TWI333705B - - Google Patents

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1333705 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用咼性能之固體電解質以實現高容 量、高安全性之链二次電池負極部件和其製造方法以及鋰 二次電池。 【先前技術】 現在公知之無機固體電解質多係關於以碟為成分之經離 子傳導性者’例如於日本特公平5-48582號公報以及John H.KENNEDY # 兩人於「IONICALLY CONDUCTIVE SULFIDE-BASED LITHIUM GLASSES」（Journal of1333705 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明[Prior Art] The inorganic solid electrolytes which are known in the prior art are related to the ion conductivity of the dish as a component, for example, in Japanese Patent Publication No. 5-48582 and John H. KENNEDY # two persons in "IONICALLY CONDUCTIVE SULFIDE-BASED LITHIUM" GLASSES" (Journal of

Non-Crystalline Solids 123(1990)’ p.328-338)中，揭示了Non-Crystalline Solids 123 (1990) 'p. 328-338), reveals

LhS-PJ5組成之非晶質固體電解質的特性。 此外’於傳導链離子之非晶質無機固體電解質中，如下 所述者公開了藉由將氧化合物添加至以硫化物為主要成分 之無機固體電解質，而使鋰離子傳導特性提高。 這些無機固體電解質之製法係藉由溶融體之急冷凝固、 或用球磨機等使粉體混合反應之機械研磨法，形成主要係 粉末以及粉末固結後之圓片狀、或急冷凝固後之塊狀、薄 片狀之形態。 於特開平4-202024號公報中’揭示了混合有氧化合物之 硫化物系高經離子傳導性之固體電解質。雖然於該文獻之 申請專利範圍中公開了以Li2〇、LiOH作為加入Li2S-P2S5系 « 硫化物中之含氧鋰化合物，但係於實施例中並未限定含氧 經化合物之添加量。 1333705 於專利第3343936號公報之實施例3中，公開了於Characteristics of an amorphous solid electrolyte composed of LhS-PJ5. Further, in the amorphous inorganic solid electrolyte which conducts chain ions, as described below, it is disclosed that lithium ion conductivity is improved by adding an oxygen compound to an inorganic solid electrolyte containing a sulfide as a main component. These inorganic solid electrolytes are produced by a rapid solidification of a molten body or a mechanical grinding method in which a powder is mixed and reacted by a ball mill or the like to form a main powder and a pellet after the powder is consolidated, or a block after rapid solidification. , the shape of the flakes. Japanese Laid-Open Patent Publication No. Hei-4-202024 discloses a solid electrolyte having a high ion conductivity of a sulfide-mixed aerobic compound. Although Li2〇, LiOH is used as an oxygen-containing lithium compound added to the Li2S-P2S5 system «sulfide in the patent application scope of this document, the addition amount of the oxygen-containing compound is not limited in the examples. 1333705 is disclosed in Example 3 of Patent No. 3343936,

