TWI260812B

TWI260812B - Thin film battery, cathode film for thin film battery and preparation method thereof

Info

Publication number: TWI260812B
Application number: TW93125448A
Authority: TW
Inventors: Maw-Kuen Wu; Chia-Lin Wang; Yang-Chung Liao; Nyan-Hwa Tai; Fong-Chi Hsu
Original assignee: Academia Sinica
Priority date: 2004-08-26
Filing date: 2004-08-26
Publication date: 2006-08-21
Also published as: TW200608620A

Abstract

According to the preparation method for cathode film for thin film battery of this invention, the cathode film of the invented thin film battery is prepared by first preparing a target material that supplies Li and Ti ions and a substrate comprising a base, a buffer layer and a precious metal current collection layer. An LiMO layer is grown on the substrate by sputtering in a vacuum chamber under higher temperature to obtain the cathode film for thin film battery of this invention. The precious metal current collection layer may contain precious metals such as Ag, Au, Pt and their alloys or oxides. The sputtering temperature may be above 300 DEG C, preferably above 500 DEG C, and most preferably above 650 DEG C. The obtained cathode film may contain Li4Ti5012. This invention also discloses the cathode film so prepared and the thin film battery using such cathode film.

Description

1260812— Γ 1 ^》'更;主養穩只)3125448 %年、0月J曰修正 i^&D 膜」？1 種 - 於關是別特池電膜 1薄垃種領一術於技關 /之是 ”屬明|綱所發 |明明本一發务、五 t 薄術科下極技著} 負前隨率之先功池丨 ( 膜薄流。電視 ^p Ultul ^^^ητη 所到及受化池小電微膜寸薄尺的件色元特子化電型，薄步有進具的，技降、積命入壽融環能循和的低長率極電 :放如自有、〇具性點還化優，變等外度中小高件微狀元較形路寸、電尺性別了全個除安或池的路電度電膜高體著所夾質間物極態電固負由、全正池丨 ΠΎ 是膜皆薄 ,於樣在一別池差電的般要一主和。池成膜所薄質解 B»色化氧金金 ttul 鋰括包料材。極池負 ^H/OH 膜用薄使態池固電稱膜又薄故供，可成組在電料成材造極，負旦里分容部電大逆而可然不。的物大匕艮 #1 //1 氧著屬隨金伴渡皆過，鋰時、電物放化充氮次 ’ 1 物第佳極優 Λ 二 ο丨壽環 4T循 • 1 L 的長中和物壓化電氧作屬工金的渡坦過平 Ctui 鋰、而性。逆差可變電能放性充池的法1260812— Γ 1 ^》'More; main raise only 3125448% year, 0 month J曰 Correct i^&D film ”? 1 kind - Yu Guan is a special cell membrane 1 thin waste collar one skill in the skill off / it is "genuine | outline issued | clearly this one hair, five t thin surgery under the extreme skills} negative The rate of the first power pool (film thin flow. TV ^ p Ultul ^ ^ ^ η τη and the small small electric micro-film thin film of the chemical pool, the special element of the color, the thin step has the introduction, technology The low-rate ultra-electricity that falls into the life and the life of the ring can be used as a self-contained, self-contained, and refining, and the other small and medium-sized high-grade micro-elements are more like the shape of the road and the electric scale. In addition to the safety or the channel, the electric circuit is high in the body of the interstitial material. The whole positive pool is thin, and the film is thin in a different pool. The thin film of the film-forming film B»coloring oxygen gold gold ttul lithium package material. The pole pool negative ^H / OH film with a thin state of the pool solid electric film is thin and therefore available, can be grouped in the electric material Into the material, the negative capacity of the sub-division department is not the same. The material is big #1 //1 Oxygen is accompanied by the gold, lithium, Electrochemical radiochemical nitrogen filling '1 thing is the best of the best Λ 2 丨丨环 4T Circulation 1 L long and medium pressure electric oxygen for the work of the gold of the crossing of the Ctui lithium, and the sex. Variable electric energy charging method

