TW201432989A - Positive-electrode material, method for producing the positive-electrode material and nonaqueous electrolyte battery - Google Patents
Positive-electrode material, method for producing the positive-electrode material and nonaqueous electrolyte battery Download PDFInfo
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Abstract
Description
本發明係關於非水電解質電池之正極材。 The present invention relates to a positive electrode material for a nonaqueous electrolyte battery.
以鹼金屬及其化合物作為負極活性物質之非水電解質電池，係藉由鹼金屬離子對正極活性物質之吸收反應而可得大的放電容量，因此，隨著電腦、手機等之小型化而廣泛應用於資訊相關機器、通訊機器等之區域。該非水電解質電池之正極活性物質現在多使用LiCoO2等。但是，為所含元素之鈷為稀少元素而且非常高價，故為電池價格提高之要因，係希望取代其之低價之正極活性物質的開發。 A nonaqueous electrolyte battery using an alkali metal or a compound as a negative electrode active material has a large discharge capacity by absorption reaction of an alkali metal ion on a positive electrode active material, and thus is widely used with miniaturization of computers and mobile phones. It is applied to areas such as information related machines and communication machines. The positive electrode active material of the nonaqueous electrolyte battery now uses LiCoO 2 or the like. However, since the cobalt contained in the element is a rare element and is very expensive, it is a factor for improving the price of the battery, and it is desired to replace the low-priced positive electrode active material.
以往以來，係討論使用含有資源豐富之含鐵的鋰鐵複合氧化物(LixFeyOz)取代LiCoO2作為正極活性物質之非水電解質電池。但是，將鋰鐵複合氧化物作為正極活性物質時，有電池電壓為1.5V之低值，能量密度小之缺點，而留有無法獲得實用的電池之問題。 Conventionally, a nonaqueous electrolyte battery using a lithium iron composite oxide (Li x Fe y O z ) containing a rich amount of iron in place of LiCoO 2 as a positive electrode active material has been discussed. However, when a lithium iron composite oxide is used as a positive electrode active material, there is a disadvantage that the battery voltage is a low value of 1.5 V, and the energy density is small, and there is a problem that a practical battery cannot be obtained.
為此，作為替代手段，如專利文獻1至3所示，考慮到於正極活性物質使用不含有結構水之結晶性FeF3的非水電解 質電池。 For this reason, as an alternative, as shown in Patent Documents 1 to 3, it is considered that a nonaqueous electrolyte battery containing crystalline FeF 3 which does not contain structural water is used for the positive electrode active material.
專利文獻1：日本特開平9-022698號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 9-022698
專利文獻2：日本特開平9-055201號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. H9-055201
專利文獻3：日本特開2000-2033號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-2033
專利文獻4：日本特開2010-170867號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-170867
若在正極活性物質之FeF3中***Li離子，認為經過FeF3並進一步藉由Li之***，會使反應進行到分解為Fe與LiF之轉換區域。但是，因FeF3中Fe與F之間的鍵結強，故難以引起到達轉換區域之反應。此外，難以從轉換區域再生為原本之FeF3，此認為是使電池性能降低之原因。因此，專利文獻1至3中，作為充放電之電壓範圍，僅在反應未進行到轉換區域之插層(intercalation)區域之電壓範圍(若為鋰離子二次電池則為4.5V至2V)會充放電。在該電壓範圍之充放電中，Li***/脫離於FeF3，僅有進行可逆的FeF3+xLi→LixFeF3反應，可得理論容量為230mAh/g左右。 When Li ions are inserted into FeF 3 of the positive electrode active material, it is considered that the reaction proceeds to a conversion region of Fe and LiF after passing through FeF 3 and further by insertion of Li. However, since the bond between Fe and F in FeF 3 is strong, it is difficult to cause a reaction to reach the conversion region. Further, it is difficult to regenerate from the conversion region to the original FeF 3 , which is considered to be a cause of degrading battery performance. Therefore, in Patent Documents 1 to 3, as the voltage range of charge and discharge, only the voltage range of the intercalation region where the reaction does not proceed to the conversion region (4.5 V to 2 V for a lithium ion secondary battery) Discharge. In the charge and discharge of this voltage range, Li is inserted/desorbed from FeF 3 , and only the reversible FeF 3 +xLi→Li x FeF 3 reaction is performed, and the theoretical capacity is about 230 mAh/g.