LkS-PJ5系硫化物中添加U3p〇4。該實施例顯示其係藉由 添加3 mol% Li3P〇4(氧含量2.7原子％)使離子傳導率以及耐 電壓性提高。 於特開平2 0 (H - 2 5 0 5 8 0號公報之申請專利範圍中，公開了 aLi3P〇4_bLl2S_cP2S5組成之非晶質鋰離子傳導性固體電解 質’其中限定了 a<0.3，b>〇,3，c>0.2之組成範圍。 於米田等2人之「LuO-Uj-Pd5系非晶質部件中之鋰離 子傳導特性和混合陰離子效果」（第28次固體離子學討論會 演講要旨集 <2002年 1U>，p.24_25)中，表示 Li2〇Li2S_p2S5 組成在氧含量為1.9原子％時之離子傳導率最高。 在另一方面，關於以磷為主要成分之結晶固體電解質 方面並,又有關於含有氧之報告，例如，於特開 號公報以及濱等4人之"新賴之U2S_p2S5系玻璃陶曼之合成 和高經離子傳導性"（第26次固體離子學討論會演講要旨集 2000年11月>ρ·ΐ74-175)中，揭示了加熱Li2S_p2S^成非晶 質粉末使其結晶，此外，於村山、等4人之”新顆服系硫 代物之合成和物理特性、構造”（第28次固體離子學討論會 成之粉末顆粒狀結晶質固體電解質。 另一方然曾有人嘗試於負極上使用鐘金屬作為達 成經二次電池之高容量化的手法’但是藉由於充放電時與 包含於電池内之有機雷越#& ’機電解液的反應’會於負極上引起鋰金 屬之樹枝狀晶體的生長，掺Λ 我 w成正極之内部短路，以至於最 92-i00.doc 後會有***之虞。此外’該樹枝狀晶體之生長亦被認為係 充放電容量下降的原因之一。 已揭示之作為抑制樹枝狀晶體生長之方法之一，係於鋰 、-屬表面上形成聚合物膜或形成氣化物膜 '碳氧化合物 膜、氧化物膜（美國專利第5,314,765號說明書之申請專利範 圍第1項）、硫化物膜（美國專利第6,〇25,〇94號說明書之申請 專利範圍第4項、特開2000-340257號公報之申請專利範圍 第7項、特開2002-329524號公報之申請專利範圍第丨_3、9 項）等之無機膜。 尤其係，於特開2000-340257號公報、特開2002_329524 號公報中，揭示了於硫化物系固體電解質中含有氧。 【發明内容】 使用於鋰二次電池中之固體電解質所要求之特性係：高 链離子傳㈣、低電子傳導性以及良好之耐電壓特性。此 外，與於鋰金屬上形成固體電解質相關者還需要對鋰金屬 為女疋、固體電解質保護膜與鐘金屬之界面具密封性、以 及對有機電解液之安定性。特別重要的是，#使用固體電 解貝作為鋰金屬表面之保護膜時，必須使該固體電解質不 與鋰金屬發生反應，而且不會藉由鋰金屬發生還原分解。 關於鋰離子傳導性被認為須有至少1 0·4 s/cm以上之高離 子傳導性。雖然有機電解液通常具有1〇·3 s/cm之離子傳導 率，但是鋰離子之傳輸率為〇·2_〇·3左右，故實際上之鋰離 子傳導率為10-4s/cn^此外，鋰金屬上之保護膜如果有1〇.4 S/cm以上之離子傳導率就被視為無法防止離子之流動。 考慮到電子傳導性相對於離子傳導性必須低10的 4=，故以〜以下之低電子傳導體為較佳。 導丨生^時，固體電解質膜表面就會析出鋰金屬。 牙電堡性而言，則必須在細4VT還不發生分解。 特別係’必須對經今眉莖+A上 ^ 、屬4之負極活性物質之還原性穩 疋’難引起還原分解，又吝 刀鮮不產生或不增大電子傳導性。 本發明之目的係提供—錄 促択種滿足上述固體電解質所要求之 特性者、抑制因從鋰 生屬負極所發生之樹枝狀晶體而引起 之短路、能量密度高、充放電循環特性好之安定性、安全 性高之鋰二次電池。 潛心研究上述課題士 . 夂、，〇果係.糟由鋰、磷、硫以及氧元 素構成固體電解質之έ 士、 电鮮買之組成’並且控制其中之氧含量，就可 以解決了上述課題。 亦即，本發明係如下所述者： ⑴-種鋰二次電池負極部件，其係藉由於基材上層疊鋰 金屬膜、及無機固體電解質膜而形成，其特徵係：用下述 組成式來表示之含有雜、米^ '碟、硫、氧的無機固體電解質膜，： aLi' bP * cSd〇 硫、0 :氧） (Li :經、P :鱗、s 各元素之組成範圍係 0.20 ^ a ^ 0.45 > 0.10^ 0.20 , 0.35 S c S 0.60、 0.03 ^ 0.13 92400.doc •10- 1333705 續確保ΙΟ·4 S/cm以上之高離子傳導性，並且，除了耐電壓 性、低電子傳導性之外，還能夠達到抑制與鐘金屬發生反 應，而使固體電解質膜之覆蓋效果達到安定。 此外，形成於無機固體電解質膜下之鋰金屬膜的氧含 置，也對無機固體電解質膜之耐還原分解性產生影響。藉 由增加鋰金屬膜之氧含量，就能夠提高形成於其上之無機 固體電解質膜之安定性。亦即，隨著鋰金屬膜中之氧含量 變多，形成於其上之無機固體電解質膜之安定性亦隨之增 加，無機固體電解質膜中之氧含量變少之問題可獲解決，曰 藉由控制鋰金屬膜中之氧含量就能夠提 ，質之還原分解的效果。就此而言，以鐘金屬膜= 里為1原子％以上、1 〇局不〇/丨”丁在±上 原子/〇以下為較佳，以係1原子。/〇以 上' 5原子％以下為更佳。 當鐘金眉中之氧含量不到旧子叫，鐘金屬之還原力較 強如此就必/員增加氧含量，因為氧含量對於增強無機固 體電解質膜之耐還原性係、不可或缺的。此外，當經金屬膜 中之氧含量係超過10原子％之情況時，就會對鐘二次電池 之負、極γ來負面衫響。雖然氧含量落在從5原子％到1〇原子 %之範圍對實用上# & …、。1題’但若落於5原子％以下之範圍 中’則電池性能之安定性要更高。 另外’於鐘金屬膜與無機固體電解質膜之界面上，也可 以特定之厚度形成4人旦 3里夕之經金屬膜層，該鐘金屬膜層 之氧含量以55原子〇/η丨ν卞从 ... 下為限。不過，以該厚度係0.5 μιη以 下為車父佳，以係〇.3 _以下為更佳。 92400 doc -12- 1333705 下面藉由實施例進一步詳細地說明本發明。 如下面前述之製造例丨、2、3所 ..耒研究無機固體電解質 膜之，.且成、鋰金屬膜之形成以及氧 ^ ^ 巩3里之控制，確認任何 信況下都不會發生問題。 (製造例1)(固體電解質膜之形成） 按如下所示順序藉由雷射燒钱法於玻璃基材上形成鐘 (LD-磷（P)-硫（s)-氧（0)組成之無機固體電解質膜。 於填充著露點為-8(TC之氬氣之球形盒内，混合硫化裡 (LW)、五硫化磷（ϊ^5)、五氧化磷（PA)，然後將混合粉 末加入金屬模中並加壓來做成盤狀之目標物、 、 在不暴露於大氣中之情況下，藉由球形盒内部於成膜裝 置内移動益設置目標物，將雷射匯聚到目標物上使原料氣 化來於玻璃製基材上形成膜。不對基材進行特別加熱。 膜形成後.，用7 7 <社製ESCA54〇〇MC進行膜組成之分 析之結杲係鋰（Li)-磷（P)_硫（s)_氧（〇)組成分別為％原子％、 13原子％、54原子％、7原子％ ^ . 對每個玻璃基材都截斷膜形成後之試料，用掃描型電子 顯微鏡（SEM)來觀察，發現固體電解質膜厚係〇 5 。 於形成於玻璃基材上之無機固體電解質膜上形成金梳形 電極，藉由複數阻抗法從室溫變化到17〇乞之溫度來測定無 機固體毛解質膜之離子傳導率。17〇。〇退火後之離子傳導特 性變成25 C下之離子傳導率為3X1 〇-4 S/cm，活性化能量為 3 8 kJ/mol 〇 (製造例2)(固體電解質膜之形成） 92400.doc -14- 1333705 支樓台上。將作為原料之鋰金屬片加入到加熱容器 Ί It 真空吸引到蒸鍵裝置内。導入微量氧並加熱該加熱容器以 使鋰形成膜。 膜形成後，用7 7彳社製ESCA5400MC進行氧深度方向 之刀析’其結果係表面為52原子°/〇，當深度成為〇 46 !^瓜時 則為5原子％。表面之氧於試料處理階段使表面被氧化。 表面之氧化層能夠於無機固體電解質形成膜前，藉由離子 轟擊處理來除去。 (實施例1) 使用厚度為10 μπι之壓延銅箔作為基材，與製造例3同樣 藉由蒸鍍法於其上形成鋰金屬膜。鋰金屬膜之膜厚係 5 μπι。臈厚之測定藉由觸針式位差計來測定。進而，與製 造例1同樣，於形成0.5 μπι厚之鋰金屬膜之基材上進行離子 轟擊後，藉由雷射燒蝕法形成經（Li)_磷（Ρ)_硫（s)_氧（〇)組成 之無機固體電解質膜。無機固體電解質膜無色透明，試料 之色調成為底層之鋰金屬色。這些一連串製作步驟係於乾 燥氬氣氣體内進行。 無機固體電解質膜之組成藉由X射線光電子分光分析法 (XPS)來進行分析。於分析裝置中使用了 7 7 γ杜製 ESCA5400MC，使用限定之容器，並不使試料在不與大氣 接觸的情況下設置於分析裝置内。其結果係，剛做成後之 無機固體電解質膜之組成為Li: 26原子％、^ 15原子％、s : 5 5原子％、〇 : 4原子％。 此外，於深度方向之縱剖面中，由於越過了無機固體電 92400.doc -16· 1333705 解質層，所以隨深度之增加Li量增加，其他元素減少。而 且，於檢測不到Ρ和s之點的〇含量係3原子％。 試料做成後，保管於乾燥氬氣内，調查隨時間之安定性。 於經過做成後3個月之階段中，無機固體電解質層之透明性 沒有變化，試料之色調也沒有變化。此外，雖然藉由奶 分析該無機固體電解質層之組成，但是與剛做成後相比沒 有變化。 (實施例2) 用實施例1之方法形成鋰金屬膜以及無機固體電解質膜 後，然後藉由蒸錢法於無機固體電解質膜上形成金電極作 為遮蔽物。 測疋形成金電極之試料的直流電阻。雖然測定係使金探 針與金電極接觸’而於與銅落之間進行，但是當使金電極 側為負時’鐘離子係在無機固體電解質膜中從鐘金屬側流 向金電極側’測定峨離子料為基礎之電阻值。另外， 田使金電極側為正時’由於不存在從金電極側傳導之經離 子所以就可以測定無機固體電解質膜之電子傳導率。其 結果係於離子傳導方向之敎下顯示出5 Ω之值，於電; 向之測疋下顯示出1 Μ Ω之值。進而，雖然以測量隨 時間之變化為目的而於3個月後再次進行測^，但是仍顯示U3p〇4 was added to the LkS-PJ5 system sulfide. This example shows that the ionic conductivity and the withstand voltage are improved by adding 3 mol% of Li3P〇4 (oxygen content of 2.7 at%). An amorphous lithium ion conductive solid electrolyte composed of aLi3P〇4_bLl2S_cP2S5, which defines a <0.3, b>〇, is disclosed in Japanese Patent Application Laid-Open No. Hei. The composition range of 3,c>0.2. Lithium-ion conduction characteristics and mixed anion effects in the LuO-Uj-Pd5-based amorphous component of two people, such as Mi Tian (the 28th Solid Ionology Symposium) In 2002, 1U>, p.24_25), the Li2〇Li2S_p2S5 composition has the highest ion conductivity at an oxygen content of 1.9 atom%. On the other hand, regarding the crystalline solid electrolyte containing phosphorus as a main component, For the report on oxygen, for example, in the special publication and the four people of Bin, etc., "New Synthetic U2S_p2S5 Glass Ottoman's Synthesis and High-Through Ion Conductivity" (Speaking at the 26th Solid Ion Symposium) In the November 2000 issue, ρ·ΐ74-175, it is disclosed that the Li2S_p2S^ is formed into an amorphous powder to be crystallized, and in addition, the synthesis and physics of the new thiophene of the four people in Mt. Characteristics, Structure" (28th Solid Ionology) The discussion became a powdery granular crystalline solid electrolyte. On the other hand, there have been attempts to use the bell metal on the negative electrode as a means of achieving high capacity of the secondary battery, but by charging and discharging and organically contained in the battery. Lei Yue #& 'The reaction of the electrolyte' will cause the growth of dendrites of lithium