小於10⑽時 ，或肢過0.5時，石墨粉末之結晶性會不m 作複合十石墨材料粉末時，接独之溶解心、低電位部分 A基準為〇〜30〇mV)之容量會變不充分，故不佳。 成為心材 < 石墨粉末之粒徑分布宜為〇ι〜ΐ5〇 ”左右 。在石墨粉末之表面低結晶性碳材料附著之複合石墨材料 粉末的粒徑依料ff上芯材即石墨粉末的粒徑。因此， 依心材（粒控，最終生成物之粒徑亦略受限^。芯材之粒 徑小於0.1㈣時，通過電池分隔膜之空孔而引起内部短: :危險性會變高，故不佳。大於150心時，在負極之均 :性、活性物質之充填密度、製作負極之步驟上的操作性 寺會降低，故不佳。 此處，所謂粒徑係粉末之平均值在以雷射繞射式粒度分 布計所測定之粒度分布中，顯示料之值定義為粒徑。 在上述石墨粉末之表面形成低結晶性碳材料之方法中， =謂氣相法係使氣體狀之原料或狀之原料藉噴霧或氣泡法 寺疋万法輸送至反應系h ’藉由原料之熱分解而於石墨粉 末之表面從氣相形成碳之方法。熱分解溫度係因原料而異 ，但可在450〜150CTC左右之溫度範圍下進行。 原料係可舉例：m燒、㈣等之脂肪族飽和烴、 ==之脂肪族不飽和烴、$、甲苯、二甲苯、莕、二苯 (这寺《芳香族烴。又’亦可適當使用氬、氮等之純氣作 為載體氣體。X ’添加氫’認為亦可抑制在氣相中之煤灰 的發生等方法。 87955 -15- 200408154 在上述石墨粉末表面形成低結晶性碳材料之方法中，所 謂液相法係使碳前驅物經由液相而被碳化之原料附著於石 墨的表面’燒成此等而於表面形成碳之方法。原料可舉例 •奈、菲（phenanthrene)、厄錦'(acenaphthylene)、蔥、三鄰 亞苯、嵌二莕（pyrene)、2-苯並菲（Chrysene)、二苯嵌蒽等 之芳香族烴、此等在加熱加壓下聚縮合所得到之焦油或瀝 2、或、以等之芳香族烴的混合物作為主成分為焦油或瀝 青、柏油、油類。此等原料之來源係不論石油系或煤系。 又，蜒成之前，亦可使被覆碳前驅物之石墨粉末供給至 洗淨步驟。藉由加入洗淨步驟，可除去碳前驅物之低分子 成分，可提高來自碳前驅物之碳化率，同時並得到當粒子 間燒成時可抑制融接、或凝集之效果。此處，用於=之 线溶劑可舉例：甲苯、奎林（Q_lme)、丙輞、己垸、 本、二甲苯、甲基茶、醇類、煤系油、石油系油等。此等 〇中^甲苯、、奎林、丙嗣、苯、二甲苯1醇、煤系輕 ' 油石油系輕油、中油等更佳。 初在上述石墨粉末表面形成低結晶性碳材料之方法中 明固相法係使碳前驅物妳 里 _ 、、由口相而被石反化之原料附著於石 4表面’减成此等而於表㈣成竣之方法。 脂係經由固相而完诸 奴树 末的矣 瓦 2使如此之樹脂附著於石墨粉 末的表面，係可舉例 以上之溫户宴沾 '、.树知落解於溶劑中並加熱至融點 又、、万法，以形成液狀，藉由記載於上 法之說明的方法，以混 '上述政相 混合樹脂與石墨粉末二表面之方法。又’亦可 " 釦在燒成時保持於融點附近以進行 87955 -16· 200408154 混合。 具體之原料可舉例：暫 …⑯ 爾竭亞胺樹脂；聚醯胺樹脂； 水乙炔、永（對苯）、聚（對苯乙晞 •撼膝冉匕 /、車尼系树脂、紛樹脂 ，槺醛树脂；、纖維素；聚丙晞 ^ ^ 水（α -鹵化丙缔睛）筌> 丙烯鉍系樹脂；聚氯化乙烯、 ）寺（ ^ ,—市永偏虱乙烯、氯化聚氯化乙 ’市等之鹵化乙缔樹脂等。燒成條件你7、含 薛、土、pa、 成仏件係可通甲記載於上述液 層法义燒成方法與燒成環境。 又’所謂依上述方法所得到之 于」又低結晶性碳材料，更佳得 以X射線廣角繞射法之_)面的平均面間隔（撕2)為大於 340麵、⑽2)面方向之結晶格厚度（Le)為小相細(更佳 係小於1〇麵)、(11〇)面方向之結晶格厚度㈣為小於5〇_ 以上（更佳係小於1 〇 ηηι以上）、R枯 上）尺值為大於0.4(更佳係大於 0.5)。 相對於上述活性物質100重量份，混合黏接材n份而 形成負極。此黏接材係可使用聚四氣乙埽、聚偏氣乙埽等 之氟系聚合物、聚乙烯、聚丙缔等之聚埽烴系聚合物、合 成橡膠類，但，不限於此。若點接好夕 右粘接材多於30重量份，負極 之電阻或分極等會變大，放電容量會變小，故盔法製作每 用之鍾聚合物電池。反之，黏接材若小w重量份，黏接: 會消失，無實用性。在負極製作中，為提高黏接性，在黏 接劑之融點前後的溫度亦可進行熱處理。 為得到具有上述壓縮比之負極’在上述黏接材之中亦宜 使用合成橡膠類作為黏接材。具有上述壓縮比，且沖壓後 之塗膜密度具有1墙以上之物性的負極，係伴隨充放電 87955 -17- 200408154 、並因負極之膨脹收縮的反覆進行易引起循環劣化。橡膠 系之黏接材因具有很強的黏接能與橡膠彈性，故依隨活性 物質之膨脹收縮，可抑制負極之循環劣化。 成為在本發明之化學交聯凝膠的原料之聚合性單體，有 電解質之溶劑溶液與親和性，只要為具有可聚合之官能基 的化合物即可，並無特別限定。可舉例如：具有聚醚構造 及不飽和雙鍵基者、賦予寡酯丙烯酸酯、聚酯、聚胺、聚 硫醚、聚硫颯等之聚合物的聚合性單體或二種以上併用。 又，宜從與溶劑之親和性具有聚醚構造及不飽和雙键基者 。聚醚構造單元可舉例：環氧乙烷、環氧丙烷、環氧丁烷 、縮水甘油基醚類等。可適當使用此等之單獨或二種以上 之組合。又，2種以上組合時，其形態不論嵌段、隨機均可 適宜使用。其中，以丙晞酸酯系之材料由多官能單體與單 官能單體所構成的聚合性單體之使用，因賦予依隨負極之 體積變化的強度與彈性之凝膠，故佳。 丙烯酸酯系之單體係可適當地使用一以丙烯酯化聚醚多 元醇之末端羥基者。多官能單體係以乙二醇、甘油、三羥 甲基丙烷等之多價醇作為起始劑，再加成聚合環氧乙烷 (EO)單獨或EO與環氧丙烷（PO)所得到之聚醚多元醇的末端 羥基以丙烯酸進行酯化而得者。又，單官能單體係以甲醇 、乙醇、丙醇等之一價醇作為起始劑，再加成聚合環氧乙 烷（EO)單獨或EO與環氧丙烷（PO)所得到之聚醚多元醇的末 端羥基以丙烯酸進行酯化而得者。 此處，多官能單體係於凝膠電解質的電解液之保液性顯 87955 -18- 200408154 不重要的角色’以平均分子量為5,0〇〇〜10,000的範圍更佳 採用上述範圍内之多官能單體時，調整前驅物時，可很 备易地洛解於電解液中，又，具有凝膠電解質製成時優1 的保液性。 另外’單盲能单體係平均分子量愈小愈能提高凝膠電解 貝 <柔軟性，宜使用平均分子量200〜3,000左右者。 又，用於電解質之電解液可舉例：pc、EC、碳酸丁缔酿 等之環狀碳酸醋類、碳酸二甲酿、碳酸二乙酿、碳酸乙甲 酷、破酸二丙酿等之鏈狀碳酸類、r -丁 h酯、7 -戊内酿等 I内酉曰力員、四氫呋喃、2_甲基四氫呋喃等之呋喃類、二乙 醚、1，2-二甲氧基乙烷、u二乙氧基乙烷、乙氧基甲氧基 乙垸、二氧雜環己燒等之醚類、二甲颯、環丁碼、甲基環 丁碼乙如、蟻酸甲酯、醋酸甲酯等，可使用此等。 電解質鹽可舉例：過氯酸鋰（LiC104)、硼氟化鋰（LiBF4) 、鱗氣化！里（UPF6)、六氟化坤酸鐘（LiAsF6)、六氣化錄酸鍾 (LiSbFJ、二氟甲烷磺酸鋰（LiCF3S〇3)、三氟醋酸鋰 (LiCFsCOO)、二氟甲烷磺酸醯亞胺鋰（LiN(CF3S〇2)2)等之鋰 鹽，可混合此等之一種以上而使用之。 電解質係藉由在前述所選擇之溶射料電解f鹽而調 製電解液’與上述聚合性單體混合，聚合所得到者。 上述，水合性單體與電解液之比率係就匹敵於電解液之 性能、與、不產生液體戍漏之電解液的保持性而言，宜電 解液：單體為70:30〜99:1，更宜為8〇:2〇〜97:3。 混合使用單官能單體與多官能單體時，單體之混合比係 87955 -19- 200408154 宜以多官能單體：單官能單體為4: 6〜 、 高分子固體電解曾之交聯 *園混合。 了見^〈光能量的方法、以加熱之方法。若需要，亦 可使用聚合起始劑。尤其在紫 而 宜加人蓊。/、， ’、卜、'泉或加熱 < 交聯方法中， 且加入數/〇以下之聚合起始劑。 甲其甘 氷合起始劑係亦可添加三 土甲夕烷基—苯甲酮、安息香、2_甲美 夭 ^ 二苯甲酮、安息香甲基蒽土。曰4-甲氧土 取入却本甲基二甲基縮酮等之光 水5起七劑、或、過氧化苯甲酿 你长織田 Τ乙酮、«，^ - 偶亂又井丁腈等之聚合起始劑。 紫外線聚合、紫外線之波長堂 反長且為25〇〜〜360 nm。使用起 :劑時，若依本發明，亦可以很少的起始劑得到良好的聚 泰殘存聚合起始劑、以聚合起始劑所產生的副生成物 有時對電池特性會有不良影響，宜止於必需最小限量。起 始劑之量係依起始劑之種類而異，但，相對於由聚合性單 體與電解液所構成的前驅物，—般宜抑制至3咖_以下。 在本發明之组聚合物二次電池的正極，係可使用含有例 如鍾之氧化物作為正極活性物質。正極活性物質之且體例 可舉例：LlCG〇2、LlNl〇2、LlFe〇2、LiMn〇2、LiMn2〇4、 或取代其等之過渡金屬的-部分之材料等。再者依導電材 、黏接材及情形，混合固體電解質等而形成正極。 此混合比係相對於活性物質100重量份，可使導電材為5 〜50重量份，黏接材為1〜30重量份。於此導電材中係可使 用碳黑（乙炔碳黑、熱碳黑、通道碳黑等）之碳類、或、石墨 粉末、金屬粉末等，但，不限於此。 87955 -20- 200408154 於此黏接材係可使用聚四氟乙烯、聚偏氟乙烯等之氟系 聚合物、聚乙烯、聚丙烯等之聚烯烴系聚合物、合成橡膠 類，但不限於此。 若導電材少於5重量份、或黏接材多於3 0重量份，正極之 電阻或分極等會變大，放電容量會變小，故無法製作實用 上之鋰聚合物電池。若導電材多於50重量份（依所混合之導 電材的種類重量份會改變），正極内所含有之活性物質量會 減少，故作為正極之放電容量會變小。黏接材若少於1重量 份，黏接能力會消失，若多於30重量份，與導電材之情形 相同地，正極内所含有之活性物分量會減少，進一步，如 上述記載般，正極之電阻或分極等會變大，放電容量會變 小，故不實用。在正極製作中，為提高黏接性，宜在各別 之黏接劑的融點前後之溫度下進行熱處理。 【實施方式】 實施例1、比較例1 為觀察對高分子固體電解質之前驅物的硬化影響，以混 合石墨材料粉末之狀態進行前驅物之硬化實驗。 前驅物之調整 以已溶解1 mol/升之LiBF4的EC與r - 丁内酯之1 : 1的混合 溶劑作為電解液。含有環氧乙烷與環氧丙烷之共聚合物所 構成的平均分子量7500〜9000之四官能丙浠酸S旨單體、與 平均分子量200〜300之單官能丙烯酸酯單體就重量比為7 :3的單體，以電解液與單體之比率為95 : 5之方式混合於 電解液中。於其溶液中相對於全重量加入熱聚合起始劑200 87955 -21 - ZUU4U8n4 <熱聚合起始劑為第三丁基過氧化 p ριτι作為如驅物所使用 新癸酸酯。 以石墨粉末與前驅物之比就重量比& &彳.彳Λ、、# ^ , 里里比成為1 : 10足万式混合 兩者，在8(Tc恆溫槽下保梏2 保持24 j時，確認前驅物之硬化狀 石 、’末係X k姆卡爾公司製人造石墨（Km)作為芯材 2用以使低結晶性碳材料附著之複合石墨材料粉末變更 材:晶^材料之量/(高結晶性石墨粉末之量+低結晶性礙 :《里)的平均值者而進行硬化實驗(實施例1)。又，不使 性碳材料被覆之情形作為比較例i。結果表示於表! 〇係充刀硬化，液狀之部分亦無狀況，〇係凝膠 柔軟，但液狀之部分未殘留之狀況，X係未充分硬化 ，而硯祭到液狀之部分的狀況。 表1 實施例1, Said after the ® film density is 1.5 g / cm3w L mixed with more than two kinds of composite graphite g / ⑽ or more ′ should be ancient eight ^ / ^ each end. After the right punching, the coating film smashes ... En can get a high capacity negative electrode. However, if the compression ratio of Duen is small, the obtained 々 古 'and Τ are low in quality, and the negative poem characteristics such as 44 and 的 of the negative electrode borrowed materials will deteriorate. And, when the coating film 冲压 y # 永 ^ 1 · 8 g / cm3 after pressing is left, and the degree of glandularity is suppressed to v ,,, or above, the voids in the negative electrode will not be separated, so in the negative electrode The electrolyte ^ 、, -1 ... 