另一方面，若反應進行到轉換區域，則FeF3會分解而由Fe3+電解還原至Fe0，故理論上可得700mAh/g以上之容量，係期待二次電池之大幅高容量化。為此，如專利文獻4所示，藉由FeF3之微粒子化，而檢討利用到達轉換區域之反應，但尚末滿足其循環特性(壽命)。 On the other hand, when the reaction proceeds to the conversion region, FeF 3 is decomposed and electrolyzed to Fe 0 by Fe 3+ electrolysis, so theoretically, a capacity of 700 mAh/g or more can be obtained, and a large capacity of the secondary battery is expected to be increased. For this reason, as shown in Patent Document 4, the reaction to reach the conversion region is examined by the fine particles of FeF 3 , but the cycle characteristics (life) are satisfied.
本發明係鑑於如此課題而研究者，其目的係提供在 利用FeF3到達轉換反應時，可得安定循環特性之非水電解質蓄電池用之正極材、及其製造方法，進一步提供使用該正極材之非水電解質電池。 The present invention has been made in view of such a problem, and an object of the present invention is to provide a positive electrode material for a nonaqueous electrolyte secondary battery which can obtain stable cycle characteristics when FeF 3 is used for a conversion reaction, and a method for producing the same, and further provide a positive electrode material. Non-aqueous electrolyte battery.
本發明之一態樣係非水電解質電池用之正極材。該正極材係含有平均粒徑200nm以下的微粒子，該微粒子包含將FeF3以3價金屬取代之氟化金屬。 One aspect of the present invention is a positive electrode material for a nonaqueous electrolyte battery. The positive electrode material contains fine particles having an average particle diameter of 200 nm or less, and the fine particles include a metal fluoride in which FeF 3 is substituted with a trivalent metal.
上述態樣之正極材係用以下通式(1)表示。 The positive electrode material of the above aspect is represented by the following general formula (1).
Fe(1-x)AlxF3(1) Fe (1-x) Al x F 3 (1)
(但x係0.01≦x≦0.5。) (But x is 0.01≦x≦0.5.)
本發明之其他態樣係正極材之製造方法。該正極材之製造方法的特徵係具備：藉由使用金屬鹽、及氟化銨之水溶液之沉澱法，而合成氟化金屬銨鹽前驅物之步驟；燒製所得氟化金屬銨鹽前驅物之步驟。 Another aspect of the present invention is a method of producing a positive electrode material. The method for producing a positive electrode material includes a step of synthesizing a metal fluoride ammonium salt precursor by a precipitation method using a metal salt and an aqueous solution of ammonium fluoride; and firing the obtained metal fluoride ammonium salt precursor step.
上述態樣之製造方法中，金屬鹽可為硝酸鹽。將含有3價鐵離子與其他1種類之3價金屬離子之水溶液、以及氟化銨水溶液醇中等量滴加，藉此可得氟化金屬銨鹽前驅物。醇可為乙醇。含有3價鐵離子之水溶液或是含有其他1種之3價金屬離子之水溶液、與氟化銨水溶液之濃度比，係以含有3價鐵離子之水溶液或是含有其他1種之3價金屬離子之水溶液為1時，氟化銨水溶液之濃度可為0.1至10。燒製氟化金屬銨鹽前驅物之步驟，可具有在低溫燒製氟化銨鹽前驅物後進一步以高溫燒製之2階段步驟。此外，可包括使燒製所得氟化金屬之平均粒徑成為10至200nm之微細化步驟。 In the above production method, the metal salt may be a nitrate. An aqueous solution containing a trivalent iron ion and another type of trivalent metal ion and an aqueous solution of an ammonium fluoride aqueous solution are added in an appropriate amount to obtain a metal fluoride ammonium salt precursor. The alcohol can be ethanol. An aqueous solution containing trivalent iron ions or an aqueous solution containing one other trivalent metal ion and a concentration ratio of an aqueous solution of ammonium fluoride to an aqueous solution containing trivalent iron ions or containing one other trivalent metal ion When the aqueous solution is 1, the concentration of the aqueous ammonium fluoride solution may be from 0.1 to 10. The step of firing the ammonium fluoride ammonium salt precursor may have a two-stage step of further firing at a high temperature after firing the ammonium fluoride salt precursor at a low temperature. Further, a refining step of making the average particle diameter of the fluorinated metal obtained by firing into 10 to 200 nm may be included.
本發明之另一其他態樣係非水電解質電池。該非水電解質電池之特徵係使用上述之任一態樣之正極材。 Another aspect of the invention is a non-aqueous electrolyte battery. The nonaqueous electrolyte battery is characterized by using the positive electrode material of any of the above aspects.
另外，適宜組合上述各要素者亦包括於本案專利申請之專利所保護之發明範圍。 In addition, the combination of the above-mentioned various elements is also included in the scope of the invention protected by the patent application of the present patent application.
根據本發明，係可利用FeF3至轉換反應，同時使非水電解質蓄電池之循環特性安定化。 According to the present invention, the FeF 3 to conversion reaction can be utilized while the cycle characteristics of the nonaqueous electrolyte secondary battery are stabilized.