metal on the negative electrode, and the internal short circuit of the doped yttrium, so that there will be an explosion after the most 92-i00.doc In addition, the growth of the dendrites is also considered to be one of the causes of the decrease in charge and discharge capacity. One of the methods for inhibiting the growth of dendrites has been disclosed as forming a polymer film or forming on a surface of lithium or a genus. A vaporized film 'carbon oxide film, an oxide film (Application No. 1 of the specification of U.S. Patent No. 5,314,765), a sulfide film (No. 4 of the specification of U.S. Patent No. 6, 〇25, 〇94) Inorganic membranes, such as the patent application scope of the Japanese Patent Application Laid-Open No. 2000-340257, No. JP-A-2002-329524, and the patent application No. _3, 9). In the sulfide-based solid electrolyte, oxygen is contained in the lithium-based secondary battery. The characteristics required for the solid electrolyte used in the lithium secondary battery are: high-chain ion transmission (four), low. Electronic conductivity and good withstand voltage characteristics. In addition, in connection with the formation of solid electrolytes on lithium metal, it is necessary to seal the interface between lithium metal, virgin, solid electrolyte protective film and clock metal, and to organic electrolyte. Stability. It is particularly important that when solid electrolyte is used as a protective film on the surface of a lithium metal, the solid electrolyte must not react with lithium metal and does not undergo reductive decomposition by lithium metal. Lithium ion conductivity is considered to have a high ion conductivity of at least 10.4 s/cm or more. Although the organic electrolyte usually has an ion conductivity of 1 〇·3 s/cm, the lithium ion transmission rate is about 〇·2_〇·3, so the actual lithium ion conductivity is 10-4 s/cn^ The protective film on lithium metal is considered to be unable to prevent the flow of ions if it has an ion conductivity of 1 〇.4 S/cm or more. In view of the fact that the electron conductivity is required to be 10% lower than the ion conductivity, it is preferable to use a low electron conductor of 〜 or less. When the lead is generated, lithium metal is precipitated on the surface of the solid electrolyte membrane. In the case of the tooth-electricity, it must be decomposed in the fine 4VT. In particular, it is necessary to reduce the reductive stability of the negative active material of the current eyebrow +A and ^4, and it is difficult to cause reductive decomposition, and the squeegee does not produce or increase the electron conductivity. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preventing and satisfying the characteristics required for the above solid electrolyte, suppressing short circuit caused by dendrites generated from a lithium-based negative electrode, and having high energy density and good charge-discharge cycle characteristics. Lithium secondary battery with high performance and safety. The above-mentioned problems can be solved by studying the above-mentioned subjects. The 夂, 〇 系 . . 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In other words, the present invention is as follows: (1) A lithium secondary battery negative electrode member formed by laminating a lithium metal film on a substrate and an inorganic solid electrolyte membrane, characterized in that the following composition formula is used An inorganic solid electrolyte membrane containing impurities, rice, dish, sulfur, oxygen, etc.: aLi' bP * cSd〇 sulfur, 0: oxygen) (Li: warp, P: scale, s, the composition range of each element is 0.20 ^ a ^ 0.45 > 0.10^ 0.20 , 0.35 S c S 0.60, 0.03 ^ 0.13 92400.doc •10- 1333705 Continued to ensure high ionic conductivity above S·4 S/cm and, in addition to withstand voltage, low electrons In addition to the conductivity, it is also possible to suppress the reaction with the metal, and the coverage of the solid electrolyte membrane is stabilized. Further, the oxygen content of the lithium metal film formed under the inorganic solid electrolyte membrane is also applied to the inorganic solid electrolyte membrane. The effect of reducing the reductive decomposition property can increase the stability of the inorganic solid electrolyte membrane formed thereon by increasing the oxygen content of the lithium metal film, that is, as the oxygen content in the lithium metal film increases, forming Inorganic solids thereon The stability of the decomposing film is also increased, and the problem of less oxygen content in the inorganic solid electrolyte membrane can be solved, and the effect of reductive decomposition of the substance can be improved by controlling the oxygen content in the lithium metal film. In the case of the bell metal film = 1 atom% or more, 1 〇 〇 丨 丨 丨 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± Good. When the oxygen content in Zhong Jinmei is less than that of the old one, the reducing power of the bell metal is so strong that the oxygen content is increased because the oxygen content is indispensable for enhancing the reduction resistance of the inorganic solid electrolyte membrane. Further, when the oxygen content in the metal film exceeds 10 atom%, the negative and the extremely γ of the secondary battery are negatively swayed. Although the oxygen content falls from 5 atom% to 1 atom%. The range is practical for # & ..., 1 question 'but if it falls within the range of 5 atom% or less', the stability of the battery performance is higher. In addition, 'the interface between the metal film and the inorganic solid electrolyte membrane , can also form a specific thickness of 4 people and 3 eves In the metal film layer, the oxygen content of the metal film layer is limited to 55 atomic 〇/η丨ν卞. However, the thickness is 0.5 μm or less for the car, and the system is 3.3 _ or less. More preferably. 