4 ber is insufficient, and sometimes the battery characteristics sufficient from the characteristics can not be obtained. / The composite graphite material powder in the present invention is by the gas phase method, liquid phase method, solid phase As shown in Fig. 1, a method such as "method" is obtained by attaching a low-crystalline carbon material 2 to the surface of the highly crystalline graphite powder r. Used in the core material (graphite powder can be natural graphite, granular (scaly or even lumpy) (Fibrous, fibrous, whisker-like, spherical, broken, etc.) artificial graphite, or intermediate carbon fine particles, mesophase blue powder, isocyanate powder and other graphitized products, one or more. Here The graphite powder that becomes the core material is more preferably the average of the (002) plane by the x-ray wide-angle diffraction method. The interval (d〇 02) is 0.335 to 0.340 nm, the crystal lattice thickness (Lc) in the (002) plane direction is 10 nm or more (more preferably 40 nm or more), and The crystal lattice thickness (La) is 10nm or more (more preferably 50nm or more), and the spectral intensity comparison with a fluorine laser Raman near 1360 cm-1 is compared with around 1580 cm-1 < i Jinfeng The strength ratio (hereinafter referred to as the r value) is 0.5 or less (more preferably 0.4 to 87955 -14-200408154 to 0.340 thief, or when Lc and La are less than 10 肢, or when the limb exceeds 0.5, graphite powder When the crystallinity is not used as the composite ten graphite material powder, the capacity of the dissolved core and low potential part A (the reference of the low potential part is 0 to 30 mV) will not be sufficient, so it is not good. The particle size distribution should preferably be about 0 to about 50 ”. The particle size of the composite graphite material with low-crystalline carbon material attached to the surface of the graphite powder depends on the particle size of the core material, that is, the graphite powder. Therefore, Espresso wood (grain control, the particle size of the final product is also slightly limited ^. When the particle size of the core material is less than 0.1 ，, the internal shortness caused by the pores of the battery separator film:: the danger will become higher, so Poor. If it is more than 150 cores, the negative electrode will have a lower average: properties, filling density of active material, and operability in the process of making the negative electrode, which is not good. Here, the average value of the so-called particle size powder is between In the particle size distribution measured by the laser diffraction particle size distribution meter, the value of the display material is defined as the particle size. In the method for forming a low-crystalline carbon material on the surface of the graphite powder described above, a gas phase method is used to make a gas The raw materials or raw materials are transported to the reaction system by spraying or bubble method. The method of forming carbon from the gas phase on the surface of graphite powder by thermal decomposition of the raw materials. The thermal decomposition temperature varies depending on the raw materials, but can It is carried out at a temperature range of about 450 ~ 150CTC. Examples of raw materials are: aliphatic saturated hydrocarbons such as methane, osmium, etc., aliphatic unsaturated hydrocarbons ==, toluene, xylene, osmium, dibenzene (this temple "Aromatic hydrocarbons. Also 'can be used appropriately Pure gases such as nitrogen and nitrogen are used as carrier gases. X 'addition of hydrogen' is considered to also suppress the occurrence of coal ash in the gas phase. 87955 -15- 200408154 In the method for forming a low-crystalline carbon material on the surface of the above graphite powder The so-called liquid phase method refers to a method in which a carbon precursor is carbonized through a liquid phase and a carbonized raw material is attached to the surface of graphite. The method of firing these to form carbon on the surface. Examples of the raw materials include Nai, phenanthrene, and Erjin. aromatic hydrocarbons such as (acenaphthylene), shallots, vicinal phenylene, pyrene, 2-benzophenanthrene (Chrysene), diphenylanthracene, etc., and tars obtained by polycondensation under heat and pressure The main components of the mixture of aromatic hydrocarbons such as tar 2, or tar are tar or bitumen, asphalt, oil. The source of these raw materials is irrespective of petroleum or coal. Before coating, it can also be covered. The graphite powder of the carbon precursor is supplied to the washing step. By adding the washing step, the low molecular components of the carbon precursor can be removed, the carbonization rate from the carbon precursor can be increased, and at the same time, it can be suppressed when firing between particles. Fusion, or agglutination Here, examples of the linear solvent used for = include toluene, quinine (Q_lme), propane, hexane, benzine, xylene, methyl tea, alcohols, coal-based oil, petroleum-based oil, and the