TW201201440A - Alloy cathode for lithium battery, its manufacturing method and lithium battery - Google Patents

Alloy cathode for lithium battery, its manufacturing method and lithium battery Download PDF

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Publication number
TW201201440A
TW201201440A TW100118455A TW100118455A TW201201440A TW 201201440 A TW201201440 A TW 201201440A TW 100118455 A TW100118455 A TW 100118455A TW 100118455 A TW100118455 A TW 100118455A TW 201201440 A TW201201440 A TW 201201440A
Authority
TW
Taiwan
Prior art keywords
aluminum
negative electrode
porous body
lithium battery
resin
Prior art date
Application number
TW100118455A
Other languages
Chinese (zh)
Inventor
Nobuhiro Ota
Takahsi Uemura
Akihisa Hosoe
Masatoshi Majima
Koji Nitta
Original Assignee
Sumitomo Electric Industries
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries filed Critical Sumitomo Electric Industries
Publication of TW201201440A publication Critical patent/TW201201440A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides an alloy cathode for lithium battery, its manufacturing method and lithium battery. The alloy cathode for lithium battery is constituted by non-aqueous electrolyte. By filling metal lithium in a porous aluminum body, the skeleton of the porous aluminum body is further formed by using aluminum. Moreover, by forming an aluminum coating material with an aluminum layer on the surface of a core material constituted of any metal selected from the group consisting of copper, nickel and iron, the skeleton of the porous aluminum body is formed to increase the capacity and intensity and provide excellent charging and discharging cycles.

Description

201201440 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用鋁多孔體之鋰電池用合金負極 和其製造方法及鋰電池。 【先前技術】 近年來，業界正活躍地研究個人數位助理、電動車輕 及家庭用電力儲存裝置所使用之鋰離子電池等鋰二次電 池。 作為該鋰二次電池之一代表例，非專利文獻丨中揭示 有Li-Al (負極）/Mn〇2 (正極）鋰二次電池。 但是，上述鋰二次電池由於作為負極之Li—A1合金較 脆弱，故而於實現工業上之量產方面存在困難。 另外，於提高放電深度而進行充放電之情形時，於較 少次數之充放電循環中便招致大幅度之放電容量之劣化。 例如於以100%之放電深度進行充放電之情形時，其循環壽 命之限度為數十個循環左右。因此，通常以1〇%左右之放 電深度進行充放電。 [非專利文獻1]高村勉監修「最新電池手冊」朝倉書 店股份有限公司、1996年12月26日發行、第6〇9〜61〇^ 【發明内容】 蓉於該等問題，期待開發出—種適合工業上之量產， 並且即便提高放電深度並以較多次數之充放電循環進行充 放電之情形時，亦無導致放電容量劣化之虞的鋰電池用合 金負極。 201201440 上述課題可藉由以下所示之各發明而解決。 (1 )本發明之鋰電池用合金負極係使用非水電解液 者，其特徵在於：於鋁多孔體中填充有鋰金屬。 本發明人針對解決上述課題進行努力研究。結果發 現：有效的是使用铭多孔體中填充有鐘金屬所製得之Li — A1合金代替先前之板狀體之U_A1合金作為負極。 即，於鋁多孔體中填充有鋰金屬之Li—A1合金負極， 由於具有成為芯之骨架，故而並無如先前之Li — A1合金負 極之脆弱性’適合工業上之量產。 另外，即便以高放電深度亦可確保充分之循環壽命。 即，本發明人進行研究，結果得知：隨著錢電循環， 充電時Ai會膨服，放電時A1會收縮.，而引起電極整體之 膨服收縮’因而電極界面上會產生裂縫等，發生微粉化， 導致活性物質之脫離此會對提高放電深度之情形時之充 放電循環特性產生不良影響。 .相對於此，本發明之於铭多孔體中填充有鐘金屬之U A1。金負極，由於A1濃度形成隨著遠離多孔體之骨架、 即多孔體之骨架之中央部而降低之濃度梯度，故可使充放 電循環所伴隨之膨脹收縮之應力分散而獲得❹"其結果 為’即便提高放電深度之情形時，亦可抑制電極之裂縫， 抑制微粉化之發生，確保充分之充放電循環。 另外，明白充放電循環壽命降低之原因亦在於··因U 金屬負極之Li樹技狀結晶成長，而導致長時間使用之情形 時發生短路。就該方面而言，本發明之於鋁多孔體中填充 201201440 有鐘金屬之Li— A1合金負極，由於該u樹枝狀結晶成長停 留於多孔内，故而可抑制由短路引起之循環壽命之降低。 (2)另外’如上述之鐘電池用合金負極，上述鋁多孔 體之骨架係由鋁所形成。 由於銘多孔體之骨架本身係由鋁所形成，故而僅利用 骨架便可形成Li - A1合金。因此，可提供孔隙率高且容量 密度大之鋰電池用合金負極。 (3 )另外’如上述之鋰電池用合金負極，上述鋁多孔 體之骨架係由鋁被覆材所形成，該鋁被覆材係於由銅、錄、 鐵中之任一種金屬所構成之芯材的表面形成鋁層而成者。 本發明之裡電池用合金負極係使用銅、鎳、鐵中之任 一種金屬作為鋁多孔體之骨架之芯材。該等金屬由於不會 與鋰或鋁合金化，另一方面，由於機械強度高，故而可形 成強度優異之多孔體。因此，於由該等金屬所構成之芯材 之表面形成有鋁層之多孔體可提供對膨脹收縮較強之鋰電 池用合金負極。 (4)另外，如上述之鋰電池用合金負極，上述鋰金屬 之體積於上述鋁多孔體之空孔中所占之比率為5〇%以上、 未達100%。 於本發明中’由於鋰金屬之體積比率未達1 〇〇%，填充 Li後之鋁多孔體中殘留有空孔，故而即便生成樹枝狀結晶 之情形時，樹枝狀結晶亦主要生成於空孔内。因此，有效 地抑制樹枝狀結晶短路。另一方面，若鋰金屬之體積比率 未達50/〇，則有無法充分地發揮作為鐘電池用合金負極之 201201440 實用性作用之虞。 (5)另外，如上述之鋰電池用合金負極，形成上述鋁 多孔體之骨架之鋁、或上述鋁被覆材之鋁層之表面的氧量 為3.1質量％以下。 本發明之鋰電池用合金負極之紹多孔體由於形成鋁多 孔體之骨架之鋁、或上述鋁被覆材之鋁層之表面之氧量為 3.1質量以下’故而可提供前所未有之容量密度更高之電 池用合金負極。 由於A1原本易被氧化，故而至今為止尚無表面之氧量 充分少之鋁多孔體。例如日本特開平8_17〇126號公報所 記載之於形成於發泡樹脂之表面的A1之共晶合金之皮膜之 表面塗佈A1粉末後，於非氧化性之環境中進行熱處理而製 作之紹多孔體之情形時，由於表面會生成氧化皮膜，故而 表面之氧量較高。於表面之氧量.較高之情形時，由於所填 充之Li會被氧氣（ο。氧化，而轉化為無法作為活性物質 之LhO,故而無法獲得大容量密度。另外，所生成之Li2〇 由於成為電阻層，故而特性降低。 因此，本發明人研究氧量少之鋁多孔體，而成功開發 出氧量為3 · 1質量％以下之鋁多孔體。 本發明之特徵在於使用此種鋁多孔體，由於使用表面 之氧量為3.1質量％以下之鋁多孔體，故而可獲得容量密度 更大之經電池用合金負極。 此處，關於本發明之鋰電池用合金負極之製造方法， 一面參照圖式一面詳細地進行說明。製造方法之第一階段 6 201201440 第一階段係於此銘多孔體 係製造具有連通孔之紹多孔體 中填充Li金屬。 圖1A〜1C係表示此第一階段之概略之模式圖。圖以 係表示具有連通孔之樹脂！之剖面之一部分的放大模式 圖’表示將樹脂i作為骨架而形成有孔之情形。圖ΐβ係表 示於具有連通孔之樹脂1之表面形成有鋁層2之情形（鋁 層被膜樹脂3)。圖1C係表示使樹脂1熱分解而_被膜 樹脂3消失後之情形（鋁多孔體4)。 、 圖2係表示熱分解樹脂i而使其自紹層被膜樹脂3消 失之步驟。將鋁層被膜樹脂3及正極5浸潰於熔鹽6中， 將鋁層2保持為低於鋁之標準電極電位的電位。藉由浸潰 於炼鹽中並將銘層2保持為低於銘之標準電極電位：電 位，可抑制…之氧化。再者，正極 出不溶性則可適宜選擇，例如可使用由.、欽等所；成: 電極。 於該狀態下，若將熔鹽6加熱至樹脂i之分解溫度以 上，則鋁層被膜樹脂3中僅樹脂丨分解消失。豆沾果為， 可獲得紹多孔體4。藉由該方法所製造之紹多孔體4於製造 法之特質上為中线維狀。就該方面而言，其構造不同於 如日本特開2002- 371327中所揭示之铭發泡體。再者，於 分解樹脂丨時’為了防止銘线融，而將加熱溫度設為銘 之點以下β且體而言，/f去f, Γ 〃、瓶叩。杈佳為以鋁之熔點即6601以下進 行加熱。 本發明中之樹脂只要為以紐之熔點以下之溫度進行熱 201201440 分解者，則可選擇任意之樹脂。例如 β 眾胺甲酸酯 (―)、聚丙烯、聚乙稀等。其中，由於發泡胺甲 酸乙酯（ureth_)係孔隙率較高且易熱分解之素材，故而 發泡胺甲酸乙_較佳為用作本發明之製造方法所使用之樹 脂。另外，較佳為樹脂之孔隙率為80%〜98%，孑匕隙直徑為 5〇〆m〜50〇A m左右者。較佳為樹脂具有連通孔。藉此， 可獲得無閉合孔之鋁多孔體。 3 以上所說明之銘多孔體之表面之紹的氧量非常低，為 順分析之析出極限即質量％以下。另外，連通孔由於 具有但無閉合孔，it而未使用共晶合金等，故而僅由銘構 成。 其次’作為第二階段，於|g多孔體4中填充u金屬。 用以填充之方法並無特別限定，例如可使用藉由含入之方 法或真空蒸鍍法、電鍍法等公知方法。 ⑷另外’如上述之鋰電池用合金負極，上述鋁多孔 體具有連通孔’不具有閉合孔，並且僅由銘所構成。 先前之鋁多孔體、例如日本特開2〇〇2— 371327號公報 中所記載之於使A1熔融之狀態下添加發泡劑使其發泡而成 之紹多孔體中大量存在閉合孔。另外，於上述日本特開平8 -17〇126號公報中所記載之紹多孔體由於為共晶金屬，故 而含有Bi、Ca、其他Ai以外之金屬。如此，於閉合孔大量 存在之情形時，由於無法填充充分量之u，故而無法獲得 大容量密度。另外，由於含有A1以外之金屬，故而作為u —A1合金之負極之功能降低。 8 201201440 另一方面，於本發明之鋰電池用合金負極中，由於可 填充充分量之Li金屬，故而可獲得容量密度更大之鋰電池 用合金負極。另外’由於銘多孔體僅由銘所構成，故而可 充分發揮作為負極之功能。 (7 )本發明之鋰電池，其特徵在於：具備上述（工） 〜（6)之鋰電池用合金負極。 本發明之鋰電池由於將具備上述特徵之鋰電池用合金 作為負極，故而可提供容量密度大，且充放電循環特性優 異之鋰電池。 (8) 本發明之鋰電池用合金負極之製造方法，其特徵 在於具有如下步驟： 鋁層形成步驟：其係將鋁層形成於具有連通孔之樹脂 的表面； 鋁多孔體製作步驟··其係於將上述樹脂浸潰於熔鹽之 狀態下，一面將上述鋁層保持為低於鋁之標準電極電位的 電位，一面將上述樹脂加熱至鋁之熔點以下的溫度，使上 述樹脂熱分解而製作I呂多孔體；及 鋰金屬填充步驟：其係將鋰金屬填充於上述鋁多孔體。 根據本發明之鋰電池用合金負極之製造方法，可提供 一種鋰電池用合金負極，其使用有如上述之鋁層之表面之 氧量為3.1質量％以下，具有連通孔，不具有閉合孔，進而 僅由鋁所構成之鋁多孔體，並且容量密度大，且微粉化與 樹枝狀結晶短路之抑制效果高。 (9) 本發明之鋰電池用合金負極之製造方法’其特徵 201201440 在於具有如下步驟： 金屬層形成步驟··其係將由銅、鎳、鐵中之任一種金 屬所構成之金屬層形成於具有連通孔之樹脂的表面； 鋁層形成步驟··其係將鋁層形成於上述金屬層的表面，· 鋁多孔體製作.步驟：其係於將上述樹脂浸潰於熔鹽之 狀態下…面將上述紹層保持為低於紹之料電極電:的 電位，一面將上述樹脂加熱至鋁之熔點以下的溫度，使上 述樹脂熱分解而製作鋁多孔體；及 經金屬填充步驟：其係將鐘金屬填充於上述紹多孔體。 藉由本發明之鋰電池用合金負極之製造方法，可提供 一種鋰電池用合金負極’其使用有如上述之鋁層之表面2 氧量為3」質量％以[具有連通孔，不具有閉合孔，並且 鋁多孔體之容量密度較大且充放電循環優異，進而由於鋁 多孔體係將由銅、錄、鐵中之任一種金屬所構成之金屬作 為骨架’故而可提供強度較強之鋰電池用合金負極。 (10)另外，如上述之鋰電池用合金負極之製造方法， 上述鋁層之形成方法為真空蒸鍍法、濺鍍法、雷射剝蝕法 或電漿CVD法。 真空蒸鍍法例如可藉由對原料之鋁金屬照射電子束使 銘,屬熔融、蒸發’使鋁金屬附著於具有連通孔之樹脂體 之樹脂表面，而形成鋁金屬層。濺鍍法例如可對鋁金屬之 乾進，電毁照射使铭金屬氣化，使紹合金附著於具有連通 孔，樹月曰體之樹脂表面，而形成鋁金屬層。雷射剝蝕法例 如可藉由雷射照射使鋁金屬熔融、蒸發，使鋁金屬附著於 10 201201440 具有連通孔之樹脂體之樹脂表面，而形成鋁金屬層。電漿 CVD法可藉由對作為原料之鋁化合物施加高頻波使其電漿 化’使其附著於具有連通孔之樹脂之表面，而形成鋁金屬 (Π)另外，如上述之鋰電池用合金負極之製造方法， 上述銘層之形成方法為於對上述樹脂之表面進行導電化處 理後’鑛敷紹之镀敷法。 (12)另外，本發明之鋰電池用合金負極之製造方法， 其特徵在於： 上述鋁層之形成方法為將鋁鍍敷於上述金屬層表面之 鍍敷法。 