92400 doc -12- 1333705 The present invention will be further described in detail by way of examples. The following examples of the production of 丨, 2, 3, 耒, the study of inorganic solid electrolyte membranes, and lithium metal The formation of the film and the control in the oxygen gas 3 confirmed that no problem occurred under any conditions. (Manufacturing Example 1) (Formation of solid electrolyte membrane) The glass was burned by laser in the order shown below. An inorganic solid electrolyte membrane composed of a clock (LD-phosphorus (P)-sulfur (s)-oxygen (0)) was formed on the substrate. In a spherical box filled with argon with a dew point of -8 (TC), mixed sulfurized (LW), phosphorus pentasulfide (ϊ^5), phosphorus pentoxide (PA), and then the mixed powder is added to the metal mold and added Pressing the object into a disk shape, and moving the inside of the ball box to the object in the film forming apparatus without being exposed to the atmosphere, the laser is concentrated on the target to vaporize the material. A film was formed on a glass substrate. The substrate was not specifically heated. After the film formation, the crucible lithium (Li)-phosphorus (P) was analyzed by the composition of the film composition of ESCA54〇〇MC manufactured by 7 7 < The composition of sulfur (s)_oxygen (〇) is % atom%, 13 atom%, 54 atom%, and 7 atom% ^. For each glass substrate, the sample after the film formation is cut off, using a scanning electron microscope ( SEM), it was found that the solid electrolyte film thickness was 〇5. A gold comb-shaped electrode was formed on the inorganic solid electrolyte membrane formed on the glass substrate, and was measured by a complex impedance method from room temperature to a temperature of 17 Torr. Ionic conductivity of inorganic solid decomposing membrane. 17〇. Ion conduction characteristics after annealing The ion conductivity at 25 C was 3×1 〇−4 S/cm, and the activation energy was 3 8 kJ/mol 制造 (Production Example 2) (formation of a solid electrolyte membrane) 92400.doc -14- 1333705 On the pedestal. The lithium metal sheet as a raw material is added to the heating container Ί It vacuum is sucked into the steaming key device. A small amount of oxygen is introduced and the heating container is heated to form a film of lithium. After the film is formed, the oxygen depth direction is performed by ESCA5400MC manufactured by 7 7 彳. The result is that the surface is 52 atomic ° / 〇, when the depth is 〇 46 ! ^ melon is 5 atomic %. The surface oxygen is oxidized in the sample processing stage. The surface oxide layer can be used in inorganic solids Before the electrolyte was formed into a film, it was removed by ion bombardment treatment. (Example 1) A rolled lithium foil having a thickness of 10 μm was used as a substrate, and a lithium metal film was formed thereon by vapor deposition in the same manner as in Production Example 3. The film thickness of the metal film was 5 μm. The thickness of the film was measured by a stylus type difference meter. Further, in the same manner as in Production Example 1, after ion bombardment was performed on a substrate on which a 0.5 μm thick lithium metal film was formed, Formation of (Li)_ by laser ablation (Ρ)_Inorganic solid electrolyte membrane composed of sulfur (s)_oxygen (〇). The inorganic solid electrolyte membrane is colorless and transparent, and the color tone of the sample becomes the lithium metal color of the bottom layer. These series of production steps are carried out in a dry argon gas. The composition of the inorganic solid electrolyte membrane was analyzed by X-ray photoelectron spectroscopy (XPS). In the analysis apparatus, 7 7 γ-made ESCA5400MC was used, and a limited container was used, so that the sample was not in contact with the atmosphere. The composition of the inorganic solid electrolyte membrane immediately after the preparation was Li: 26 atom%, 15 atom%, s: 55 atom%, and 〇: 4 atom%. Further, in the longitudinal section in the depth direction, since the inorganic solid electric layer 92400.doc -16· 1333705 is removed, the amount of Li increases as the depth increases, and other elements decrease. Further, the content of ruthenium at the point where Ρ and s were not detected was 3 atom%. After the sample was prepared, it was stored in dry argon gas, and the stability over time was investigated. The transparency of the inorganic solid electrolyte layer did not change during the three months after the formation, and the color tone of the sample did not change. Further, although the composition of the inorganic solid electrolyte layer was analyzed by milk, it was not changed as compared with that immediately after the formation. (Example 2) After forming a lithium metal film and an inorganic solid electrolyte membrane by the method of Example 1, a gold electrode was formed on the inorganic solid electrolyte membrane by a steaming method as a shield. The DC resistance of the sample forming the gold electrode was measured. Although the measurement is performed by contacting the gold probe with the gold electrode and proceeding with the copper drop, when the gold electrode side is made negative, 'the clock ion is flowing from the clock metal side to the gold electrode side in the inorganic solid electrolyte membrane' The resistance value based on the cerium ion material. Further, the gold electrode side of the field is positive. The electron conductivity of the inorganic solid electrolyte membrane can be measured because there is no ion transmitted from the gold electrode side. The result is a value of 5 Ω at the enthalpy of the ion conduction direction, and is measured as a value of 1 Μ Ω. Further, although the measurement is performed again after 3 months for the purpose of measuring the change with time, it is still displayed.