like. Among them, toluene, quinine, propane, benzene, xylene, 1-ol, coal-based light oil, petroleum-based light oil, medium oil, etc. are more preferred. Method for forming a low-crystalline carbon material on the surface of the above graphite powder The Zhongming solid-phase method is a method for making carbon precursors __, and raw materials that are converted by stones from the oral phase to the surface of stone 4 'reduced into these and completed on the surface. The tile 2 of the end of the slave tree makes such a resin adhere to the surface of graphite powder, which can be exemplified by the above-mentioned warm household feast, and the tree knows that it dissolves in the solvent and is heated to the melting point. In order to form a liquid state, the method described in the above method is used to mix the above-mentioned political phase mixed resin and graphite powder on both surfaces. It ’s also possible to keep the buckle near the melting point during firing for 87955-16 · 200408154 mixing. Specific raw materials can be exemplified by: temporary ... imine resin; polyimide resin; water acetylene, permanent (p-phenylene), poly (p-phenyleneacetate) • Knee-shock Ran /, Cheni resin, resin, Aldehyde resin; cellulose; polypropylene ^ ^ water (α-halogenated acrylic eye) 筌 > propylene bismuth resin; polyvinyl chloride,) (^,-city permanent lice vinyl, chlorinated polychloride Chemicals, such as halogenated vinyl resins, etc. The firing conditions are as follows: 7. The materials containing Xue, soil, pa, and sintered materials can be described in the above-mentioned liquid layer method and the firing environment. The result obtained by the above method is “low-crystalline carbon material. It is better that the average interplanar spacing (tear 2) of the _) plane of the X-ray wide-angle diffraction method is greater than the crystal lattice thickness (Le ) Is the size of the small phase (more preferably less than 10 planes), the thickness of the crystal lattice in the direction of (11〇) plane ㈣ is less than 50 ° or more (more preferably less than 10 mm), and R is on the scale. Greater than 0.4 (more preferably greater than 0.5). A negative electrode was formed by mixing n parts of a bonding material with respect to 100 parts by weight of the active material. Examples of the adhesive material include fluoropolymers such as polytetrafluoroethylene, polyacetylene, polyfluorinated hydrocarbon polymers such as polyethylene and polypropylene, and synthetic rubbers, but are not limited thereto. If the connection is good, if the right bonding material is more than 30 parts by weight, the resistance or separation of the negative electrode will increase, and the discharge capacity will be reduced. Therefore, the helmet method is used to make a polymer battery for each clock. Conversely, if the weight of the adhesive material is small by weight, the adhesiveness will disappear, which is not practical. In the fabrication of the negative electrode, in order to improve the adhesiveness, heat treatment may be performed before and after the melting point of the adhesive. In order to obtain the negative electrode having the above compression ratio, it is also preferable to use a synthetic rubber as the bonding material among the bonding materials. A negative electrode having the above compression ratio and having a coating film density of 1 wall or more after stamping is accompanied by charge and discharge 87955 -17- 200408154, and it is easy to cause cycle degradation due to repeated expansion and contraction of the negative electrode. Since the rubber-based adhesive material has strong adhesive energy and rubber elasticity, the expansion and contraction of the active material can suppress the cycle deterioration of the negative electrode. The polymerizable monomer used as the raw material of the chemically crosslinked gel of the present invention is not particularly limited as long as it has a solvent solution of an electrolyte and affinity, as long as it is a compound having a polymerizable functional group. Examples thereof include a polymer having a polyether structure and an unsaturated double bond group, a polymerizable monomer imparting a polymer such as oligoester acrylate, polyester, polyamine, polythioether, polythiosulfide, or two or more kinds thereof. In addition, it is preferable to have a polyether structure and an unsaturated double bond group with an affinity for the solvent. Examples of the polyether structural unit include ethylene oxide, propylene oxide, butylene oxide, and glycidyl ethers. These may be used alone or in combination of two or more. When two or more kinds are combined, the form can be suitably used regardless of whether it is a block or a random form. Among them, the use of a polymerizable monomer composed of a polyfunctional monomer and a monofunctional monomer based on a propionate-based material is preferred because it imparts a gel having strength and elasticity in accordance with the volume change of the negative electrode. As the acrylate-based single system, a terminal hydroxyl group of a polyether polyol with propylene can be suitably used. Polyfunctional monosystems are obtained by using polyvalent alcohols such as ethylene glycol, glycerol, and trimethylolpropane as starting