適止} 合為1 6 是前 S I 此目 1 ο 因到 S 極4T • 1 負 L 的，膠式凝方 -的膠理溶處以熱是溫皆高備加製施的以一膜， _01板「L 5 彳i基到佈塗 ¾ 優法方的膠凝 - 膠溶 ο 膜及直低能較不本式成方作程製製、的徑法粒膠的凝級一# ^ ^ 1奈溶 —A i 、以 4T佳是 Li制但的控。化構等晶結快結分較有成度具：速到括積得包沉均佳較有法具鍍膜濺薄以的〇製中鑛件所元使路可電，別膜個薄或製路鍍電} g 體 η * 1 積 r e 到 t t 合 u p 結s 接cAppropriate} Combination 1 6 is the former SI This item 1 ο Because the S pole 4T • 1 negative L, the gel-type square - the gel solution dissolves with heat, the temperature is high, and the application is made with a film, _01 Plate "L 5 彳i base to cloth coating 3⁄4 优法方的凝凝-胶胶ο 膜 and straight low energy can not be made in this way, the diameter of the granules of the granules # ^ ^ 1 solution - A i , 4T is better than Li. However, the chemical structure and other crystal knots are more versatile: the speed to the inclusion of the package is even better than the method of coating with thin coating The element can make electricity, and the film is thin or the circuit is plated} g body η * 1 product re to tt and up s s

)lt 鍵[93125448 五、發明說明（2))lt key [93125448 V. Description of invention (2)

修正勻性、容易控制成分與表面型能鍍法鍍製Li 仏/專膜，而具有"炎點。因此，如何以濺人士的一大課題。又的功能’成為此行業【發明内容】本發明之目的即在提供為薄膜電池之負極薄膜。本發明之目的也在提供製法。種新穎的薄膜電池及適合作種溥膜電池及其負極薄膜之本發明之目膜之材料之製造本發明之目的更薄膜之製法。依據本發明可提供Li及Ti離及一貴金屬集電鍍L i Μ 0層，而完中，該貴金屬集氧化物。濺鍍溫佳為6 5 0°C以上< 發明並揭示以此成之薄膜電池。【實施方式】 =在提供一種以LiM0為薄膜電池以及據此製成之負極薄膜。在、供-種適合用在積體電路製程之負極 :薄膜電池負極薄膜之製法，係先製備一之靶材，以及一具有—基層，一緩衝層 2基板。於真^腔中以高溫在基板上濺 ^發明之薄膜電池負' 極薄膜。在本發明電層可為銀、金、鉑等貴金屬，其合金或度可為3 0 (TC以上，較佳為5 〇叱以上，最所形成之負極薄膜材料可為L i 4T i 50 12。本方法製成之負極薄膜及利用該負極薄膜製 .本發.明之溥膜電池負極薄膜之製法，係先製備一可提士 L 1及T 1離子之靶材，以及一具有一基層，一緩衝層及一貝金屬集電層之基板。於真空腔中以高溫在基板上濺鍍 1260811 「---—~~~—93125448-—年 G 月 <?日修正五、發明說明（3) — ~ L 1 M0層，而完成本發明之薄膜電池負極薄膜。在本發明中’所形成之負極薄膜材料可為L i j i 5〇 12。該貴金屬集電層可為銀、金、鉑、鈀等貴金屬，其合金或氧化物。濺鍍溫度可為3 0 (TC以上，較佳為5 〇 ye以上，最佳為6 5 ο”以上。所形成之負極薄膜材料可為L i J i 5〇 12。以下說明本發明之詳細步驟及内容。Correction Uniformity, easy control of composition and surface type plating Li 仏 / film, and with "flame point." Therefore, how to splash a big subject. Further, the function is the industry. SUMMARY OF THE INVENTION The object of the present invention is to provide a negative electrode film for a thin film battery. The object of the present invention is also to provide a process. A novel thin film battery and a material for the film of the present invention which is suitable for use as a enamel film battery and a negative electrode film thereof. The object of the present invention is a film forming method. According to the present invention, it is possible to provide Li and Ti ions and a noble metal current collector plated Li Μ 0 layer, and in the end, the noble metal collects oxide. The sputtering temperature is preferably 650 ° C or more. The thin film battery is invented and disclosed. [Embodiment] = A thin film battery using LiM0 and a negative electrode film produced therewith are provided. The method for producing a negative electrode for a thin film battery is to prepare a target material, and a substrate having a base layer and a buffer layer 2 . In the true cavity, the negative electrode film of the thin film battery was invented on the substrate at a high temperature. The electric layer of the present invention may be a noble metal such as silver, gold or platinum, and the alloy or degree thereof may be 30 (TC or more, preferably 5 Å or more, and the most formed negative electrode film material may be L i 4T i 50 12 The negative electrode film produced by the method and the negative electrode film of the present invention, which are prepared by using the negative electrode film, are prepared by first preparing a target of a sylvestre L 1 and a T 1 ion, and having a base layer. a buffer layer and a substrate of a metal collector layer. Sputtering 1260811 on the substrate at a high temperature in a vacuum chamber. "----~~~---------------------------------------- 3) - L 1 M0 layer, and the negative electrode film of the thin film battery of the present invention is completed. In the present invention, the negative electrode film material formed may be L iji 5〇 12. The noble metal collector layer may be silver, gold or platinum. a precious metal such as palladium, an alloy or an oxide thereof. The sputtering temperature may be 30 (TC or more, preferably 5 〇 ye or more, and most preferably 6 5 ο or more). The negative electrode film material may be L i J i 5〇12. The detailed steps and contents of the present invention are described below.