出相同Υ畜。Ο . I 另外，這些一連串製作步驟係於乾燥氬氣氣體 内進行。 (實施例3) μιη之壓延銅箔作為基材，與製造例3同樣 使用厚度為1 〇 1333705 藉由蒸録法於纟上形成鐘金屬帛。冑金屬㈣之膜厚係 5 Mm。膜厚之測定藉由觸針式位差計來測定。然後，與製 造例2同樣’藉纟雷射燒μ法於鐘金屬_成基材上形成 〇·5 um厚之鋰（Li)_磷（1>)_硫（3)_氧（〇)組成之無機固體電解 質膜。無機ϋ體電解質膜無色透明，試料之色調成為底層 之經金屬色。這些-連串製作步驟係於乾燥氬氣氣體内進 行。 無機固體電解質膜之組成藉由父射線光電子分光分析法 (XPS)來進行分析。於分析裝置中使用了 7 7 γ社製 ESCA5400MC，使錄定之容器，並在不使試料與大氣接 觸的情況下設置於分析裝置内。其結果係、，剛做成後之無 機固體電解質膜之組成為u : 29原子％、ρ: 13原子％、s 53原子％、〇 : 5原子％。 此外’於深度方向之縱剖面中，由於越過了無機固體電 解質層，所以Ο含量增至最大達到52原子％，然後隨深度之 增加，Ο含量減少，U量增加。〇含量增加到1〇原子％以上 之層厚係0·23 μπ^而且，於檢測不到？和3之點的〇含量係玉 原子％。 試料做成後，保管於乾燥氬氣内，並調查隨時間之安定 性。於經過做成後3個月之階段中，無機固體電解質層之透 明性沒有變化，試料之色調也沒有變化。此外，雖然藉由 XPS分析該無機㈣電解質層之組成，但是㈣做成後相 比沒有變化。 (實施例4) 92400 doc -18- 1333705 將於實施例1中做成之試料打穿一個丨5 mm直禋之孔並設 為負極。 正極係將成為活性物質之LiC〇〇2粒子、賦予電子傳導性 之碳粒子、聚（偏二氟乙烯）與有機溶劑混合，並塗敷於鋁箔 上而做成。正極之厚度為1〇〇 ，於3 ^ A . h(毫安·小 時）/cm2(平方釐米）之容量密度下，正極之直徑係15爪爪，總 容量係5.3 m A · h。 於露點- 80C以下之氬氣氣體下，於硬幣型單元電池内設 置負極、隔板（夕孔貝聚合物膜）以及正極，然後滴下一混合 溶液，做成鋰二次電池；該混合溶液包含丨m〇1%之溶解於 碳酸乙烯酯和碳酸丙烯酯之LiPF6(作為電解鹽）。 充放電之循環實驗於2.7 m A之恆定電流條件下，於充電 4.2 V、放電3.0 V之間進行。其結果係於5〇〇循環後，内部 不發生短路’也不會看到容量之下降。 於充放電循環貫驗後，分解電池扣，取出負極進行掃描 型電子顯微鏡（SEM)觀察以及能量分散X射線分析（edx)。 觀察到：看不見鋰金屬之樹枝狀晶體生長，並且於負極表 面保持了無機固體電解質層。 (實施例5 ) 將實施例3中所製成之試料打穿一個丨5 mm直徑之孔並設 為負極。 正極係將作為活性物質之LiCo〇2粒子、職予電子傳導性 之碳粒子、聚（偏二氟乙烯）與有機溶劑混合，並塗敷於鋁箔 上而製成。正極之厚度為1〇〇 μπ1，於3 mA.h(毫安.小 92400.doc •19- 1333705 時）/cm2(平方釐米）之容量密度下，正極之直徑係15 mm，總 容量係5.3 mA · h。 於露點-80°C以下之氬氣氣體下，於鈕扣形電池内設置負 極、隔板（多孔質聚合物膜）以及正極，進而滴下使1 m〇l〇/0 之LiPF0作為電解鹽溶解於碳酸乙烯和碳酸丙烯酯之混合 溶液’做成鋰二次電池。The same squid. Ο . I In addition, these series of fabrication steps are carried out in a dry argon gas. (Example 3) A rolled copper foil of μιη was used as a substrate, and a bell jar was formed on the crucible by a steaming method in the same manner as in Production Example 3 using a thickness of 1 〇 1333705. The film thickness of base metal (4) is 5 Mm. The measurement of the film thickness was measured by a stylus type difference meter. Then, in the same manner as in Production Example 2, lithium (Li)_phosphorus (1>)_sulfur (3)_oxygen (〇) was formed on the substrate by the laser firing method. An inorganic solid electrolyte membrane composed of. The inorganic steroid electrolyte membrane is colorless and transparent, and the color tone of the sample becomes the metallic color of the underlayer. These - series of fabrication steps are carried out in a dry argon gas. The composition of the inorganic solid electrolyte membrane was analyzed by parental ray photoelectron spectroscopy (XPS). In the analysis apparatus, ESCA5400MC manufactured by γ Sigma was used, and the recorded container was placed in the analysis device without contacting the sample with the atmosphere. As a result, the composition of the inorganic solid electrolyte membrane immediately after the formation was u: 29 atom%, ρ: 13 atom%, s 53 atom%, and 〇: 5 atom%. Further, in the longitudinal section in the depth direction, since the inorganic solid electrolyte layer is crossed, the niobium content is increased to a maximum of 52 atom%, and then as the depth increases, the niobium content decreases and the U amount increases. The layer thickness of the yttrium content increased to 1 〇 atom% or more is 0·23 μπ^ and is not detected? The content of bismuth at the point of 3 is the atomic % of jade. After the sample was prepared, it was stored in dry argon gas, and the stability over time was investigated. In the stage of 3 months after the formation, the transparency of the inorganic solid electrolyte layer did not change, and the color tone of the sample did not change. Further, although the composition of the inorganic (tetra) electrolyte layer was analyzed by XPS, (4) the post-phase ratio was not changed. (Example 4) 92400 doc -18 - 1333705 The sample prepared in Example 1 was punched through a hole of 丨5 mm straight and set as a negative electrode. The positive electrode is prepared by mixing LiC 2 particles as an active material, carbon particles imparting electron conductivity, and poly(vinylidene fluoride) with an organic solvent, and applying them on an aluminum foil. The thickness of the positive electrode is 1 〇〇. At a capacity density of 3 ^ A · h (milliampere hours) / cm 2 (cm 2 ), the diameter of the positive electrode is 15 claws, and the total capacity is 5.3 m A · h. Providing a negative electrode, a separator (the polymer film) and a positive electrode in a coin-type unit cell under a argon gas having a dew point of -80 C or less, and then dropping a mixed solution to form a lithium secondary battery; the mixed solution contains丨m〇1% of LiPF6 (as an electrolytic salt) dissolved in ethylene carbonate and propylene carbonate. The charge and discharge cycle experiment was carried out under a constant current of 2.7 m A at a charge of 4.2 V and a discharge of 3.0 V. As a result, after 5 cycles, no short circuit occurred inside, and no decrease in capacity was observed. After the charge and discharge cycle, the battery buckle was decomposed, and the negative electrode was taken out for scanning electron microscope (SEM) observation and energy dispersive X-ray analysis (edx). It was observed that the dendritic crystal growth of lithium metal was not observed, and the inorganic solid electrolyte layer was maintained on the surface of the negative electrode. (Example 5) The sample prepared in Example 3 was punched through a hole having a diameter of 5 mm and was set as a negative electrode. The positive electrode is prepared by mixing LiCo 2 particles as an active material, carbon particles of electron conductivity, and poly(vinylidene fluoride) with an organic solvent, and applying them on an aluminum foil. The thickness of the positive electrode is 1 〇〇μπ1, and the capacity of the positive electrode is 15 mm at a capacity density of 3 mA.h (milliampere. small 92400.doc • 19-1333705)/cm2 (cm 2 ). The total capacity is 5.3. mA · h. A negative electrode, a separator (porous polymer film), and a positive electrode are placed in a button-shaped battery under an argon gas having a dew point of -80 ° C or less, and LiPF0 of 1 m〇l〇/0 is dropped as an electrolytic salt. A mixed solution of ethylene carbonate and propylene carbonate is made into a lithium secondary battery.