agents, followed by addition polymerization of ethylene oxide (EO) alone or EO and propylene oxide (PO). The terminal hydroxyl group of the polyether polyol is obtained by esterification of acrylic acid. In addition, monofunctional monosystems use monovalent alcohols such as methanol, ethanol, and propanol as starting agents, and then add polyethers obtained by polymerizing ethylene oxide (EO) alone or EO and propylene oxide (PO). The terminal hydroxyl group of the polyol is obtained by esterification of acrylic acid. Here, the liquid-retaining property of the polyfunctional mono-system in the gel electrolyte is 87055 -18- 200408154. The unimportant role is' A range with an average molecular weight of 5,000 to 10,000 is more preferably adopted. In the case of polyfunctional monomers, the precursor can be easily dissolved in the electrolyte when adjusting the precursor, and it has the liquid-retaining property of excellent 1 when the gel electrolyte is made. In addition, the smaller the average molecular weight of the single-single energy system, the better the gel electrolysis < softness, and the average molecular weight of about 200 to 3,000 should be used. In addition, the electrolytic solution used for the electrolyte can be exemplified by the chains of cyclic carbonates such as pc, EC, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl carbonate, and diacid dipropylene carbonate. Carbonic acid, r-butyl h-ester, 7-pentanone, etc., I, uric acid, tetrahydrofuran, 2-methyltetrahydrofuran and other furans, diethyl ether, 1,2-dimethoxyethane, u Diethoxyethane, ethoxymethoxyacetamidine, dioxane and other ethers, dimethylacetamidine, cyclobutane, methylcyclobutane, aceto, methyl formate, methyl acetate Etc. can be used. Examples of electrolyte salts: lithium perchlorate (LiC104), lithium borofluoride (LiBF4), scale gasification! Li (UPF6), Lithium hexafluoride (LiAsF6), Lithium hexafluoride (LiSbFJ, lithium difluoromethanesulfonate (LiCF3S〇3), lithium trifluoroacetate (LiCFsCOO), difluoromethanesulfonate Lithium salts such as lithium imine (LiN (CF3S〇2) 2) can be used in combination of one or more of these. The electrolyte is prepared by electrolytically preparing the electrolyte by electrolyzing the f salt in the solvent selected above and polymerizing the above. It is obtained by mixing and polymerizing the monomers. As mentioned above, in terms of the performance of the hydratable monomer and the electrolyte, which is comparable to the performance of the electrolyte, and the retention of the electrolyte that does not cause liquid leakage, the electrolyte is preferably: The monomer is 70:30 to 99: 1, and more preferably 80:20 to 97: 3. When a monofunctional monomer and a polyfunctional monomer are mixed, the mixing ratio of the monomers is 87955 -19- 200408154. Polyfunctional monomer: Monofunctional monomer is 4: 6 ~, polymer solid electrolyte has been cross-linked * garden mixed. See the method of light energy, the method of heating. If necessary, you can also use polymerization initiation Agent, especially in purple and should be added. / ,, ', Bu,' spring or heating < cross-linking method, and the number of addition / 0 or less Polymerization initiator. Methyl glycyrrhizinate initiators can also be added triclosyl alkyl-benzophenone, benzoin, 2-metamidine ^ benzophenone, benzoin methyl anthracene. 4 -Methoxanthine but seven methyl dimethyl ketal and other guangshui seven or seven, or benzyl peroxide brewed in your long Oda T ethyl ketone, «, ^-occasionally and well butyronitrile Polymerization initiator. Ultraviolet polymerization, the wavelength of ultraviolet rays is inversely long and is from 25 to 360 nm. When used: When using the agent, according to the present invention, it is possible to obtain good Jutai residual polymerization with very few initiators. The initiator and by-products produced by the polymerization of the initiator may adversely affect the characteristics of the battery and should be limited to the required minimum amount. The amount of the initiator varies depending on the type of the initiator. A precursor composed of a polymerizable monomer and an electrolytic solution is generally suppressed to 3 or less. In the positive electrode of the polymer secondary battery of the present invention, it is possible to use, for example, a bell oxide as a positive electrode active material. Examples of positive electrode active materials include: LlCG〇2, LlNl02, LlFe02, LiMn02, LiMn2. 4. Or replace some of the transition metal-partial materials, etc. Furthermore, depending on the conductive material, the bonding material and the situation, the solid electrolyte is mixed to form the positive electrode. This mixing ratio is 100 parts by weight relative to the active material. The conductive material is 5 to 50 parts by weight, and the adhesive material is 1 to 30 parts by weight. In this conductive material, carbon black (acetylene carbon black, thermal carbon black, channel carbon black, etc.), carbon, or graphite can be used. Powder, metal powder, etc., but it is not limited to this. 87955 -20- 200408154 Adhesive material can be fluoropolymer such as polytetrafluoroethylene, polyvinylidene fluoride, polyolefin such as polyethylene, polypropylene, etc. It is a polymer or a synthetic