Li 4Ti此歡材的製備利用固悲反應法（s ο 1 i d s t a t e r e a c t i ο η)燒結所需的把材。選取適當計量比例的u 2c〇和Ti02( ruti le pha^e)為起始原料，均勻混合研磨後，使用高溫箱爐以 8 0 0 C持溫預燒1 5小時，再均勻研磨而得到顆粒細小的白色粉末。經油壓機以1 2，6 0 〇kg冷壓成形，在9 5 0°C持溫燒結25小時，得到所需的靶材。刮下些許的粉末利用XRD (MAC MXP3)來做粉末結構分析。棊皇—1備— 選擇S i 0〆S i ( 1 〇〇)為基板，依序利用丙酮、甲醇及異丙醇等有機溶劑在超音波震盪器中清洗3 〇分鐘，再利用 DC磁控濺鍍法依序鍍上緩衝層及貴金屬集電層。貝金屬層作為集電層（current collector)，用來提供電子的進出。適用之材料包括銀、金、鉑、鈀等或其合金、氧化物等。其他適合用作集電層並能幫助負極薄膜結晶之材料或其組成物，也可適用。在本發明之實例中，係選用金作為貴金屬集電層。其厚度約2 〇到5 0 0 0 較好為500-2000 >通常而言，1〇〇〇土厚度，即可適用。Li 4Ti is prepared by sintering the desired material by the solid-stable reaction method (s ο 1 i d s t a t e r e a c t i ο η). Select appropriate proportions of u 2c〇 and Ti02 ( ruti le pha^e) as starting materials, uniformly mix and grind, and then pre-fire for 15 hours at 8000 ° C using a high temperature box furnace, and then uniformly grind to obtain granules. Tiny white powder. It was cold-formed by a hydraulic press at 1, 2,60 〇kg, and sintered at 950 ° C for 25 hours to obtain a desired target. A small amount of powder was scraped and XRD (MAC MXP3) was used for powder structure analysis.棊皇—1 Preparation — Select S i 0〆S i ( 1 〇〇) as the substrate, sequentially clean it in an ultrasonic oscillator with an organic solvent such as acetone, methanol and isopropanol for 3 , minutes, and then use DC magnetron The sputtering method is sequentially applied with a buffer layer and a noble metal collector layer. The shell metal layer acts as a current collector to provide electron in and out. Suitable materials include silver, gold, platinum, palladium, etc. or alloys, oxides thereof and the like. Other materials suitable for use as a collector layer and capable of helping the anode film to crystallize or a composition thereof are also applicable. In the examples of the present invention, gold is selected as the noble metal collector layer. The thickness is about 2 〇 to 50,000, preferably 500-2000 > Generally, the thickness of 1 〇〇〇 is applicable.