充放電之循環實驗於2.7 mA之恆電流條件下，於充電4.2 V、放電3.0 V之間進行。其結果係於5〇〇循環後，内部不發 生短路’也不會看到容量之下降。 於充放電循環貫驗後，分解紐扣電池，取出負極進行掃 描型電子顯微鏡（SEM)觀察以及能量分散χ射線分析 (EDX)。觀察到：未見鋰金屬之樹枝狀晶體生長，並且於負 極表面保持了無機固體電解質層。 (實施例6)-(實施例12)The charge and discharge cycle experiment was carried out under a constant current of 2.7 mA at a charge of 4.2 V and a discharge of 3.0 V. As a result, after 5 cycles, no short circuit occurred inside, and no decrease in capacity was observed. After the charge and discharge cycle, the button cell was decomposed, and the negative electrode was taken out for scanning electron microscope (SEM) observation and energy dispersive X-ray analysis (EDX). It was observed that no dendritic crystal growth of lithium metal was observed, and an inorganic solid electrolyte layer was maintained on the surface of the negative electrode. (Embodiment 6) - (Embodiment 12)

、製作構成與實施例4相同但無機固體電解質膜之組4 變的鐘二次電池’並調查其特性。其結果顯示於表心 外，雖然於本實施例中之無機固體電解質膜的形成，令 由^射燒錢來實施，但是並不局限於此，也心^ 空洛鍍法、RF韻法等其他手法來進行製作。 92400.docA clock secondary battery constituting the same composition as in Example 4 except that the inorganic solid electrolyte membrane was changed, and the characteristics were examined. The result is shown in the outside of the center of the watch. Although the formation of the inorganic solid electrolyte membrane in the present embodiment is carried out by burning the money, it is not limited thereto, and the method is also a hollow plating method, an RF rhyme method, or the like. Other methods to make. 92400.doc