於水溶液中鍍敷鋁實際上幾乎不可能，因此進行於熔 鹽中鍍敷鋁之熔鹽電解鍍敷。於該情形時’較佳為於預先 導電化處理树月曰之表面後’於熔鹽中鍍敷紹。201201440 VI. [Technical Field] The present invention relates to an alloy negative electrode for a lithium battery using an aluminum porous body, a method for producing the same, and a lithium battery. [Prior Art] In recent years, the industry is actively researching lithium secondary batteries such as lithium ion batteries used in personal digital assistants, electric vehicle light, and household power storage devices. As a representative example of the lithium secondary battery, a Li-Al (negative electrode) / Mn 〇 2 (positive electrode) lithium secondary battery is disclosed in the non-patent document. However, the lithium secondary battery described above is weak in the Li-Al alloy as a negative electrode, and thus it is difficult to achieve industrial mass production. Further, when charging and discharging are performed while increasing the depth of discharge, a large discharge capacity is deteriorated in a small number of charge and discharge cycles. For example, when charging and discharging are performed at a depth of discharge of 100%, the cycle life limit is about several tens of cycles. Therefore, charging and discharging are usually performed at a discharge depth of about 1%. [Non-Patent Document 1] Takamura Aya, "The Latest Battery Handbook", Asakura Shoten Co., Ltd., issued on December 26, 1996, and the 6th, 9th, 9th, and 61st [Summary of the Invention] When it is suitable for mass production in the industrial production, and even if the depth of discharge is increased and charging and discharging are performed in a plurality of charge and discharge cycles, there is no alloy negative electrode for lithium batteries which causes deterioration in discharge capacity. 201201440 The above problems can be solved by the inventions shown below. (1) The alloy negative electrode for a lithium battery of the present invention is a non-aqueous electrolyte, characterized in that the aluminum porous body is filled with lithium metal. The inventors of the present invention have made an effort to solve the above problems. As a result, it was found that it is effective to use the Li-Al alloy obtained by filling the bell-shaped metal in the porous body in place of the U_A1 alloy of the previous plate-like body as the negative electrode. In other words, the Li-Al alloy negative electrode in which the aluminum porous body is filled with lithium metal has a skeleton which becomes a core, and thus has no materiality as the density of the negative Li-Al alloy negative electrode, which is suitable for industrial mass production. In addition, a sufficient cycle life can be ensured even at a high discharge depth. That is, the inventors conducted research and found out that with the circulation of money and electricity, Ai will be swollen during charging, and A1 will shrink during discharge, causing expansion and contraction of the electrode as a whole, and thus cracks may occur at the electrode interface. The occurrence of micronization causes the release of the active material to adversely affect the charge and discharge cycle characteristics in the case of increasing the depth of discharge. On the other hand, in the porous body of the present invention, the U A1 of the bell metal is filled. In the gold negative electrode, since the A1 concentration forms a concentration gradient which is lowered away from the skeleton of the porous body, that is, the central portion of the skeleton of the porous body, the stress of expansion and contraction accompanying the charge and discharge cycle can be dispersed to obtain ❹" 'When the depth of discharge is increased, the crack of the electrode can be suppressed, the occurrence of micronization can be suppressed, and a sufficient charge and discharge cycle can be ensured. In addition, it is understood that the reason why the charge-discharge cycle life is lowered is that a short circuit occurs when the Li-tree crystal growth of the U-metal negative electrode is caused by long-term use. In this respect, in the aluminum porous body of the present invention, the Li-Al alloy negative electrode of 201201440 bell alloy is filled, and since the growth of the u dendritic crystal is retained in the porous body, the decrease in cycle life due to the short circuit can be suppressed. (2) Further, the alloy negative electrode for the above-mentioned clock battery, wherein the skeleton of the aluminum porous body is formed of aluminum. Since the skeleton of the porous body itself is formed of aluminum, the Li - A1 alloy can be formed only by using the skeleton. Therefore, an alloy negative electrode for a lithium battery having a high porosity and a high capacity density can be provided. (3) In the alloy negative electrode for a lithium battery as described above, the skeleton of the aluminum porous body is formed of an aluminum coating material, and the aluminum coating material is a core material composed of any one of copper, nickel, and iron. The surface forms an aluminum layer. In the alloy negative electrode for a battery of the present invention, any one of copper, nickel, and iron is used as the core material of the skeleton of the aluminum porous body. Since these metals are not formed with lithium or aluminum alloy, on the other hand, since the mechanical strength is high, a porous body excellent in strength can be formed. Therefore, the porous body in which the aluminum layer is formed on the surface of the core material composed of the metals can provide an alloy negative electrode for lithium batteries which has a large expansion and contraction. (4) In the alloy negative electrode for a lithium battery as described above, the ratio of the volume of the lithium metal to the pores of the aluminum porous body is 5% by weight or more and less than 100%. In the present invention, since the volume ratio of lithium metal is less than 1% by weight, voids remain in the aluminum porous body after filling Li, so that dendrites are mainly formed in the pores even when dendrites are formed. Inside. Therefore, the dendrite short circuit is effectively suppressed. On the other hand, when the volume ratio of lithium metal is less than 50 / 〇, the effect of 201201440, which is an alloy negative electrode for a clock battery, cannot be sufficiently exhibited. (5) In the alloy