11‧‧‧外裝部品 11‧‧‧ Exterior parts
12‧‧‧正極 12‧‧‧ positive
13‧‧‧外裝部品 13‧‧‧External parts
14‧‧‧負極 14‧‧‧negative
15‧‧‧隔膜 15‧‧‧Separator
17‧‧‧密封墊片 17‧‧‧Sealing gasket
18‧‧‧彈簧 18‧‧‧ Spring
19‧‧‧隔片 19‧‧‧ spacer
100‧‧‧電池 100‧‧‧Battery
第1圖係前驅物1至3、比較前驅物1、2之各X射線繞射圖形。 The first figure is the X-ray diffraction pattern of the precursors 1 to 3 and the comparative precursors 1, 2.
第2圖係實施例1之正極材及比較例1之正極材之各X射線繞射圖形。 Fig. 2 is a graph showing the X-ray diffraction patterns of the positive electrode material of Example 1 and the positive electrode material of Comparative Example 1.
第3圖係前驅物1及實施例1之正極材之SEM像(倍率×10,000)。 Fig. 3 is an SEM image (magnification × 10,000) of the positive electrode material of the precursor 1 and the first embodiment.
第4圖係實施例1之正極材之SEM像(倍率×20,000)。 Fig. 4 is a SEM image (magnification × 20,000) of the positive electrode material of Example 1.
第5圖係比較前驅物1及比較例1之正極材之SEM像(倍率×10,000)。 Fig. 5 is a comparison of SEM images (magnification × 10,000) of the positive electrode materials of the precursor 1 and the comparative example 1.
第6圖係表示循環特性評價所使用之錢幣型之非水電解質電池之構造的示意剖面圖。 Fig. 6 is a schematic cross-sectional view showing the structure of a coin-type nonaqueous electrolyte battery used for evaluation of cycle characteristics.
第7圖係實施例1之正極材(以球磨機粉碎後)之SEM像(倍率×10,000)。 Fig. 7 is an SEM image (magnification × 10,000) of the positive electrode material (after pulverization by a ball mill) of Example 1.
第8圖係比較例1之正極材(以球磨機粉碎後)之SEM像(倍率×10,000)。 Fig. 8 is an SEM image (magnification × 10,000) of a positive electrode material (after pulverization by a ball mill) of Comparative Example 1.
第9圖係實施例2、比較例3、4之正極材之各X射線繞射圖形。 Fig. 9 is a graph showing the X-ray diffraction patterns of the positive electrode materials of Example 2 and Comparative Examples 3 and 4.
本發明人等為了解決上述課題而累積精心研究結果發現，藉由使用金屬硝酸鹽與氟化銨之水溶液之沉澱法而合成氟化金屬銨鹽前驅物，並將其燒製，藉此而得之在FeF3摻雜特定元素(Al等)之例如Fe(1-x)AlxF3，使用其而在利用至轉換反應時也可得安定之循環特性，從而完成本發明。 In order to solve the above problems, the present inventors have accumulated intensive studies and found that a metal fluoride ammonium salt precursor is synthesized by a precipitation method using an aqueous solution of a metal nitrate and ammonium fluoride, and is fired therefrom. The FeF 3 is doped with a specific element (Al or the like) such as Fe (1-x) Al x F 3 , and the cycle characteristics of stability can be obtained by using it to the conversion reaction, thereby completing the present invention.
(正極材) (positive electrode material)
實施形態之正極材係使用非水電解質電池之正極材。實施形態之正極材係具有包括下述通式(1)所表示之氟化金屬的微粒子，其平均粒徑為10至200nm。 In the positive electrode material of the embodiment, a positive electrode material of a nonaqueous electrolyte battery is used. The positive electrode material of the embodiment has fine particles including a metal fluoride represented by the following general formula (1), and has an average particle diameter of 10 to 200 nm.
Fe1-xMexF3(1) Fe 1-x Me x F 3 (1)
(但是，Me係在水溶液中可能以3價離子存在之元素，x為0.01≦x≦0.5。) (However, Me is an element that may exist as a trivalent ion in an aqueous solution, and x is 0.01≦x≦0.5.)
通式(1)中Me之元素例如可舉出Al等。另外，包含氟化金屬之微粒子之平均粒徑若大於200nm，則難以利用至轉換反應。另一方面，若包含氟化金屬之微粒子之平均粒徑小於10nm，則材料之處理或電極混合劑製作時之分散會變得困難。 The element of Me in the formula (1) is, for example, Al or the like. Further, when the average particle diameter of the fine particles containing the metal fluoride is more than 200 nm, it is difficult to utilize the conversion reaction. On the other hand, if the average particle diameter of the fine particles containing the metal fluoride is less than 10 nm, the treatment of the material or the dispersion at the time of preparation of the electrode mixture becomes difficult.