第10頁相一.-- -.. 年雄喊驗)正替換4 〇 —Γ_m ^3125448_年 C _ 五、發明說明（4) ~~' 緩衝層（bu f f e 〇可改善貴金屬層與基板間的附著力。適用之材料為Ti、Co、Cr、Mo、Zr、W，等或其合金或矽化物。厚度可為10-1000，較好為1〇〇足右。薄屋鍍_皇> 將製備之基板以銀膠黏在基板治具上，如為量測電化學性質的試片，則以S i基板遮住一角落，以便之後電極線的連接。銀膠烘乾之後將基板放入真空腔體内，進行真空濺鍍。執行真空濺鍍之方式並無特殊限制，可為任何適用之機器。在本發明之實例中，係使用射頻磁控濺錢 (radio frequency magnetron sputtering)。利用機械泵浦和擴散泵浦抽氣，直到腔體壓力值小於1 〇 _5 t〇rr。加熱基板治具（5°C / m i η)直到所需的工作溫度。工作溫度宜在南溫範圍，例如在3 0 0°C以上，較佳者為5 〇〇°C 以上。而在7 0 0°C以上，可獲得優異之效果。經由流量控制器（mass f l〇w control ler)通入3〇sccn^ 工作氣體。工作氣體可為Ar和0钓混合氣，其比例可約為 3 : 2，並控制腔體的壓力值在約3 0 m t 〇 r r左右。點燃電漿，逐漸增加濺鍍功率至工作功率，並先預打 2 0分鐘清除附著於靶材表面的污染物，再打開擋板 ' (shutter)，進行薄膜鍍製。鍍製時間視需要而定，— 般可為約2小時。完成後以5°C /mi η降溫。樣品量測以X光繞射儀量測薄膜的結構及結晶性。儀器為mac MXP3。以Cu-Κα (波長λ = 1.5405A)為入射光源，工彳乍電Page 10 Phase One.---.. Year-old screaming) Replace 4 〇-Γ_m ^3125448_year C _ V. Invention description (4) ~~' Buffer layer (bu ffe 〇 can improve precious metal layer and substrate The adhesion between the materials is Ti, Co, Cr, Mo, Zr, W, etc. or its alloy or telluride. The thickness can be 10-1000, preferably 1 〇〇 to the right. > The prepared substrate is adhered to the substrate fixture with silver glue. For the test piece for measuring electrochemical properties, the Si substrate is covered with a corner to connect the electrode wires. After the silver glue is dried, The substrate is placed in a vacuum chamber for vacuum sputtering. The method of performing vacuum sputtering is not particularly limited and may be any suitable machine. In the example of the present invention, radio frequency magnetron sputtering is used. Pumping with mechanical pumping and diffusion pumping until the chamber pressure is less than 1 〇 _5 t 〇 rr. Heat the substrate fixture (5 ° C / mi η) until the desired operating temperature. The working temperature should be The south temperature range is, for example, above 300 ° C, preferably above 5 ° ° C. Above 700 ° C, Excellent results. 3 〇sccn^ working gas is supplied via the mass controller (mass fl〇w control ler). The working gas can be a mixture of Ar and 0, which can be about 3:2, and the cavity is controlled. The pressure value is around 30 mt 〇rr. Ignite the plasma, gradually increase the sputtering power to the working power, and pre-play for 20 minutes to remove the contaminants attached to the surface of the target, then open the baffle' (shutter) For film plating, the plating time is as needed, usually about 2 hours. After completion, the temperature is lowered at 5 ° C /mi η. The sample is measured by X-ray diffractometer to measure the structure and crystallinity of the film. The instrument is mac MXP3. Cu-Κα (wavelength λ = 1.5405A) is the incident light source.