negative electrode for a lithium battery, the amount of oxygen on the surface of the aluminum layer forming the aluminum porous body or the aluminum layer of the aluminum coating material is 3.1% by mass or less. The porous body of the alloy negative electrode for a lithium battery of the present invention can provide an unprecedented capacity density because the aluminum forming the skeleton of the aluminum porous body or the surface of the aluminum layer of the aluminum coating material has an oxygen content of 3.1 or less. Alloy anode for battery. Since A1 is easily oxidized, there has been no aluminum porous body having a sufficiently small amount of oxygen on the surface. For example, the surface of the film of the eutectic alloy formed on the surface of the foamed resin described in Japanese Unexamined Patent Publication No. Hei No. Hei. In the case of a body, since the surface forms an oxide film, the amount of oxygen on the surface is high. In the case where the amount of oxygen on the surface is high, since the filled Li is oxidized by oxygen, it is converted into LhO which cannot be used as an active material, so that a large capacity density cannot be obtained. Therefore, the present inventors have studied an aluminum porous body having a small amount of oxygen and successfully developed an aluminum porous body having an oxygen content of 3.1 mass% or less. The present invention is characterized in that the aluminum porous body is used. In the case of using an aluminum porous body having a surface oxygen content of 3.1% by mass or less, a battery negative electrode for a battery having a larger capacity density can be obtained. Here, the method for producing an alloy negative electrode for a lithium battery of the present invention is referred to The first stage of the manufacturing method 6 201201440 The first stage is to fabricate a porous body in a porous body having a continuous pore in the porous system. Fig. 1A to Fig. 1C show the outline of the first stage. A schematic diagram showing a portion of a cross section of a resin having a communicating hole, which is a schematic view showing a case where a resin i is used as a skeleton to form a hole. Fig. 1 shows a case where the aluminum layer 2 is formed on the surface of the resin 1 having the continuous pores (aluminum layer coating resin 3). Fig. 1C shows a case where the resin 1 is thermally decomposed and the film resin 3 disappears (aluminum porous body) 4) Fig. 2 shows a step of thermally decomposing the resin i and disappearing from the film-forming resin 3. The aluminum layer film resin 3 and the positive electrode 5 are immersed in the molten salt 6, and the aluminum layer 2 is kept lower than The potential of the standard electrode potential of aluminum. By immersing in the salt and keeping the layer 2 below the standard electrode potential: potential, it can suppress the oxidation of .... Further, the positive electrode is insoluble and can be suitably selected. For example, it is possible to use an electrode such as ., 钦, etc. In this state, when the molten salt 6 is heated to a temperature higher than the decomposition temperature of the resin i, only the resin ruthenium in the aluminum layer film resin 3 is decomposed and disappeared. The porous body 4 can be obtained. The porous body 4 produced by the method has a midline shape on the trait of the manufacturing method. In this respect, the structure is different from that disclosed in Japanese Laid-Open Patent Publication No. 2002-371327. Insulation foam. In addition, when decomposing resin 丨, 'to prevent When the wire is melted, the heating temperature is set to be lower than the point β, and the body is /f to f, Γ 〃, and the bottle 叩. 杈 preferably is heated at a melting point of aluminum, that is, 6601 or less. The resin in the present invention is only Anyone who has decomposed heat at the temperature below the melting point of New Zealand can choose any resin, such as β-carbamate (-), polypropylene, polyethylene, etc. Among them, due to foaming urethane (ureth_) It is a material which has a high porosity and is easily decomposed by heat, and therefore, the foamed amine formate is preferably used as a resin used in the production method of the present invention. Further, it is preferred that the resin has a porosity of 80% to 98%. The crevice has a diameter of about 5 〇〆 m to 50 〇 A m. Preferably, the resin has a communicating hole, whereby an aluminum porous body having no closed pores can be obtained. 3 The oxygen content on the surface of the porous body described above is very low, which is the precipitation limit of the analytical analysis, that is, the mass% or less. Further, since the communication hole has but no closed hole, it does not use a eutectic alloy or the like, and therefore it is constructed only by the name. Next, as the second stage, the u metal is filled in the |g porous body 4. The method for filling is not particularly limited, and for example, a known method such as a method of inclusion, a vacuum vapor deposition method, or a plating method can be used. (4) In addition, the alloy negative electrode for a lithium battery as described above, the aluminum porous body having a communication hole ' does not have a closed hole, and is composed only of the name. A large number of closed pores are formed in the porous body in which the foaming agent is added and the foaming agent is foamed in a state in which A1 is melted as described in Japanese Laid-Open Patent Publication No. Hei. In addition, since the porous body described in the above-mentioned Japanese Patent Publication No. Hei 8-17-126 is a eutectic metal, it contains Bi, Ca, and other metals other than Ai. Thus, in the case where a large number of closed holes exist, since a sufficient amount of u cannot be filled, a large capacity density cannot be obtained. Further, since a metal other than A1 is contained, the function as a negative electrode of the u-Al alloy is lowered. 