•2CK 丄 W705 表1 試驗結果 固體電解質膜 組成（XPS分析 值） 實施例• 2CK 丄 W705 Table 1 Test results Solid electrolyte membrane Composition (XPS analysis value) Example

• 1 L• 1 L

S 調化個 } 色變(3月後 值 阻 電 流 直 Ω |離子傳導側 時變(3月 隨間化個後 電子傳導側 充放電 循環 S/cm kJ/ m〇lS 调化 } } Color change (after 3 months value resistance current straight Ω | ion conduction side time change (after March), electron conduction side charge and discharge cycle S/cm kJ/ m〇l

氣作構成與實施例4相同但無機固體電解質之組成逸朋 眭I月範圍的鋰二次電池作為比較例，並調查其電池相 ./、、’ °果顯不於表2中。此外，以比較例1表示之試料在 個月後之變質狀、、兄# 欠貝肽况顯示於表3中。 於比較例1中，由一 持長時間安定性，：氧含量低，無機固體電解質膜未能維 中，由於氯人旦所从電池性能就較低。此外，於比較例: 就變得不足。 斤以離子傳導率變低，所以電池性能 92400.doc -21 - I333705 表2 比 較 例 固n (X [電解質膜組成 PS分析值） 試驗結果 Li P S 〇 色調變 化（3個 月後） 直流電阻值（Ώ ) 複數阻抗法離 子傳導率（170 °C退火） 充放 電循 環 離子 傳導 側 電子 傳導 側 隨時間變 化（3個月 後） S/cm kJ/mol 1 26 15 57 2 有 3 1M 有 5xl(T 35 150 1 21 13 41 15 無 100 1M 無 2χΐσ5 「51 200 表3 比 較 例 固體1 (3個月 (xps^ Li :解質膜組成 後） 卜析值） 試驗結果 P S 0 色調 (3個月後） 直流電阻值（Ω ) (1個月後） 離子傳 導側 電子傳 導側 1 ~~~~- 65 5 28 2 黑色化、綠色 化、不透明化 1000 1M (比較例3、4)The composition of the inorganic solid electrolyte was the same as in Example 4, but the lithium secondary battery of the composition of the inorganic solid electrolyte was used as a comparative example, and the battery phase of the battery was not investigated in Table 2. Further, the deterioration of the sample shown in Comparative Example 1 after the month and the condition of the broiler of the brother # are shown in Table 3. In Comparative Example 1, since the long-term stability was maintained, the oxygen content was low, and the inorganic solid electrolyte membrane was not maintained, and the performance of the battery was low due to the chlorine. In addition, in the comparative example: it becomes insufficient. The ionic conductivity is lower, so the battery performance is 92400.doc -21 - I333705 Table 2 Comparative example solid n (X [electrolyte membrane composition PS analysis value) Test result Li PS 〇 color change (after 3 months) DC resistance value (Ώ) Complex Impedance Ion Conductivity (170 °C Annealing) Charge-discharge cycle ion conduction side electron conduction side changes with time (after 3 months) S/cm kJ/mol 1 26 15 57 2 There are 3 1M with 5xl ( T 35 150 1 21 13 41 15 No 100 1M No 2 χΐ σ5 "51 200 Table 3 Comparative Example Solid 1 (3 months (xps^ Li: after decomposing film composition) Analysis value) PS 0 tone (3 months) After) DC resistance value (Ω) (after 1 month) Ion conduction side electron conduction side 1 ~~~~- 65 5 28 2 Blackening, greening, opacity 1000 1M (Comparative examples 3, 4)