126081¾ i i Γ « Y a 修正案號 93125448 年 --—- 五、發明說明（5) 壓40 kV、電流30 mA，掃描速率為20/min ’進行㊀/2㊀董測。由XRD粉末繞射儀結果得知，經過高溫燒結的L 1 J 1 5〇 12 革巴材具有尖晶石結構的單一純相，如第1圖所不。實驗結果顯示，當在基板溫度為5 0 0°C時，進行賤鍵 L i 4T i 50 !满膜具有結晶化的尖晶石結構。隨著濺鍍時基板溫度上升，其結晶性明顯大幅度增加’且以（1 1 1)平面為其優選方位，如第2圖所示。以場發射掃描電子顯微鏡觀察薄膜表面型態、晶粒大小、橫截面、薄膜厚度。利用鑽石刀在試片背面晝上一道割痕，將試片折斷，以獲得L i 4T i 5〇 1與膜的橫截面’將試片橫截面直立固定在導電膠帶上，置於JE〇L-6 5 〇〇電子顯微鏡，觀察之。第3圖、第4圖為L i 4T i 50 !在不同藏嫉溫度下在 Au/Ti/Si02/Si薄膜表面形貌和橫截面圖。圖中顯示’在 5 0 0°C下成長的薄膜為平坦而且緻密的枉狀晶結構。隨著濺鍍溫度的上升，晶粒尺寸明顯變大但依舊緻密的排列。當濺鍍溫度超過6 5 0°C，薄膜將呈現粗糙且鬆散排列的柱狀晶結構。電化學性質的量測將1M LiPF瘳於體積比為1 : 1的EC/EMC ( 1 : 1)混合溶液，製成電解液。在手套箱中（DLX-ΟίΠ-D MOD，1260813⁄4 i i Γ « Y a Amendment Case No. 93125448 ---- V. Description of invention (5) Press 40 kV, current 30 mA, scan rate is 20/min ‘1⁄2 to measure. From the results of the XRD powder diffraction apparatus, it was found that the high-temperature sintered L 1 J 1 5〇 12 leather material had a single pure phase of a spinel structure, as shown in Fig. 1. The experimental results show that when the substrate temperature is 500 ° C, the 贱 bond L i 4T i 50 ! full film has a crystallized spinel structure. As the temperature of the substrate rises during sputtering, the crystallinity is significantly increased by a large extent, and the (1 1 1) plane is its preferred orientation, as shown in Fig. 2. The surface morphology, grain size, cross section, and film thickness of the film were observed by a field emission scanning electron microscope. Use a diamond knife to cut a test piece on the back of the test piece, and break the test piece to obtain the cross section of the film L i 4T i 5〇1 and the film. The test piece cross-section is erected on the conductive tape and placed on the JE〇L. -6 5 〇〇 Electron microscope, observe it. Fig. 3 and Fig. 4 are the surface topography and cross-sectional view of the Au/Ti/SiO2/Si film at different Tibetan mastiff temperatures. The figure shows that the film grown at 500 ° C is a flat and dense 枉-like crystal structure. As the sputtering temperature increases, the grain size becomes significantly larger but still densely aligned. When the sputtering temperature exceeds 650 °C, the film will exhibit a coarse and loosely arranged columnar crystal structure. Measurement of electrochemical properties 1M LiPF was dissolved in an EC/EMC (1:1) mixed solution of a volume ratio of 1:1 to prepare an electrolyte. In the glove box (DLX-ΟίΠ-D MOD,

Vacuum Atmospheres Company)另字製備完成的 L i 4T i 5〇 } 膜和電解液置於模具内。以L i J i 5〇 j專膜為一電極再搭配鋰金屬箔為另一電極，中間以隔膜隔開以防止正負極材料直接接觸而短路。將上蓋套上0 - r i n g鎖緊以維持氣密度。Vacuum Atmospheres Company) L i 4T i 5〇 } The membrane and electrolyte are placed in the mold. The L i J i 5〇 j film is used as an electrode and the lithium metal foil is used as the other electrode, and the middle is separated by a diaphragm to prevent direct contact between the positive and negative electrodes and short circuit. Lock the upper cover with 0 - r i n g to maintain the air density.