8 201201440 On the other hand, in the alloy negative electrode for a lithium battery of the present invention, since a sufficient amount of Li metal can be filled, an alloy negative electrode for a lithium battery having a larger capacity density can be obtained. In addition, since the porous body is composed only of the name, it functions as a negative electrode. (7) The lithium battery of the present invention comprising the alloy negative electrode for a lithium battery according to the above (6) to (6). In the lithium battery of the present invention, since the alloy for a lithium battery having the above characteristics is used as a negative electrode, a lithium battery having a large capacity density and excellent charge and discharge cycle characteristics can be provided. (8) A method for producing an alloy negative electrode for a lithium battery according to the present invention, comprising the steps of: forming an aluminum layer by forming an aluminum layer on a surface of a resin having a continuous hole; and manufacturing the aluminum porous body. The resin is thermally decomposed by heating the resin to a temperature equal to or lower than the melting point of aluminum while the resin is immersed in a molten salt while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum. Making a Ilu porous body; and a lithium metal filling step: filling the aluminum porous body with lithium metal. According to the method for producing an alloy negative electrode for a lithium battery of the present invention, it is possible to provide an alloy negative electrode for a lithium battery, which has an oxygen content of 3.1% by mass or less on the surface of the aluminum layer as described above, has a communication hole, and does not have a closed hole, and further The aluminum porous body composed only of aluminum has a large capacity density, and the effect of suppressing micronization and dendrite short-circuiting is high. (9) A method for producing an alloy negative electrode for a lithium battery according to the present invention, characterized in that the method of forming a metal layer is as follows: a metal layer forming step is formed by forming a metal layer made of any one of copper, nickel, and iron a surface of the resin that communicates with the hole; an aluminum layer forming step: the aluminum layer is formed on the surface of the metal layer, and the aluminum porous body is formed. The step is: in the state in which the resin is impregnated in the molten salt... Maintaining the above-mentioned layer at a potential lower than that of the electrode electrode, heating the resin to a temperature equal to or lower than the melting point of aluminum, thermally decomposing the resin to produce an aluminum porous body; and filling the metal through the step: The bell metal is filled in the above-mentioned porous body. According to the method for producing an alloy negative electrode for a lithium battery of the present invention, it is possible to provide an alloy negative electrode for a lithium battery which uses a surface of the aluminum layer as described above and has an oxygen content of 3% by mass to [having a communication hole and having no closed hole, Further, the aluminum porous body has a large capacity density and is excellent in charge and discharge cycles, and further, since the aluminum porous system uses a metal composed of any one of copper, nickel, and iron as a skeleton, it is possible to provide a strong alloy anode for a lithium battery. . (10) Further, in the method for producing an alloy negative electrode for a lithium battery as described above, the method for forming the aluminum layer is a vacuum deposition method, a sputtering method, a laser ablation method or a plasma CVD method. The vacuum vapor deposition method can form an aluminum metal layer by, for example, irradiating an electron beam with an aluminum metal of a raw material to melt and evaporate the aluminum metal to the surface of the resin having a resin body having a continuous hole. The sputtering method can, for example, dry the aluminum metal, and the electro-destructive irradiation vaporizes the metal, so that the alloy adheres to the surface of the resin having the communicating holes and the sap of the tree, thereby forming an aluminum metal layer. The laser ablation method is such that the aluminum metal can be melted and evaporated by laser irradiation to adhere the aluminum metal to the surface of the resin of the resin body having the communication holes of 10 201201440 to form an aluminum metal layer. The plasma CVD method can form an aluminum metal by applying a high-frequency wave to a high-temperature wave as a raw material to cause it to adhere to a surface of a resin having a continuous hole, and an alloy negative electrode for a lithium battery as described above. In the manufacturing method, the method for forming the inscription layer is a plating method in which the surface of the resin is subjected to a conductive treatment. (12) A method for producing an alloy negative electrode for a lithium battery according to the present invention, characterized in that the method for forming the aluminum layer is a plating method in which aluminum is plated on the surface of the metal layer. It is practically impossible to plate aluminum in an aqueous solution, and thus electrolytic salt plating of molten aluminum is performed in molten salt. In this case, it is preferred to plate the molten salt after the surface of the pre-conducting treatment tree.

金屬層表面之塗佈法。The coating method of the surface of the metal layer.

鋁粉末、黏合劑（黏合劑樹脂） 形時，此鋁糊例如為混合 及有機溶劑而成者。具體 201201440 :言，於將麵糊塗佈於樹脂之表面後，進行加熱而使有機 溶剤及黏合劑樹脂消失’同時使㈣燒結。燒結時之加熱 可以-階段進行，亦可分複數次進行。例如可藉由於塗佈 紹糊後以低溫進行加熱使有機溶劑消失後，將其浸潰於熔 鹽中並加熱，而於樹脂分解之同時進行鋁糊之燒結。 藉由本發月，可&供谷量密度較大且充放電循環優異 之經電池用合金負極和其製造方法及鋰電池。 【實施方式】 以下，基於圖式說明本發明之實施形態。再者，於以 下之圖式中對於相同或相當之部分標註相同之參照符號， 不重複其說明。另外，圖式之尺寸比率未必與說明者一致。 (實施形態1 ) Α·：ϋ電池用合金負極 本實施形態中之鐘電池用合金負極，於銘多孔體中填 充有經金屬，鋁多孔體之骨架係由鋁所形成。並且，本實 施形態中之裡電池用合金負極係藉由下述製造方法而製造 (參照圖1Α〜圖1C )。 B.鐘電池用合金負極之製造方法 多孔性之樹脂1係使用具有連通孔之發泡樹脂或不織 布’特佳為孔隙率為80%〜98%、孔隙直徑為50 " m〜500 // m左右之樹脂’較佳為使用發泡胺甲酸乙酯。 以下，按照鋁層形成步驟、鋁多孔體製作步驟、及鐘 金屬含入（填充）步驟之順序說明鋰電池用合金負極之製 造方法。 12 201201440 (1 )鋁層形成步驟 藉由真二蒸鑛、賤鐘法、雷射剝姓法或電漿Cvd等氣 相法、鍍敷法、鋁糊塗佈法等，於樹脂丨之表面直接形成 鋁層2而製作鋁層被覆樹脂3。 為了進行電解鍍敷，而預先導電化處理樹脂丨之表面。 導電化處理係選擇鎳等導電性金屬之無電解鍍敷、鋁等之 蒸鍍或濺鍍、或含有碳等導電性粒子之導電性塗料之塗佈 等任意方法。用於鍍敷鋁之鍍敷浴係使用例如AWL—XU (X:驗金屬）_Mclx(M為選自Cr、Mn、及過渡金屬元 素之添加元素）之多成分系的熔鹽。於熔鹽中浸潰樹脂ι， 並將經導電化處理之樹脂作為負極進行電解錢敷。 鋁層之形成亦可如上所述藉由塗佈鋁糊而進行。鋁糊 係混合鋁粉末與黏合劑（黏合劑樹脂）及有機溶劑而成者， 於樹脂1 t表面塗佈規定量之铭糊冑，於絲化性環境下 進行燒結。 (2 )鋁多孔體製作步驟 其次’使樹脂1熱分解而將其除去。^ 2係用於說明 多孔性樹脂於熔鹽6中分解之步驟的模式圖。於含有選自 由UC卜KC卜NaC卜A1C13所組成之群令之j種以上之鹽 中，以鋁之熔點以下之溫度、較佳為5〇〇(>c〜它之溫度 加熱表面形成有鋁層之樹脂（即鋁層被膜樹脂3)，對:: 或鈦製之正極5之間施加規定電壓，將紹層被職脂3、之 鋁層保持為低於鋁之標準電極電位的電位（高於K、 Na之還原電位的電位），使多孔性樹脂i熱分解將其除去， 13 201201440 而製作圖lc之紹多孔體4β (3)鐘金屬含入（填充）步驟 、其次，於所製作之鋁多孔體中含入規定量之鋰金屬， 〇鋁之合金（Li_Al合金）而製作鋰電池用合 極。