rubber, but is not limited thereto. If the conductive material is less than 5 parts by weight, or the bonding material is more than 30 parts by weight, the resistance or separation of the positive electrode will increase, and the discharge capacity will become small. Therefore, a practical lithium polymer battery cannot be produced. If the conductive material is more than 50 parts by weight (which varies depending on the type of conductive material to be mixed), the amount of active material contained in the positive electrode will decrease, so the discharge capacity as a positive electrode will become small. If the adhesive material is less than 1 part by weight, the adhesive ability will disappear. If it is more than 30 parts by weight, the amount of active material contained in the positive electrode will decrease as in the case of a conductive material. Further, as described above, the positive electrode The resistance or the polarization will become larger, and the discharge capacity will become smaller, so it is not practical. In the production of the positive electrode, in order to improve the adhesion, it is appropriate to perform heat treatment at a temperature before and after the melting point of each adhesive. [Embodiment] Example 1 and Comparative Example 1 In order to observe the hardening effect on the precursor of the polymer solid electrolyte, a precursor hardening experiment was performed in the state of mixed graphite material powder. Precursor adjustment A 1: 1 mixed solvent of EC and r-butyrolactone in a solution of 1 mol / L of LiBF4 was used as the electrolyte. A weight ratio of a tetrafunctional propionic acid S monomer having an average molecular weight of 7500 to 9000 composed of a copolymer of ethylene oxide and propylene oxide, and a monofunctional acrylate monomer having an average molecular weight of 200 to 300 is 7 : 3 monomers were mixed in the electrolyte so that the ratio of the electrolyte to the monomers was 95: 5. To its solution, a thermal polymerization initiator 200 87955 -21-ZUU4U8n4 was added with respect to the total weight. ≪ The thermal polymerization initiator was tert-butyl peroxide p ριτι as a neodecanoate used as a flooding agent. The weight ratio is based on the ratio of the graphite powder to the precursor & & 彳. 彳 Λ ,, # ^, and the Lirie ratio becomes 1:10. At time j, confirm the precursor's hardened stone, 'the end of X Kmkar's artificial graphite (Km) as the core material 2 composite graphite material powder change material for attaching low crystalline carbon materials: crystal Amount / (amount of high crystalline graphite powder + low crystalline hindrance: the average value of "Li") and the hardening test was performed (Example 1). The case where the carbon material was not covered was used as Comparative Example i. Results are shown In the table! 〇 is filled with a knife and hardened, and the liquid part is no condition. 〇 is a gel that is soft, but the liquid part is not left. X is not sufficiently hardened, and the liquid is burned to the liquid part. Table 1 Example 1
___^種類 〜 ------- 、卜 人 "—----- 被覆比 硬化狀況 \ JLm. % 0.05 〇 —石墨 ~^τχ--- —墨 __合石墨 —--—___ 土 0.1 ◎ 0.2 ◎ 0.28 ----—-- ◎ --__JCS25 ~~—--- X 一、 n肌兀孤艮好〇 "文去欠更起始劑之量而進行實驗後，即使變更， 硬：度之傾向亦相同，被覆比大者可充分硬化。 吏起始釗相對於前驅物的全量，增加至5000 ppm左 寺/、石墨材料，可得到某種程度之硬化狀況。因此， 87955 -22- 200408154 衩合石墨材料粉末係不依起始劑濃度而硬化，尤其，起妒 劑在5000 ppm以下之區域，比僅芯材之情形效果還大。 貫施例2 (正極之製作） 於正極活性物質使用鈷酸鋰（LlCo〇2)。暫時以研雉使黏 接材即聚偏氟化乙婦溶解於溶劑N_m㈣酮的黏接 劑溶液中，使上述正極活性物質與乙块碳黑之混合物分散 ，俾製作糊劑。 將如此所得到之糊劑塗布於鋁箔集電體上，再以6〇它暫 時乾燥，15Gt：下熱處理後進行沖壓。以負極大小為35χ3 cm(塗工部3x3cm)，於無塗工部焊接銘落⑼心），為進一 步除去水分，在18(TC下減壓乾燥後作為試驗用之正極。塗 膜:密度為2.9 g/cm3。 ' (負極之製作） =負極活性物質使用提姆卡爾公司製人造石墨⑽⑼作 為心材’使用-於表面附著低結晶性碳材料之複合石墨材 料粉末（粒徑η :碳材料之量/(高結晶性石墨粉末之量+低結晶性碳材料： 里）人―0.18)80重量份、與、天然石墨（馬達加斯嘉）作為芯材 ’於表面附著低結晶性碳材料之複合石墨材料粉末(粒㈣ ”2)=0.336 nm、R值划、低結晶性碳材料之 =、结晶性石墨粉末之量+低結晶性韻料之量）=〇()5)2〇重 混合物’作為負極活性物質。再以料使黏接材即 水偏鼠化乙缔分散於一已溶解於溶劑…甲 87955 - 23- 200408154 溶液中，以形成糊劑，將如此所得到之糊劑塗布於2〇从m 之銅箔上，再以6(TC暫時乾燥，24(rc下熱處理後進行沖壓 使負極大小為3 ·5 X 3 cm(塗工邵3 X 3 cm)，於無塗工部焊 接鎳箔（50 vm)之導線，為進一步除去水分，在15〇它下真 空乾燥後作為負極。塗膜密度為158 g/cm3。 (前驅物之調整） 以已溶解1.8 mol/升之UBF4的EC與r -丁内酯之丨：i的混 合溶劑作為電解液。含有環氧乙烷與環氧丙烷之共聚合物 所構成的平均分子量7500〜9〇〇〇之四官能丙烯酸酯單體、 與平均分子量200〜300之單官能丙烯酸醋單體就重量比為 7. 3的早體，以電解液與單體之比率為97: 3之方式混合於 電解液中。於其溶液中相對於全重量加入熱聚合起始劑2〇〇 ρρχη形成前驅物。 (電池之製作） 使用聚I旨製之不織布作為分隔膜’以如上述般做法所得 至=電極對向重疊’插人^已加工呈袋狀之料層的袋子 。於此’置入上述之前驅物，在減壓下進行熱#口。然後 丄在80t下保持4小時’進行熱聚合，製作聚合物電池。所 件到 < 電池在電流值4 mA、充電41 v_cccv(電流電壓— 仆放電2.75V-CC(電流一定）之條件下反覆充放電，測定 =特性。所使用之材料、混合比率等表示於表^，塗膜___ ^ Types ~ -------, Bu Ren " ------- Covering specific hardening condition \ JLm.