第12頁 95Ι26Θ§1|^ ___案號9312^^g_7年(p月日修正五、發明說明（6) ~——一~·— 完成電池組裝。以循環伏安法分析L i J i 5〇 !與膜的氧化還原峰和鐘定薄膜的純度。在1〜2 V間以0 · 5 mV/ s掃描速率進行量^，第5圖顯示對不同溫度下濺鍍所得之L i j丨5〇 ^满膜'，上述電解液（1M LiPF6 in EC-EMC( 1: 1))中以 0. 5mV/s掃描速度，在卜2V進行循環伏安法量測之結果。圖中顯示，儘管在不同的濺鍍溫度下，仍然可以在i 5 v〜 1 · 6 V間得到一對因為s p i n e 1和r 〇 c k - s a 11兩相進行相轉變’所產生氧化還原峰及鋰離子嵌入脫出電極的電化學可逆性。在不同賤鍍溫度下的氧化還原峰有著明顯不同$形狀和電流密度尺度。隨濺鍍溫度升高所鍍製的薄膜其氧^ 還原峰有著較高的對稱性和大一個數量級以上的電&密度，如第5圖（d)所示。此外，氧化和還原電位將隨著沉積度的上升而更加靠近。利用定電流（1 〇 A / c m 2)的方式，以1 v、2 V為截止電壓進行充放電的量測。第β圖為L i J i 5〇 J專膜在不同錢艘溫度下的電池放電效能圖。由圖可知，在7 〇〇。〇下成長的薄膜’電容量大約為53 // Ahcur2// m—卜其值遠大於在6〇(rc 所沉積的薄膜，符合循環伏安法所觀測到的結果。此外，隨著濺鍍溫度的上升，放電曲線在1 · 5 5 Μ右的平台越來越明顯，在7 0 0°C下濺鍍的薄膜具有近乎水平的平台。藉由循環伏安法和電池定電流充放電量測，可以明顯觀察到薄膜製程溫度在65(rc以上時，電容量值大幅增’ 加。以上是對本發明之薄膜電池、薄膜電池之負極薄膜及Page 12 95Ι26Θ§1|^ ___ Case No. 9312^^g_7年(p Month Day Correction V, Invention Description (6) ~——一~·—Complete the battery assembly. Analyze L i J i by cyclic voltammetry 5〇! With the redox peak of the film and the purity of the film, the amount is measured at a scan rate of 0 · 5 mV/s between 1 and 2 V. Figure 5 shows the L ij丨 obtained by sputtering at different temperatures. 5 〇 ^ full film ', the above electrolyte (1M LiPF6 in EC-EMC (1:1)) at a scanning speed of 0.5 mV / s, the results of cyclic voltammetry measurement at 2V. Although at different sputtering temperatures, a pair of redox peaks and lithium ions embedded in the phase transition between spine 1 and r 〇ck - sa 11 can be obtained between i 5 v and 1 · 6 V. Electrochemical reversibility of the electrode. The redox peaks at different ruthenium plating temperatures have significantly different shape and current density scales. The plated film has a higher symmetry of oxygen reduction peaks as the sputtering temperature increases. And a greater than an order of magnitude of electric & density, as shown in Figure 5 (d). In addition, the oxidation and reduction potentials will vary with the degree of deposition. And closer. Using a constant current (1 〇A / cm 2), the charging and discharging measurements are performed with 1 v and 2 V as the cutoff voltage. The β-graph is L i J i 5〇J film in different money The discharge performance of the battery at a temperature. It can be seen from the figure that the film grown at 7 〇〇 has a capacitance of approximately 53 // Ahcur2// m—the value is much larger than that at 6 〇 (rc deposited film) In line with the results observed by cyclic voltammetry. In addition, as the sputtering temperature increases, the discharge curve becomes more and more obvious on the platform of 1 · 5 5 Μ right, and the film sputtered at 700 ° C has Near-horizontal platform. By cyclic voltammetry and battery constant current charge and discharge measurement, it can be clearly observed that when the film process temperature is above 65 (rc or more, the capacitance value is greatly increased). The above is the thin film battery of the present invention, Negative film of thin film battery and

第13頁Page 13

I2608U _/案號93125448 _^5"年G月曰修正_ 五、發明說明（7) 其製法說明。習於斯藝之人士，應可由以上說明得知本發明之精神，並據以作出各種變化與衍生。唯只要不脫離本發明之精神，均應包含於其申請發明專利範圍之内。 _2608l2 Iff "93125448 fly 年。月 f 曰修正圖式簡單說明【圖示簡單說明】第1圖表示本發明Li 4Ti 50 i靶材之XRD粉末繞射圖形。第2圖表示依本發明方式在不同濺鍍溫度下製成之 1^41^501满膜沉積在八11/1^/8丨02/8丨基板上之\1^繞射圖形。第3圖表示本發明方式在不同濺鍍溫度下製成之 1^41^501/專膜沉積在八11/1^/8丨02/8丨基板上之\{^表面形貌圖。第4圖表示本發明方式在不同濺鍍溫度下製成之 1^41^501/專膜沉積在八11/1^/8丨02/8丨基板上之乂1^橫截面圖。第5圖表示本發明方式在不同濺鍍溫度下製成之 1^41^501/專膜沉積在八11/1^/8丨02/8丨基板上之\{^之結果示意圖。第6圖為L i 4T i 50 j專膜在不同濺鍍溫度下的電池放電效能圖。【主要元件符號說明】 ΦI2608U _ / Case No. 93125448 _^5" Year G Month 修正 Amendment _ V. Description of the invention (7) Description of its method. Those skilled in the art should be aware of the spirit of the present invention from the above description and make various changes and derivatives. It should be included in the scope of the invention patent application without departing from the spirit of the invention. _2608l2 Iff "93125448 fly year. Month f 修正 Correction Schematic description [Simplified illustration] Fig. 1 shows an XRD powder diffraction pattern of the Li 4Ti 50 i target of the present invention. Fig. 2 is a view showing a ?1^ diffraction pattern of a 1^41^501 full film deposited on a substrate of eight 11/1^/8丨02/8 Å at different sputtering temperatures according to the present invention. Fig. 3 is a view showing the surface topography of the 1^41^501/specific film deposited on the eight 11/1^/8丨02/8 丨 substrate at different sputtering temperatures in the mode of the present invention. Fig. 4 is a cross-sectional view showing the 1^41^501/specific film deposited on the eight 11/1^/8丨02/8 丨 substrate at different sputtering temperatures in the mode of the present invention. Fig. 5 is a view showing the result of the \^^ of the 1^41^501/specific film deposited on the eight 11/1^/8丨02/8丨 substrate prepared by the sputtering method at the different sputtering temperatures. Figure 6 is a diagram showing the discharge performance of the battery at different sputtering temperatures for the Li 4T i 50 j film. [Main component symbol description] Φ