具微孟貝 、 έ，例如貼合鋁多孔體與規定厚度之鋰箔後， ‘、、'至1 80 c以上，使裡箔炫融而浸透至鋁多孔體之空孔 令另外’亦可將鋁多孔體浸潰於加熱至18〇。〇以上之鐘之 熔融洽中。再者，所含入之鋰量係以鋰金屬之體積於鋁多 孔體之工孔中所占之比率成為50〇/〇以上、未達1 〇〇〇/〇之方式 進行調整。例如於貼合孔隙率為97%之鋁多孔體與厚度為 鋁多孔體之1/2之鋰箔之情形時，鋰金屬之體積於空孔中 所占之比率為51.5% 〇 C.鋰電池 於如此而製作之鋰電池用合金負極中，所生成之Li _ A1合金產生有鋁之濃度於骨架之附近較高，隨著遠離骨架 而降低之濃度梯度。因此’進行充放電時，即便Li — A1合 金膨脹收縮亦容易緩和應力，而抑制微粉化。 另外，由於鋰金屬之體積於鋁多孔體之空孔中所占之 比率為50%以上’故而確保充分高之容量密度，另一方面， 藉由將該比率設為未達100%而使填充Li後之紹多孔體中 殘留空孔，因此即便於生成鋰樹枝狀結晶之情形時亦會抑 制樹枝狀結晶短路。 (實施形態2 ) 於實施形態2中，鋁多孔體之骨架係於芯材之表面形 14 201201440 9 成有鋁層之鋁被覆材。另外，芯材係由銅、鎳、鐵中之任 一種金屬所構成，其係藉由於具有連通孔之樹脂之表面塗 佈妷粉末而進行導電處理後，以規定之厚度實施鍍敷而形 成。 除了鋁多孔體之骨架為鋁被覆材以外，實施形態2係 藉由與實施形態1相同之要點而製造鋰電池用合金負極及 鋰電池。 (實施形態3) 於上述各實施形態中’鐘金屬之含入並不限定於浸透 至鋁多孔體之空孔中，亦可為形成於鋁多孔醴之表面之形 態。 另外，鋰金屬無需為單質，亦可為與其他金屬之合金， Ll〜Si (矽）、Li — Sn (錫）尤其適合作為合金負極。 於鋁多孔體上形成此種Li— Si或Li— Sn之合金負極之 情形時’可於鋁多孔體之表面形成Li與Si或Sn之合金層， 或者亦可於「鋁骨架」或「銅等之芯材之表面上所形成之 錄層」上設置Si或Sn金屬層，進而積層Li金屬層而形成。 [實施例] (實施例1、2 ) 實施例1係具有於骨架由鋁所形成之鋁多孔體中含入 鐘金屬而形成之負極的鋰二次電池。 實施例2係具有於骨架為於Cu製之芯材之表面形成鋁 層之紹被覆材的紹多孔體中含入鐘金屬而形成之負極的链 二次電池。 15 201201440 (1 )鋁多孔體之製作 於實施例i中，準備孔隙率為97%，孔隙直徑約為· // m之聚胺曱酸酯泡沫。藉由真空蒸鍍法，於該聚胺甲酸酯 泡沫之表面形成厚度約為5〇心之紹層後，浸潰於溫度5〇〇 C之LiCl-KCl共晶炫鹽中，而將紹層於低於紹之標準電 極電位的電位下保持30分鐘。其後於大氣中冷卻至室溫， 水洗除去炫鹽而製作以銘層作為骨架之厚度為。.5贿、孔 隙率為97%之鋁多孔體。 於實施例2中，準備孔隙率為97%、孔隙直徑約為· ”之聚胺甲酸s旨泡珠。於該聚胺甲酸醋泡殊之表面塗佈碳 粉末進行導電處理後，㈣厚度為2“m之銅而形成芯材。 藉由真空蒸鑛法，於其上形成厚度約& 5Mm之紹之表層 後，浸潰於溫度500。(：之LiC卜KC1共晶炫鹽中，而將紹層 於低於鋁之標準電極電位的電位下保持3〇分鐘。其後，於 大氣中冷卻至室溫，水洗除去溶鹽而製作以於cu之芯材之 表面形成有鋁之表層的鋁被覆材作為骨架之厚度為 〇.5mm、孔隙率為％%之鋁多孔體。 於考例中，準備孔徑為200 " m〜5〇〇 v m，且孔隙葬 為97%、厚度為j 〇mm之發泡胺甲酸乙醋泡床。將該發泡 胺甲酸乙酯泡沫配置於真空蒸鍍裝置内。藉由使鋁金屬炼 融蒸务之真空蒸錢法，而於發泡胺甲酸乙醋樹脂之表面 蒸鑛紹膜。其後，藉由於大氣中進行55()t之熱處理，而除 去發泡胺f酸乙3旨料。藉此，獲得作為參相之紹多孔 體。 16 201201440 (2 )鋁多孔體之構造之確認與氧量之測定 將實施例！之銘多孔體之讓照片示於圖3。由圖3 得知構成！呂多孔體之孔為連通狀態。另外，得知實施例i 之铭多孔體不具有閉合孔。 針對實施例…呂多孔體之表面，於⑽之加速電壓 下進行EDX分析。將其結果示於圖4。未觀測到氧之波冷。 因此，得知銘多孔體之氧量$繼之檢測極限以下。此處， 由於咖之檢測極限為氧量質量％，故而可認為實施 例1之鋁多孔體之表面之氧量為31質量％以下。 針對實施例2’亦進行SEM照片之拍攝與腹分析， 確認到與實施例1相同之結果。 針對參考例之銘多孔體之表面，亦以同樣之條件進行 EDX分析。結果觀測到氧之波峰，得知紹多孔體之氧量至 少超過3·1質量％ 4原因在於：於進行熱處理時，銘多孔 體之表面發生氧化。 再者，該分析所使用之裝置為EDAX&司製造之「驗父 PhonenU」，其型號為 HIT22 i36_2 5。 (3 )負極之製作 。於銘多孔體上貼合厚度為35〇心之锂箱後，加熱至 250 (：使Ll熔融，而使Li浸透至空孔中。再者，鋰金屬之 體積於空孔中所占之比率為75〇/〇。 將於空孔中浸透有鋰金屬之鋁多孔體成形為直 l5mm之圓形，而製作鋰電池用合金負極。 二 (4 )鋰電池用正極之製作 17 201201440 以規定之比率混合Mn〇2 (活，w札肪、 /系 助劑）、PVDF (黏合劑），而製作亩 ，衣1下置搜為15mm、容量密度 為10mAh/cm2之鋰電池用正極。 (5 )鋰二次電池之製作 其次，使用負極及正極而制你加 叩I作鋰二次電池。圖5係用 於說明本實施例之鋰電池之構成沾国 馎珉的圖。於圖5中，11為鋰 一次電池’ 12為經電池用正極，]3从 ^ 1 3為間隔件，14為鋰電池 用合金負極。 具體而言，於正極12與負極14之間夾持聚丙烯製之 間隔件而進行積層，使用由溶解有i莫耳％之uci〇4之（^ ) 石反Ssl丙· 一西旨/破酸乙二g旨/二甲备且， ’ 一甲氧基乙烷之混合液所構成 的電解液進行組裝。 (比較例） 比較例係具有A1—U合金落之負極的鋰二次電池。In the case of an aluminum powder or a binder (adhesive resin), the aluminum paste is, for example, a mixture or an organic solvent. Specifically, 201201440: After applying the batter to the surface of the resin, heating is performed to remove the organic solvent and the binder resin, and (4) is sintered. The heating during sintering can be carried out in stages or several times. For example, the organic solvent may be removed by heating at a low temperature after coating, and then immersed in a molten salt and heated to sinter the aluminum paste while the resin is decomposed. By the present month, it is possible to use an alloyed alloy negative electrode having a large density and a high charge/discharge cycle, a method for producing the same, and a lithium battery. [Embodiment] Hereinafter, embodiments of the present invention will be described based on the drawings. In the following, the same or corresponding portions are denoted by the same reference numerals, and the description thereof will not be repeated. In addition, the dimensional ratio of the drawings is not necessarily consistent with the description. (Embodiment 1) 合金·: An alloy negative electrode for a battery of the present invention In the alloy negative electrode for a clock battery according to the present embodiment, a porous metal body is filled with a metal, and a skeleton of the aluminum porous body is made of aluminum. Further, in the present embodiment, the alloy negative electrode for a battery is produced by the following production method (see Fig. 1A to Fig. 1C). B. Method for Producing Alloy Negative Electrode for Clock Battery Porous resin 1 is a foamed resin or nonwoven fabric having continuous pores, particularly preferably having a porosity of 80% to 98% and a pore diameter of 50 " m~500 // The resin of about m is preferably a foamed urethane. Hereinafter, a method for producing an alloy negative electrode for a lithium battery will be described in the order of the aluminum layer forming step, the aluminum porous body producing step, and the clock metal containing (filling) step. 12 201201440 (1) The aluminum layer forming step is directly formed on the surface of the resin crucible by a gas phase method such as a true distillate, a cesium clock method, a laser stripping method or a plasma Cvd, a plating method, an aluminum paste coating method, or the like. The aluminum layer 2 is used to form an aluminum layer coating resin 3. In order to perform electrolytic plating, the surface of the resin crucible is previously electrically conductively treated. The conductive treatment is any method such as electroless plating of a conductive metal such as nickel, vapor deposition or sputtering of aluminum or the like, or application of a conductive coating containing conductive particles such as carbon. The plating bath for plating aluminum is a molten salt of a multicomponent system such as AWL-XU (X: metallization)_Mclx (M is an additive element selected from the group consisting of Cr, Mn, and a transition metal element). The resin ι is impregnated in the molten salt, and the electrically conductive resin is used as a negative electrode for electrolytic deposition. The formation of the aluminum layer can also be carried out by coating an aluminum paste as described above. Aluminum paste A mixture of aluminum powder, binder (binder resin) and organic solvent. A predetermined amount of the paste is applied to the surface of the resin 1 t, and sintered in a silky environment. (2) Step of producing aluminum porous body Next, the resin 1 is thermally decomposed and removed. ^ 2 is a schematic view for explaining the step of decomposing the porous resin in the molten salt 6. In the salt containing more than j kinds selected from the group consisting of UC, KC, NaC, A1C13, the temperature is lower than the melting