形成構成與實施例4相同但氧含有量逸脫本發明範圍之The formation configuration is the same as that of Embodiment 4, but the oxygen content is out of the scope of the present invention.

無機固體電解質作為比較例，以調查其電池循環特性。其 結果顯示於表4中。 於比較例3中，由於氧含量低，無機固體電解質膜未能維 持長時間之安定性，所以電池性能就較低。此外，於比較 (列4中，山 、 ’由於氧含量過多所以電池性能就變得不足。 表4 質膜組成 直） 鋰金屬 (XPS分析值） 試驗結果 S 0 0 色調 (1個月後） 充放電 循環 55 2 <0.5 有 150 —55 2 11 無 ~ΓοόAn inorganic solid electrolyte was used as a comparative example to investigate the battery cycle characteristics. The results are shown in Table 4. In Comparative Example 3, since the oxygen solid content was low, the inorganic solid electrolyte membrane failed to maintain long-term stability, so battery performance was low. In addition, in comparison (column 4, mountain, 'the battery performance becomes insufficient due to excessive oxygen content. Table 4 Plasma membrane composition is straight) Lithium metal (XPS analysis value) Test result S 0 0 Hue (after 1 month) Charge and discharge cycle 55 2 <0.5 has 150 —55 2 11 no~Γοό

92400.doc -22- 1333705 產業上之可利用性 4據 斤述之本發明，可獲得-種抑制因經金屬負極 發生樹枝狀晶體而引#夕 之紐路、能量密度高且充放 特性優良之安m安全性值〜 ㈣電循％ '、女！〖生俱尚之鋰二次電池。 92400 doc •23-92400.doc -22- 1333705 Industrial Applicability 4 According to the invention described above, it is possible to obtain a kind of inhibition of dendritic crystals through a metal negative electrode, which leads to a high energy density and excellent charge and discharge characteristics. The security value of the security ~ (four) electric cycle % ', female! 〖Limited lithium secondary battery. 92400 doc •23-

Claims (1)

13337051333705 第093109525號專利申請案 中文申請專利範圍替換本(9'9年8月） 拾、申請專利範圍： 1. -種鐘二次電池負極部件，其特徵在f於基材上層疊 鋰金屬膜及無機固體電解質膜而形成，該無機固體電解 質膜含有H硫、氧，且以τ述組成式表示： aLi-bPcS-dO (Li :鐘、P :磷、s :硫、〇 :氧） 各元素之組成範園係 0.20$ 0.45、 0.10$ 0.20、 0.35^ 0.60 χ 0.03 S 〇. 13 (a+b + c+d=l); 且該氧之含量係丨原子％以上、ι〇 前述鋰金屬膜含有氧 原子％以下。 3. 2.如以專鄉圍第1項之鐘二次電池負極部件，其中於前 述鋰金屬膜與前述無機固體電解質膜之界面，存在有氧 含量為1〇原子。/。以上、55原子％以下之鐘金屬膜層。 : = 極部件之製造方法，其係製造如申請 專利把圍第1或弟2項之鐘二次電池負極部件者，其特徵 在於：藉由氣相法形成前隸金屬膜及無機固體電解質 膜，该乳相法係蒸鍍法、離子噴鑛（i〇npi 鍍法或雷射燒蝕法。 ^ f藏 4. 一種鋰二次電池，其特徵係： 弟2項之裡一次電池負極部件 使用如申請專利範圍第1或 92400-990819.docPatent Application No. 093109525 (Chinese Patent Application No. 093109525) (9'9 August) Pickup, Patent Application Range: 1. - A secondary component of a secondary battery, characterized in that a lithium metal film is laminated on a substrate and It is formed by an inorganic solid electrolyte membrane containing H sulfur and oxygen, and is represented by a composition formula of τ: aLi-bPcS-dO (Li: bell, P: phosphorus, s: sulfur, antimony: oxygen) each element The composition of the garden is 0.20$ 0.45, 0.10$ 0.20, 0.35^0.60 χ 0.03 S 〇. 13 (a+b + c+d=l); and the oxygen content is more than 丨 atom%, ι〇 the aforementioned lithium metal The film contains oxygen atoms or less. 3. 2. For the secondary battery negative electrode component of the first item, the interface between the lithium metal film and the inorganic solid electrolyte membrane described above has an oxygen content of 1 atom. /. Above, 55 atomic percent or less of the metal film layer. : = manufacturing method of a pole part, which is manufactured by applying a patent to a secondary battery secondary member of the first or second item, characterized in that a front metal film and an inorganic solid electrolyte membrane are formed by a vapor phase method. The milk phase method is an evaporation method, an ion spray method (i〇npi plating method or a laser ablation method). ^ f. 4. A lithium secondary battery, characterized by: a secondary battery negative electrode component Use as claimed in the scope of the first or 92400-990819.doc