第15頁Page 15

Claims

案號 126448 修正六、申請專利範圍電極薄膜之製法，包括：提供L i及T i離子之靶材；緩衝層及一貴金 1,. 一種電池製備一可製備一基板，該基板具有一基層屬集電層；於真空腔極層，該電極降溫，完 2. 如申請專之貴金屬包括 3. 如申請專之貴金屬為金 4. 如申請專之緩衝層為金 5. 如申請專之緩衝層為ΊΊ 6. 如申請專緩衝層之厚度 5 0 0 0 > 中，5 0 0°C以上高溫下，在該基板上濺鍍電層的材料為L i 4T i 12，及成薄膜之製備。利範圍第1項之電池電極薄膜之製法，其中銀、金、翻、把，其合金或氧化物。利範圍第1項之電池電極薄膜之製法，其中〇利範圍第1項之電池電極薄膜之製法，其中屬層。利範圍第4項之電池電極薄膜之製法，其中〇利範圍第4項之電池電極薄膜之製法，其中為10〜1000足右，且其貴金屬層厚度為20- 7. —種薄膜製備一正製備一電製備一負電池之製法，包括：電極薄膜，解層，電極薄膜，將該正電極薄膜，該電解層及該負電極層堆疊，其間Case No. 126448 Amendment 6. The method for preparing the patented electrode film includes: providing a target of L i and T i ions; a buffer layer and a precious gold 1. A battery preparation method can prepare a substrate having a base layer It is a collector layer; in the vacuum cavity layer, the electrode is cooled down. 2. If the application is for precious metals, include 3. If the application is for precious metals, it is gold. 4. If the application is specially made of gold, the buffer layer is gold. The layer is ΊΊ 6. If the thickness of the special buffer layer is 5 0 0 0 >, at a high temperature above 50 ° C, the material of the electroplated layer on the substrate is L i 4T i 12, and the film is formed. preparation. The method for producing a battery electrode film according to item 1, wherein silver, gold, turn, and alloys or oxides thereof. The method for preparing a battery electrode film according to item 1, wherein the battery electrode film of the first item is in the form of a layer. The method for preparing a battery electrode film of the fourth item, wherein the battery electrode film of the fourth item of the profit range is 10 to 1000 feet right, and the thickness of the noble metal layer is 20- 7. Preparing a method for preparing a negative battery, comprising: an electrode film, a layer, an electrode film, stacking the positive electrode film, the electrolyte layer and the negative electrode layer,