point of aluminum, preferably 5 〇〇 (> The resin of the aluminum layer (that is, the aluminum layer film resin 3) applies a predetermined voltage between: or a positive electrode 5 made of titanium, and maintains the aluminum layer of the working layer 3, which is lower than the standard electrode potential of aluminum. (potentially higher than the potential of the reduction potential of K and Na), the porous resin i is thermally decomposed and removed, and 13 201201440 is used to produce the porous body 4β (3) metal inclusion (filling) step of Fig. 1c, followed by The aluminum porous body produced contains a predetermined amount of lithium metal and a tantalum aluminum alloy (Li_Al alloy) to produce a lithium battery junction. The micro-miebe, tantalum, for example, a laminated aluminum porous body and a predetermined thickness of lithium foil After that, ',, ' to 1 80 c or more, so that the inner foil can be melted and soaked into the pores of the aluminum porous body, so that the aluminum porous body can be immersed in the heating to 18 〇. Furthermore, the amount of lithium contained is the ratio of the volume of lithium metal to the pores of the aluminum porous body. When it is 50 〇 / 〇 or more and less than 1 〇〇〇 / 〇, for example, when a porous aluminum body having a porosity of 97% and a lithium foil having a thickness of 1/2 of the aluminum porous body are attached, The ratio of the volume of lithium metal to the pores is 51.5%. 〇C. Lithium battery In the alloy negative electrode for lithium batteries thus produced, the Li _ A1 alloy produced has a concentration of aluminum higher in the vicinity of the skeleton. The concentration gradient decreases as it moves away from the skeleton. Therefore, even when the Li-A1 alloy expands and contracts, it is easy to alleviate the stress and suppress the micronization. In addition, since the volume of lithium metal is in the pores of the aluminum porous body, The ratio is 50% or more, so that a sufficiently high capacity density is ensured. On the other hand, by setting the ratio to less than 100%, voids remain in the porous body after filling Li, so even if it is generated In the case of a lithium dendrite, the dendrite is also short-circuited. (Embodiment 2) In the second embodiment, the skeleton of the aluminum porous body is formed on the surface of the core material 14 201201440 9 into an aluminum coating material having an aluminum layer. In addition, the core material is made of copper, It is composed of any one of nickel and iron, and is formed by coating a surface of a resin having a continuous hole with a conductive powder and then performing plating treatment with a predetermined thickness. The skeleton of the aluminum porous body is aluminum. In the second embodiment, the alloy negative electrode and the lithium battery for a lithium battery are manufactured in the same manner as in the first embodiment. (Embodiment 3) In the above embodiments, the inclusion of the bell metal is not limited to the soaking. In the pores of the aluminum porous body, it may be formed on the surface of the porous aluminum crucible. In addition, the lithium metal need not be a single substance, and may be an alloy with other metals, L1 to Si (矽), Li-Sn ( Tin) is especially suitable as an alloy negative electrode. When such an alloy negative electrode of Li-Si or Li-Sn is formed on an aluminum porous body, an alloy layer of Li and Si or Sn may be formed on the surface of the aluminum porous body, or may be an "aluminum skeleton" or "copper". A recording layer formed on the surface of the core material is provided with a Si or Sn metal layer, and a Li metal layer is laminated. [Examples] (Examples 1 and 2) Example 1 is a lithium secondary battery having a negative electrode formed by containing a clock metal in an aluminum porous body in which a skeleton is made of aluminum. In the second embodiment, a chain secondary battery having a negative electrode formed of a bell metal in a porous body in which a skeleton is formed of an aluminum layer on the surface of a core material made of Cu is used. 15 201201440 (1) Production of aluminum porous body In the example i, a polyamine phthalate foam having a porosity of 97% and a pore diameter of about // m was prepared. After forming a layer having a thickness of about 5 〇 on the surface of the polyurethane foam by vacuum evaporation, the layer is immersed in a LiCl-KCl eutectic salt at a temperature of 5 〇〇C, and The layer was held at a potential lower than the standard electrode potential for 30 minutes. Thereafter, it was cooled to room temperature in the air, washed with water to remove the dazzling salt, and the thickness of the inscription layer was used as a skeleton. .5 Bribe, an aluminum porous body with a porosity of 97%. In Example 2, a polyurethane s-ball having a porosity of 97% and a pore diameter of about ” is prepared. After the surface of the polyurethane foam is coated with carbon powder for conducting treatment, (iv) thickness A core material is formed for 2"m of copper. The surface layer having a thickness of about & 5 Mm was formed thereon by vacuum evaporation, and then immersed at a temperature of 500. (: LiCBu KC1 eutectic salt, and the layer is kept at a potential lower than the standard electrode potential of aluminum for 3 minutes. Thereafter, it is cooled to room temperature in the atmosphere, washed with water to remove dissolved salts. An aluminum coated material having a surface layer of aluminum formed on the surface of the core material of cu is used as an aluminum porous body having a skeleton thickness of 〇5 mm and a porosity of %%. In the test, a pore diameter of 200 " m~5〇 was prepared. 〇vm, and the void is buried in 97%, the thickness of j 〇mm foaming urethane acetate bubble bed. The foaming urethane foam is placed in a vacuum evaporation device. The vacuum evaporation method is carried out, and the surface of the foamed amine acetate resin is evaporated to form a film. Thereafter, the foaming amine f acid B is removed by heat treatment of 55 () t in the atmosphere. Thereby, a porous body as a phase is obtained. 