% 0.05 〇—Graphite ~ ^ τχ --- — 墨 __ 合 Graphic ———— ___ Soil 0.1 ◎ 0.2 ◎ 0.28 ------------ ◎ --__ JCS25 ~~ ----- X I. The n muscles are good. After quoting the amount of the initiator, the experiment is performed. Even if it is changed, the tendency of hardness is the same, and the larger the coverage ratio, the harder it is. Compared with the total amount of the precursors, the starting material of Li Shizhao is increased to 5000 ppm Zuo Si / graphite material, and a certain degree of hardening can be obtained. Therefore, 87955 -22- 200408154 hardened graphite powder does not harden depending on the concentration of the initiator. In particular, the area where the jealous agent is below 5000 ppm is more effective than the case of the core material alone. Example 2 (manufacturing of a positive electrode) As the positive electrode active material, lithium cobaltate (LlCoO2) was used. Temporarily dissolve the adhesive material, namely polyvinylidene fluoride, in an adhesive solution of the solvent N_m fluorenone, disperse the mixture of the positive electrode active material and the carbon black, and prepare a paste. The paste thus obtained was applied to an aluminum foil current collector, and then temporarily dried at 60 ° C, followed by heat treatment at 15 Gt: and then punching. The size of the negative electrode was 35 × 3 cm (3x3 cm in the coating section), and the welding was performed on the non-coating section. In order to further remove the moisture, it was used as the positive electrode for the test after drying under reduced pressure at 18 TC. Coating film: Density is 2.9 g / cm3. '(Production of the negative electrode) = The negative electrode active material uses artificial graphite made by Timcar Company as the core material.' Use-a composite graphite material powder (particle diameter η: of carbon material) Amount / (amount of high crystalline graphite powder + low crystalline carbon material: Li)-0.18) 80 parts by weight, and natural graphite (Madagascar) as the core material, where the low crystalline carbon material is attached to the surface Composite graphite material powder (grain ”2) = 0.336 nm, R value, low crystallinity of carbon material =, amount of crystalline graphite powder + amount of low crystallinity material) = 〇 () 5) 20 The mixture is used as the negative electrode active material. The adhesive material, namely water-ratified ethylene, is dispersed in a solution that has been dissolved in a solvent ... A 87955-23- 200408154 to form a paste, and the paste thus obtained is used. Coated on 20mm copper foil, then temporarily dried at 6 (TC, 24 (rc After heat treatment, stamping was performed to make the size of the negative electrode 3 · 5 X 3 cm (coated Shaoxing 3 X 3 cm), and a nickel foil (50 vm) wire was welded to the uncoated part. In order to further remove moisture, vacuum was applied at 150 ° C. After drying, it was used as a negative electrode. The coating film density was 158 g / cm3. (Precursor adjustment) A mixed solvent of EC and r-butyrolactone: i which had dissolved 1.8 mol / L UBF4 was used as the electrolyte. A weight ratio of a tetrafunctional acrylate monomer having an average molecular weight of 7,500 to 9,000 composed of a copolymer of ethylene oxide and propylene oxide, and a monofunctional acrylic monomer having an average molecular weight of 200 to 300 is 7.3. The early body was mixed in the electrolytic solution such that the ratio of the electrolytic solution to the monomer was 97: 3. A thermal polymerization initiator 200 ρρχη was added to the solution to form a precursor. (Production of the battery ) Use a non-woven fabric made of Poly I as the separator film. The electrode obtained in the same way as above = the electrode pairs overlap and insert the bag that has been processed into a bag-shaped material layer. Here, insert the aforementioned precursor, and Under reduced pressure, heat # 口. Then hold at 80t for 4 hours to perform heat Polymer battery was produced. The battery was charged and discharged repeatedly under the conditions of 4 mA and 41 V_cccv (current voltage-discharge 2.75V-CC (constant current)). Materials and mixing ratios are shown in Table ^, coating film
If (冲壓則）、壓縮比、塗膜密度（沖壓後）、每—負極活性 質層的體積能量密度、循環時之容量保持率表示於表3中。 比較例2 87955 -24- 200408154 於負極活性物質’使用提姆卡爾公司製人造石墨( …入 除了早獨使用-於表面附著低結晶性碳材料之 m材料料（粒徑12 " m、d(術)气印_、r值心 :晶性彻之量/(高結晶性石墨粉末之量+低結晶性 = q)=G·18)以外，其餘與實施物同地製作負極。 二《負極的塗膜密度為“一、除使用如此所得到 —以外，其餘與實施例2相同地製作 =了用之材料、混合比率等表示於㈣：： i則）、壓縮比、塗膜密彦卜 屉的触社处 ' — (冲堡後）、母一負極活性物質 :::::量密度、循環時之容量保持率表示於表3中。 作為負/$/舌性物質，使用提姆卡爾公司製人造石墨（KS25) 石除了使用一於表面附著低結晶性碳材料之複合 =材科粉末（粒徑12 ,m、d_=G 337 nm =料之量獅晶性石墨粉末之量養晶性竣 、耘你“ 里1刀〃天然石墨（馬達加斯嘉出產 、、曰八 V m d(002)-〇.3358 nm、R值=〇1)2〇重量份之 μ物以外，其餘與實施例2相同地 極的塗膜穷声 ^所仵到《負 ，戈备 Μ ’65_ °除使用如此所得到之負極以外 ^與f施m相同地製作電池，進行充放電試驗。所使 风=料、混合比率等表示於表2中，塗膜密度（沖壓前）、 塗膜密度（沖壓後）、每一負極活性物質層的體積能 二度、循環時之容量保持率表示於表3中。 貝施例3〜5、比較例4〜5 87955 -25- 200408154 碳材料係除使用表2中所示之石墨材料粉末作為活性物 質以外，其餘與實施例2相同，製作負極及電池。結果，（ 塗膜密度（沖壓前）、壓縮比、塗膜密度（沖壓後）、每一負極 活性物質層的體積能量密度、循環時之容量保持率）表示於 表3中。表2中所謂MCMB係瀝青系之球狀碳材料即中間碳 微粒的簡稱。 表2 複合石墨1 複合石墨2 複合石墨1 : 複合石墨2 芯材 被覆比 芯材 被覆比 實施例2 KS25 0.18 天然石墨 (馬達加斯嘉出產） 0.03 8:2 實施例3 KS25 0.15 KS25 0.05 7:3 實施例4 KS25 0.22 MCMB 0.02 6:4 實施例5 天然石墨 (馬達加斯嘉 出產） 0.08 天然石墨 (馬達加斯嘉出產） 0.03 5:5 比較例2 KS25 0.18 - - 10 ： 0 比較例3 KS25 0.22 天然石墨 (馬達加斯嘉出產） 無被覆 6:4 比較例4 天然石墨 (馬達加斯嘉 出產） 無被覆 10 ： 0 比較例5 天然石墨 (馬達加斯嘉 出產） 0.05 10 ·· 0 87955 26- 200408154If (pressing), compression ratio, coating film density (after pressing), volume energy density per negative electrode active layer, and capacity retention rate during cycling are shown in Table 3. Comparative Example 2 87955 -24- 200408154 In the negative electrode active material, artificial graphite (made by Tim Carr) was used (in addition to the original material alone-m material with a low crystalline carbon material attached to the surface (particle size 12 " m, d (Surgery) Airmark _, r value heart: Except for the amount of crystallinity / (the amount of highly crystalline graphite powder + low crystallinity = q) = G · 18), the rest are made in the same place as the implementation. The