第16頁 1260812 案號 93125448 修正六、申請專利範圍以隔膜隔離；及包覆所得之組成物；其特徵在於該負電極係以下列步驟製成：製備一可提供L i及T i離子之靶材；製備一基板，該基板具有一基層，一緩衝層及一貴金屬集電層；於真空腔中，5 0 0°C以上高溫下，在該基板上濺鍍負電極層，該電極層的材料為L i 4T i 50 12;及降溫，完成薄膜之製備。其中之貴其中之貴其中之緩 8 .如申請專利範圍第7項之薄膜電池之製法金屬包括銀、金、始、把，其合金或氧化物。 9 .如申請專利範圍第7項之薄膜電池之製法金屬為金。 1 0 .如申請專利範圍第7項之薄膜電池之製法衝層為金屬層。 11.如申請專利範圍第1 0項之薄膜電池之製法，其中之緩衝層為T i。 1 2 .如申請專利範圍第1 0項之薄膜電池之製法，其中緩衝層之厚度為10〜1000泣右，且其貴金屬層厚度為20-5 0 0 0 > ·Page 16 1260812 Case No. 93125448 Amendment VI, the patent application scope is separated by a separator; and the composition obtained by coating; characterized in that the negative electrode is made by the following steps: preparing a target capable of providing Li and Ti ions Preparing a substrate having a base layer, a buffer layer and a noble metal collector layer; in the vacuum chamber, at a high temperature above 500 ° C, a negative electrode layer is sputtered on the substrate, the electrode layer The material is L i 4T i 50 12; and the temperature is lowered to complete the preparation of the film. Among them, the price is more expensive. 8. The method for manufacturing a thin film battery according to item 7 of the patent application includes silver, gold, ginseng, and alloys or oxides. 9. The method for manufacturing a thin film battery according to claim 7 of the patent scope is metal. 1 0. The method for manufacturing a thin film battery according to claim 7 is a metal layer. 11. The method of producing a thin film battery according to claim 10, wherein the buffer layer is Ti. 1 2 . The method for manufacturing a thin film battery according to claim 10, wherein the thickness of the buffer layer is 10 to 1000, and the thickness of the noble metal layer is 20-5 0 0 >

第17頁 1260812 圖式 (.tiun XJBJllfqJB)^^Page 17 1260812 Schema (.tiun XJBJllfqJB)^^

10 20 30 40 50 60 70 80 90 100 兩倍繞射角 ► 第1圖第頁 » 1260812 圊式 .(HI) (so!s· (&ην. (nl)nv. (so)！sjl (ooGnv (s) 700°C 650〇C 600°C J V ~SOCf C 20 40 50 60 兩倍繞射角 70 第2圖 1260812 式 ςχχκνν)^掷梃：i 02 02 -0. 02 -0.10 20 30 40 50 60 70 80 90 100 Double diffraction angle ► Page 1 of the picture » 1260812 圊. (HI) (so!s· (&ην. (nl)nv. (so)!sjl ( ooGnv (s) 700°C 650〇C 600°CJV ~SOCf C 20 40 50 60 Double diffraction angle 70 Fig. 2 1260812 Type ςχχκνν)^Roll: i 02 02 -0. 02 -0.

1.4 1.6 電壓(V) (a) 1.8 2.0 ςιπο/ν)^锲梃一, 021.4 1.6 Voltage (V) (a) 1.8 2.0 ςιπο/ν)^锲梃一, 02

.2 ΛΊ.2 ΛΊ

電壓(V) (b) 第5圖第頁 1260812 式圖 2 0. 1 ο ο· ο·-0. (g3/v)^锲梃锏 2 -0. 2 α 1 ο 0.0.-0. ςιικνν)^衡梃鯽 2 -0. i 1 i ' « ^ .650°C 1 1 1 1 1 ,1.598 V I : 1 . 1 . 1 . 1.532 V 1 . 1 . 1 1.0 1.2 1.4 1.6 1.8 2.0 電壓(v) (c) · 1 署婦， _700°C 爾 I 1 1 1.588 V - ---------------------------—- Λ 1 . 1 . 1 . 1.543 V " 1 . 1 . 1 1.0 1.2 1.4 1.6 1.8 2.0 電壓(V) (d) 第5圖 1260812 圖式Voltage (V) (b) Fig. 5, page 1260812 Equation 2 0. 1 ο ο· ο·-0. (g3/v)^锲梃锏2 -0. 2 α 1 ο 0.0.-0. ςιικνν )^衡梃鲫2 -0. i 1 i ' « ^ .650°C 1 1 1 1 1 , 1.598 VI : 1 . 1 . 1 . 1.5 . 1.5 V 1 . 1 . 1 1.0 1.2 1.4 1.6 1.8 2.0 Voltage (v (c) · 1 woman, _700 °C I I 1 1.588 V - --------------------------------- Λ 1 1 . 1 . 1.543 V " 1 . 1 . 1 1.0 1.2 1.4 1.6 1.8 2.0 Voltage (V) (d) Figure 5 Figure 1260812

第6圖第二·4頁Figure 6 Page 2 of 4