16 201201440 (2) Confirmation of the structure of the aluminum porous body and measurement of the amount of oxygen The photo of the example of the porous body of the example is shown in Fig. 3. The hole of the porous body of Lu is in a connected state. In addition, it is known that the porous body of the embodiment i does not have a closed hole. For the surface of the Example...lu porous body, EDX analysis was carried out under the accelerating voltage of (10). The results are shown in Fig. 4. No oxygen wave was observed. Therefore, the oxygen amount of the porous body was observed. Here, the detection limit of the coffee is the oxygen mass%, and therefore the amount of oxygen on the surface of the aluminum porous body of the first embodiment is considered to be 31% by mass or less. The SEM photograph is also taken for the example 2'. The abdominal analysis confirmed the same results as in Example 1. The surface of the porous body of the reference example was also subjected to EDX analysis under the same conditions. As a result, the peak of oxygen was observed, and it was found that the oxygen content of the porous body was at least more than 3. · 1% by mass 4 The reason is that the surface of the porous body is oxidized during the heat treatment. The device used in this analysis is the "Father's PhonenU" manufactured by EDAX & Division, model number HIT22 i36_2 5. 3) Fabrication of the negative electrode. After bonding the lithium box with a thickness of 35 inches to the porous body of Yuming, heat it to 250 (: so that Ll is melted, and Li is soaked into the pores. Furthermore, the volume of lithium metal is empty. The ratio in the hole is 75〇 /〇. A porous aluminum body impregnated with lithium metal in a hole is formed into a circular shape of a straight l5 mm, and an alloy negative electrode for a lithium battery is fabricated. Preparation of a positive electrode for a lithium battery is used 2012 201201440 Mixing Mn at a prescribed ratio 〇2 (live, w za fat, / auxiliaries), PVDF (adhesive), and make a mu, the first one of the clothing is 15mm, the capacity density is 10mAh/cm2 for the lithium battery positive electrode. (5) lithium two Next, the secondary battery and the positive electrode are used to make a lithium secondary battery. Figure 5 is a diagram for explaining the composition of the lithium battery of the present embodiment. In Fig. 5, 11 is lithium. The primary battery '12 is the positive electrode for the battery, and the third is the separator from ^1 3, and 14 is the alloy negative electrode for the lithium battery. Specifically, a separator made of polypropylene is sandwiched between the positive electrode 12 and the negative electrode 14 to be laminated, and (^) which is dissolved by i mol% of uci〇4 is used. An acid solution composed of a mixture of 'monomethoxy ethane and acid mixture was assembled. (Comparative Example) A comparative example is a lithium secondary battery having a negative electrode of an A1-U alloy.

製作鋁之比率為50原子％、直徑為l5mm之Al—U A 金羯作為經電池用合金負極’使用該負極及與實施例同： 地製作之链電池用正極’與實施例同樣地製作鐘二次電池。 (實施例1、2及比較例之鐘二次電池之特性評價） (1 )良率 於實施例1、2之情形時， 相對於此’比較例之良率較低 形時，良率如此低之原因在於 於操作時會發生裂縫或缺損。 組裝電池時之良率為100〇/〇， ，約為50%。於比較例之情 :鋰電池用合金負極較脆弱， (2 )充放電循環特性 18 201201440 1.試驗方法 將截止電壓設為2_〇ν〜3.3V，於6mA/h與18mA/h 之兩種放電深度下進行充放電循環試驗，而調查放電容量 成為初期之5 0%以下的循環數。 2 ·試驗結果 將實施例1、2及比較例之試驗結果示於表1。 [表1] 循史 良數 放電深度 10% (1.7mAh) 50% (8.5mAh) 實施例1 使用A1多孔體 1000 500 實施例2 使用Al—Cu多孔體 1000 500 比較例 A1 (A150at%) — Li 合金 200 50 由表1得知，實施例1、2之循環特性優異。實施例之 楯環特性如此優異之原因在於：使用了微粉化與樹枝狀結 晶短路之抑制效果較高之鋰電池用合金負極。 另外，如上所述，實施例係使Li含入無閉合孔且氧量 車乂少之鋁多孔體中，因此係具有容量密度較高之鋰電池用 合金負極的鋰二次電池。 以上，對本發明之實施形態進行了說明，但本發明並 不限疋於上述實施形態。可於與本發明相同及均等之範圍 内’對上述實施形態實施各種變更。 [產業上之可利用性] 根據如上所述之本發明，由於使鋰含入無閉合孔且氧 量較少之鋁多孔體，故而可提供容量密度較大且充放電循 19 201201440 環優異之鋰電池用合金負極和其製造方法及鋰電池。 【圖式簡單說明】 圖1A’係表示鋁多孔體之製造步驟中具有連通孔之樹 脂之剖面之一部分的模式圖。 圖1B，.係表示鋁多孔體之製造步驟中於具有連通孔之 樹脂之表面形成有鋁層之.情形（鋁層被膜樹脂）的模式圖。 圖1C，係表示鋁多孔體之製造步驟中使樹脂熱分解而 使其自鋁層被膜樹脂消失後之情形（鋁多孔體）的模式圖。 圖2，係用以課明樹脂於熔鹽中分解之步驟的模式圖。 圖3 ’係本發明之紹多孔體之sem照片。 圖4，係表示本發明之鋁多孔體之edx分析結果的圖。 圖5 ’係說明本發明之鋰電池之圖。 【主要元件符號說明】 1 樹脂 2 紹層 3 鋁層被覆樹脂 4 鋁多孔體 5 正極 6 炫鹽 11 裡二次電池 12 鋰電池用正極 13 間隔件 14 鋰電池用合金負極 20An Al-UA metal ruthenium having a ratio of aluminum of 50 atom% and a diameter of 15 mm was produced as the alloy negative electrode for a battery, and the negative electrode of the same type as that of the example was used: Secondary battery. (Evaluation of Characteristics of Clock Secondary Batteries of Examples 1, 2, and Comparative Examples) (1) When the yield is in the cases of Examples 1 and 2, the yield is lower than when the yield of the comparative example is low. The reason for the low is that cracks or defects occur during operation. The yield when assembling the battery is 100 〇 / 〇, which is about 50%. In the case of the comparative example: the alloy anode for lithium battery is weak, (2) charge and discharge cycle characteristics 18 201201440 1. The test method sets the cutoff voltage to 2_〇ν~3.3V, at 6mA/h and 18mA/h. The charge and discharge cycle test was carried out at the depth of discharge, and the number of cycles in which the discharge capacity was 50% or less in the initial stage was investigated. 2 Test Results The test results of Examples 1, 2 and Comparative Examples are shown in Table 1. [Table 1] Well-known discharge depth 10% (1.7 mAh) 50% (8.5 mAh) Example 1 Using A1 porous body 1000 500 Example 2 Using Al-Cu porous body 1000 500 Comparative Example A1 (A150 at%) - Li Alloy 200 50 As seen from Table 1, the cycle characteristics of Examples 1 and 2 were excellent. The reason why the anthracene ring characteristics of the examples are so excellent is that an alloy negative electrode for a lithium battery having a high suppression effect of micronization and dendritic crystal short-circuiting is used. Further, as described above, in the embodiment, Li is contained in an aluminum porous body having no closed pores and a small amount of oxygen, so that it is a lithium secondary battery having an alloy negative electrode for a lithium battery having a high capacity density. Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. Various modifications may be made to the above-described embodiments within the scope of the invention and the scope of the invention. [Industrial Applicability] According to the present invention as described above, since lithium is contained in an aluminum porous body having no closed pores and a small amount of oxygen, it is possible to provide a large capacity density and excellent charge and discharge cycle 19 201201440 An alloy negative electrode for a lithium battery, a method for producing the same, and a lithium battery. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A' is a schematic view showing a part of a cross section of a resin having a communicating hole in a manufacturing step of an aluminum porous body. Fig. 1B is a schematic view showing a case where an aluminum layer is formed on the surface of a resin having a communicating hole in the manufacturing step of the aluminum porous body (aluminum layer film resin). Fig. 1C is a schematic view showing a state (aluminum porous body) in which the resin is thermally decomposed in the manufacturing step of the aluminum porous body to be removed from the aluminum layer film resin. Figure 2 is a schematic view showing the steps of decomposing the resin in the molten salt. Figure 3 is a photograph of a sem of a porous body of the present invention. Fig. 4 is a view showing the results of edx analysis of the aluminum porous body of the present invention. Figure 5 is a view showing the lithium battery of the present invention. [Description of main component symbols] 1 Resin 2 Coating layer 3 Aluminum layer coating resin 4 Aluminum porous body 5 Positive electrode 6 Hyun salt 11 Secondary battery 12 Positive electrode for lithium battery 13 Spacer 14 Alloy negative electrode for lithium battery 20

Claims (1)

201201440 七、申請專利範圍： 1 · 一種鋰電池用合金負極，係使用非水電解液者其特 徵在於· ^ 於銘多孔體中填充有鋰金屬。 2. 如申請專利範圍第1項之鋰電池用合金負極，其中， 該銘多孔體之骨架係由鋁所形成。 3. 如申晴專利範圍第1項之鋰電池用合金負極，其中， 該鋁多孔體之骨架係由鋁被覆材所形成，該鋁被覆材係於 由銅、鎳、鐵中之任一種金屬所構成之芯材的表面形成鋁 層而成者。 4. 如申請專利範圍第1項之鋰電池用合金負極，其中， 該鋰金屬之體積於該鋁多孔體之空孔中所占的比率為5〇% 以上、未達100%。 5·如申請專利範圍第1項之鋰電池用合金負極，其中， 形成該鋁多孔體之骨架的鋁、或該鋁被覆材之鋁層表面的 氧量為3.1質量％以下。 6. 如申請專利範圍第1項之鋰電池用合金負極，其中， 該鋁多孔體具有連通孔’不具有閉合孔，並且僅由紹所構 成。 7. —種鋰電池，其特徵在於： 具備申明專利範圍第1至6項中任一項之.鐘電池用合 金負極。 8_—種經電池用合金負極之製造方法，其特徵在於具有 如下步驟： 21 201201440 铭層形成步驟：其係將鋁層形成於具有連通孔之樹脂 的表面； 銘多孔體製作步驟：其係於將該樹脂浸潰於熔鹽之狀 態下，一面將該鋁層保持為低於鋁之標準電極電位的電 位’ 一面將該樹脂加熱至鋁之熔點以下的溫度，使該樹脂 熱分解而製作鋁多孔體；及 鋰金屬填充步驟：其係將鋰金屬填充於該鋁多孔體。 9. 一種鋰電池用合金負極之製造方法，其特徵在於具有 如下步驟： 金屬層形成步驟：其係將由銅、鎳、鐵中之任一種金 屬所構成之金屬層形成於具有連通孔之樹脂的表面； 鋁層形成步驟：其係將鋁層形成於該金屬.層的表面； 鋁多孔體製作步驟：其係於將該樹脂浸潰於熔鹽之狀 態下，一面將該鋁層保持為低於鋁之標準電極電位的電 位，一面將該樹脂加熱至鋁之熔點以下的溫度，使該樹脂 熱分解而製作鋁多孔體；及 鋰金屬填充步驟：其係將鋰金屬填充於該鋁多孔體。 10. 如申請專利範圍第8或9項之鋰電池用合金負極之 製造方法’其巾，該鋁層之形成方法為真空蒸鍍法、濺鍍 法、雷射剝蝕法或電漿CVD法。 U.如申請專利範圍第8項之鋰電池用合金負極之製造 方法，其中，該鋁層之形成方法為於對該樹脂之表面進行 導電化處理後’鍍敷鋁之鍍敷法。 I2·如申請專利範圍第9項之鋰電池用合金負極之製造 22 201201440 方法，其中，該鋁層之形成方法為將鋁鍍敷於該金屬層表 面之鍵敷法。 13.如申請專利範圍第8或9項之鋰電池用合金負極之 製造方法，其中，該鋁層之形成方法為將鋁糊塗佈於該樹 脂表面或該金屬層表面之塗佈法。 23201201440 VII. Patent application scope: 1 · An alloy negative electrode for lithium batteries, which is characterized by the use of non-aqueous electrolytes, is characterized by the fact that Yu Ming is filled with lithium metal. 2. The alloy negative electrode for a lithium battery according to the first aspect of the patent application, wherein the skeleton of the porous body is formed of aluminum. 3. The alloy negative electrode for a lithium battery according to claim 1, wherein the skeleton of the aluminum porous body is formed of an aluminum coating material, and the aluminum coating material is one of copper, nickel, and iron. The surface of the core material is formed by forming an aluminum layer. 4. The alloy negative electrode for a lithium battery according to the first aspect of the invention, wherein the ratio of the volume of the lithium metal to the pores of the aluminum porous body is 5% by weight or more and less than 100%. 5. The alloy negative electrode for a lithium battery according to the first aspect of the invention, wherein the aluminum forming the skeleton of the aluminum porous body or the surface of the aluminum layer of the aluminum coating material has an oxygen content of 3.1% by mass or less. 6. The alloy negative electrode for a lithium battery according to claim 1, wherein the aluminum porous body has a communication hole' which does not have a closed hole, and is constituted only by the above. 7. A lithium battery, characterized by: a metal alloy negative electrode for a clock battery according to any one of claims 1 to 6. 8_—the method for producing an alloyed negative electrode for a battery, comprising the steps of: 21 201201440 forming a layer of an ingot: forming an aluminum layer on a surface of a resin having a continuous hole; When the resin is immersed in a molten salt, the aluminum layer is maintained at a potential lower than the standard electrode potential of aluminum, and the resin is heated to a temperature equal to or lower than the melting point of aluminum to thermally decompose the resin to produce aluminum. a porous body; and a lithium metal filling step: filling the aluminum porous body with lithium metal. A method for producing an alloy negative electrode for a lithium battery, comprising the steps of: forming a metal layer by forming a metal layer composed of any one of copper, nickel, and iron in a resin having a communicating hole; Surface; aluminum layer forming step: forming an aluminum layer on the surface of the metal layer; aluminum porous body forming step: maintaining the aluminum layer low while the resin is immersed in the molten salt And heating the resin to a temperature lower than a melting point of aluminum to thermally decompose the resin to form an aluminum porous body; and a lithium metal filling step of filling the aluminum porous body with lithium metal at a potential of a standard electrode potential of aluminum . 10. The method for producing an alloy negative electrode for a lithium battery according to the invention of claim 8 or 9, wherein the aluminum layer is formed by a vacuum evaporation method, a sputtering method, a laser ablation method or a plasma CVD method. U. The method for producing an alloy negative electrode for a lithium battery according to the eighth aspect of the invention, wherein the method for forming the aluminum layer is a plating method of plating aluminum after the surface of the resin is subjected to a conductive treatment. I2. The manufacture of an alloy negative electrode for a lithium battery according to claim 9 of the invention. The method of forming the aluminum layer is a keying method of plating aluminum on the surface of the metal layer. 13. The method for producing an alloy negative electrode for a lithium battery according to claim 8 or 9, wherein the method for forming the aluminum layer is a coating method in which an aluminum paste is applied to the surface of the resin or the surface of the metal layer. twenty three
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