coating film density of the negative electrode is "1. Except that it is obtained in this way, the rest are produced in the same manner as in Example 2 = the materials used, the mixing ratio, etc. are shown in ㈣: i)), the compression ratio, and the coating film Bu Tie's contact office '— (after Chongbao), mother-negative active material ::::: Volume density, capacity retention rate during cycling are shown in Table 3. As negative / $ / tongue materials, use The artificial graphite (KS25) stone manufactured by Mukar Company uses a composite of a low-crystalline carbon material attached to the surface = material powder (particle size 12, m, d_ = G 337 nm = the amount of lion crystal graphite powder) Endurance of crystal growth, work hard for you "1 knife of natural graphite (manufactured by Madagascar, 曰 八 V md (002) -0.3358 nm, R value = 〇1) Except for 20 parts by weight of μ, the rest of the coating film of the same ground electrode as in Example 2 was exhausted ^ to "negative, Ge Bei M '65_ ° Except using the negative electrode thus obtained ^ Batteries were fabricated in the same manner as in Fm, and the charge and discharge tests were performed. The wind = material, mixing ratio, etc. are shown in Table 2, coating film density (before stamping), coating film density (after stamping), and each negative electrode active material. The volume energy of the layer is two degrees, and the capacity retention rate at the time of cycling is shown in Table 3. Examples 3 to 5 and Comparative Examples 4 to 5 87955 -25- 200408154 carbon materials except the graphite material powder shown in Table 2 Except for the active material, the negative electrode and the battery were produced in the same manner as in Example 2. As a result, (coating film density (before stamping), compression ratio, coating film density (after stamping), volume energy density of each negative electrode active material layer, The capacity retention rate during cycling is shown in Table 3. In Table 2, the so-called MCMB pitch-based spherical carbon material is the abbreviation of intermediate carbon particles. Table 2 Composite graphite 1 Composite graphite 2 Composite graphite 1: Composite graphite 2 Core material Cover ratio than core material Cover ratio Example 2 KS 25 0.18 Natural graphite (made in Madagascar) 0.03 8: 2 Example 3 KS25 0.15 KS25 0.05 7: 3 Example 4 KS25 0.22 MCMB 0.02 6: 4 Example 5 Natural graphite (made in Madagascar) 0.08 Natural graphite (Made in Madagascar) 0.03 5: 5 Comparative Example 2 KS25 0.18--10: 0 Comparative Example 3 KS25 0.22 Natural graphite (made in Madagascar) Uncoated 6: 4 Comparative Example 4 Natural graphite (made in Madagascar (Manufactured) Uncoated 10: 0 Comparative Example 5 Natural graphite (manufactured by Madagascar) 0.05 10 ·· 0 87955 26- 200408154
如以上之結果所示般，甚每★ 僱％特性優之鋰聚合物 “度且As shown in the above results, the lithium polymer with excellent properties
Ri, τ 早獨使用稷合石墨材料粉夫 時（比較例2與5)，電極之 才枓心末 A # ^ ^ -1 JL 山度低，又，使用天然石墨作 為无填助劑時（比較你，么；~ 、 u ”、、法仔到充分的循環特性。此係 早獨使用複合石墨時，沖厭祕把 ΤΓ 此係 中i性低，故起因於密度無法提高 ，又，使用天然石墨作為#轰 … " 、 乍為无填助劑時，從實施例1之鲈果可 推論出因天然石墨备Ρ且戚Α 口 土…〜 則驅物的聚合，殘存於電池中之 未反應單fa有不氣影響。 實施例6 於正極及負極係除使用. —、 η 、 史J表4所不〈子复合石、墨才才料粉末以 外，，、餘與實施例2相同方法製作。 (正極用之前驅物的調整） 以已落解2.5 m〇I/升之哪4的此與γ _丁内酉旨與μ之以 ·· 1的混合溶劑作為電解液。含有環氧乙烷與環氧丙燒之共 聚合物所構成的平均分子量75〇〇〜9_之四官能丙婦酸醋 87955 -27- 200408154 單體、與平均分子量200〜300之單官能丙烯酸酯單體就重 量比為9 : 1的單體，以電解液與單體之比率為97 : 3之方式 混合於電解液中。於其溶液中相對於全重量加入UV起始劑 2000 ppm形成前驅物。 (負極用之前驅物的調整） 以已溶解1 mol/升之LiBF4的EC與r - 丁内酯與PC之1 ·· 2 :1的混合溶劑作為電解液。含有環氧乙烷與環氧丙烷之共 聚合物所構成的平均分子量7500〜9000之四官能丙烯酸酯 單體、與平均分子量200〜300之單官能丙烯酸酯單體就重 量比為8 : 2的單體，以電解液與單體之比率為95 : 5之方式 混合於電解液中。於其溶液中相對於全重量加入UV起始劑 2000 ppm形成前驅物。 (電池之製作） 於正極上重疊聚酯製不製布作為分隔膜，含浸正極用之 前驅物後，被石英製之板挾住，照射30 mW/cm2之UV光30 秒，使分隔膜與正極與電解質層形成一體化。 於負極含浸負極用之前驅物，同樣地照射UV光，負極與 電解質層會一體化。所得到之極以活性物質層呈對向之方 式貼合，插入於已加工成袋狀的鋁積層之中，在減壓下進 行熱封，以製作鋰聚合物電池。所得到之電池在電流值4 mA 、充電4.1 V-CCCV、放電2.75 V-CC之條件下反覆充放電， 測定循環特性。所使用之材料、混合比率等表示於表4中， 塗膜密度（沖壓前）、壓縮比、塗膜密度（沖壓後）、每一負極 活性物質層的體積能量密度、循環時之容量保持率表示於 -28- 87955 表5中。 實施例7 除使用SBR(苯乙烯丁二缔橡膠)：2份與⑽侧·"八 乍為負極之黏接材，使用水作為分散劑以夕卜 … 例6相同地製作鋰聚合物電池， ％、貝她 、人士 ^订p平估。混合比率等差千 於表4中，塗膜密度（沖壓前 寺表不 ^ G、、、侑比、塗膜密度（沖愚德、 、母一負極活性物質層的體積 後） 持率表示於表5中。_”贫度、循環時之容量保 比較例6 除使用表4所示之複人 6相同方法而製作科粉末以外，其餘與實施例 表4 作“物電池。結果表示於表5中。Ri, τ When the graphite powder powder was used alone (Comparative Examples 2 and 5), the electrode was only at the end of the heart A # ^ ^ -1 JL was low, and when natural graphite was used as an unfilled additive ( Compare you, ~; u, u, and zifa to full cycle characteristics. When this compound was used alone alone, the boring secret made ΤΓ low in this system, so it was caused by the inability to increase the density. When natural graphite is used as a # blaster, and it is an unfilled auxiliary at first, it can be inferred from the sea bass fruit of Example 1 that natural graphite is prepared from P and Qi A mouth soil ... ~ The polymer is polymerized and remains in the battery. The unreacted single fa has a gas-free effect. Example 6 The same as in Example 2 except that it is used in the positive and negative electrode systems. Method: (Adjustment of the precursor for the positive electrode) A mixed solvent of 2.5 μm / I which has been resolved with γ_butyrin and μ μ ·· 1 is used as the electrolyte. Contains a ring Tetrafunctional acetic acid vinegar with an average molecular weight of 7500 ~ 9_ composed of a copolymer of ethylene oxide and propylene oxide. 200408154 monomer and monofunctional acrylate monomer having an average molecular weight of 200 to 300 are monomers with a weight ratio of 9: 1, and are mixed in the electrolyte in such a manner that the electrolyte to monomer ratio is 97: 3. Add 2000 ppm of UV initiator to the total weight of the solution to form a precursor. (Adjustment of the precursor for the negative electrode) EC and r-butyrolactone and PC with 1 mol / L of LiBF4 dissolved 1 ·· 2 : 1 mixed solvent as electrolyte. It contains tetrafunctional acrylate monomer with average molecular weight of 7500 ~ 9000 composed of copolymer of ethylene oxide and propylene oxide, and monofunctional acrylate monomer with average molecular weight of 200 ~ 300. A monomer with a weight ratio of 8: 2 was mixed in the electrolyte in such a manner that the electrolyte to monomer ratio was 95: 5. In the solution, 2000 ppm of UV initiator was added to the total weight to form a precursor. (Production of the battery) A polyester non-woven fabric is laminated on the positive electrode as a separator. After impregnating the precursor with the positive electrode, it is held by a quartz plate and irradiated with 30 mW / cm2 of UV light for 30 seconds to make the separator. It is integrated with the positive electrode and the electrolyte layer. With the precursor, the UV light is similarly irradiated, and the negative electrode and the electrolyte layer are integrated. The obtained electrode is bonded with the active material layer facing each other, and is inserted into the aluminum laminate that has been processed into a bag shape. Heat sealing was performed under pressure to produce a lithium polymer battery. The obtained battery was repeatedly charged and discharged under conditions of a current value of 4 mA, a charge of 4.1 V-CCCV, and a discharge of 2.75 V-CC to determine the cycle characteristics. Materials used, The mixing ratio and others are shown in Table 4. The coating film density (before stamping), compression ratio, coating film density (after stamping), volume energy density of each negative electrode active material layer, and capacity retention rate during cycling are shown in -28- 87955 in Table 5. Example 7 Except the use of SBR (styrene butadiene rubber): 2 parts are bonded to the negative electrode "Bacha" as the negative electrode, and water is used as a dispersant to produce a lithium polymer battery. ,%, Betta, and people ^ set p estimate. The mixing ratio is even worse than that in Table 4. The coating film density (G ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,-)) and the coating film density (after Chong Yude,, and the volume of the mother-negative active material layer) are shown in Table 4. In Table 5. _ "Comparative Example 6 of Poorness and Capacity Guarantee at Cycle Time, except that the powder was produced by the same method as that of Furen 6 shown in Table 4, and the rest was used as" physical battery "in Table 4 of the Example. The results are shown in the table. 5 in.
從上述結果可 正因複合石墨材料粉末相異，循理特 87955 -29- 200408154 性會有很大差異。此係比較例之複合石墨材料粉末 始劑所產生的自由基會被石墨粉末消耗，纟負極：e 很多未反應單體，進—步，使用SBR(苯乙埽丁子 作為負極的黏接材時，可得到更優之性能。—布橡膠） 若依本發明，藉由使用—已混合複合石墨材料粉末 種類以上的負極活性物質，可得到高能量密度且長期可靠 性（循環特性）優之鋰聚合物電池。 非 心：而，依本發明所提供之鋰聚合物電池係使用化學交聯 ’時，故即使電池曝露於高溫下時，無凝膠溶解而進行液 狀化。因而，可得到很難引起電池之膨脹等的高 電池。 」里聚：物電池之特徵，在於可薄型化且形狀為自由點， 2内藏^電子機器的間隙而使用之，可更有效地發揮其 ^ 。在使用者操法簡單地更換之使用方法中，長期可靠 %池〈不易膨脹係非常重要，且此工業上的意義很重 大者。 【圖式簡單說明】 、表下本♦明之杈合石墨材料粉末的一例之斷面圖。 【圖式代表符號說明】 1 ......高結晶性石墨粉末 2 ......低結晶性碳材料 87955 -30-From the above results, due to the differences in the powders of composite graphite materials, the properties of Xuan Lite 87955 -29- 200408154 will be very different. In this comparative example, the free radicals produced by the composite graphite material powder initiator will be consumed by the graphite powder. 纟 Negative electrode: e Many unreacted monomers, further, when using SBR (phenyl ethyl hydrazone as the adhesive material for the negative electrode) More excellent performance can be obtained.-Cloth rubber) According to the present invention, by using a negative active material that has been mixed with more than one type of composite graphite material powder, lithium with high energy density and excellent long-term reliability (cycle characteristics) can be obtained. Polymer battery. Unexpected: When the lithium polymer battery provided by the present invention uses chemical cross-linking, even when the battery is exposed to a high temperature, there is no gel to dissolve and liquefy. Therefore, a high battery can be obtained which is difficult to cause battery swelling and the like. Liju: The characteristics of the battery are that it can be thinned and its shape is a free point. 2 It can be used with a built-in gap between electronic devices, and it can be used more effectively. In the use method that the user's method is simple to replace, the long-term reliability is very important, and the industrial significance is very important. [Brief Description of the Drawings] The table below is a cross-sectional view of an example of the graphite powder powder. [Explanation of Symbols of Drawings] 1 ...... Highly crystalline graphite powder 2 ...... Low crystalline carbon material 87955 -30-