上述通式(1)所表示之正極材，係可利用至轉換反應。進一步，將該正極材裝入非水電解質電池時，可得安定之循環特性。 The positive electrode material represented by the above formula (1) can be used until the conversion reaction. Further, when the positive electrode material is charged into a nonaqueous electrolyte battery, stable cycle characteristics can be obtained.
(正極材之製造方法) (Method of manufacturing positive electrode material)
實施之形態之正極材之製造方法係包括：將含有3價鐵離子 與其他1種類之3價金屬離子之水溶液、以及氟化銨水溶液於醇中等量滴加之步驟；以及將所得氟化(鐵、其他金屬)銨鹽作為前驅物，並燒製該前驅物之步驟。 The method for producing a positive electrode material of the embodiment includes: containing a trivalent iron ion And an aqueous solution of one of the other kinds of trivalent metal ions, and an aqueous solution of ammonium fluoride in an amount of an appropriate amount of the alcohol; and the step of using the obtained fluorinated (iron, other metal) ammonium salt as a precursor and firing the precursor .
金屬鹽較佳為硝酸鹽、氫氧化物鹽、氯化物鹽、金屬溴化物鹽、金屬氟化物鹽等，但其中更佳為硝酸鹽。 The metal salt is preferably a nitrate, a hydroxide salt, a chloride salt, a metal bromide salt, a metal fluoride salt or the like, but more preferably a nitrate.
醇較佳為使用甲醇、乙醇、丙醇、異丙醇、丁醇等，最佳為乙醇。 The alcohol is preferably methanol, ethanol, propanol, isopropanol, butanol or the like, and most preferably ethanol.
含有3價鐵離子之水溶液或是含有其他1種之3價金屬離子之水溶液、與氟化銨水溶液之濃度比，以含有3價鐵離子之水溶液或是含有其他1種之3價金屬離子之水溶液為1時，氟化銨水溶液之濃度為0.1至10，較佳為1至8，更佳為2至6。 An aqueous solution containing trivalent iron ions or an aqueous solution containing one other trivalent metal ion, and a concentration ratio of an aqueous solution of ammonium fluoride to an aqueous solution containing trivalent iron ions or containing one other trivalent metal ion When the aqueous solution is 1, the concentration of the aqueous ammonium fluoride solution is from 0.1 to 10, preferably from 1 to 8, more preferably from 2 to 6.
得到氟化(鐵、其他金屬)銨鹽前驅物後所實施之燒製步驟，較佳為包括將所得氟化(鐵、其他金屬)銨鹽前驅物以低溫燒製後進一步以高溫燒製之2階段步驟。藉由以2階段燒製，而可得更高純度之生成物。 The step of firing after obtaining the fluorinated (iron, other metal) ammonium salt precursor preferably comprises baking the obtained fluorinated (iron, other metal) ammonium salt precursor at a low temperature and further firing at a high temperature. 2-stage step. A higher purity product can be obtained by firing in two stages.
上述2階段之步驟中，初期步驟中溫度為100℃以上，較佳為150℃以上，更佳為200℃以上。 In the above two-step step, the temperature in the initial step is 100 ° C or higher, preferably 150 ° C or higher, more preferably 200 ° C or higher.
上述2階段之步驟中，後期步驟中溫度為250℃以上，較佳為300℃以上，更佳為350℃以上。 In the above two-stage step, the temperature in the later step is 250 ° C or higher, preferably 300 ° C or higher, more preferably 350 ° C or higher.
此外，以該手法所得之前驅物(NH4)3Fe(1-x)MexF3(Me係在水溶液中可以3價離子存在之元素)，係以掃描型電子顯微鏡(SEM)觀測之平均粒子徑為200至500nm以下之微結晶。所得前驅物(微結晶)係視需要藉由球磨機等之微細化技術，而成形為平均粒徑10至200nm以下(以掃描型電子顯微鏡(SEM)觀測)之微粒 子。如此所得該正極材之BET比表面積為8m2/g以上，較佳為10m2/g以上。 Further, the precursor (NH4) 3Fe (1-x) Me x F 3 (Me is an element which can exist as a trivalent ion in an aqueous solution) obtained by this method is an average particle observed by a scanning electron microscope (SEM). Microcrystals having a diameter of 200 to 500 nm or less. The obtained precursor (microcrystal) is formed into fine particles having an average particle diameter of 10 to 200 nm or less (observed by a scanning electron microscope (SEM)) by a micronization technique such as a ball mill. The BET specific surface area of the positive electrode material thus obtained is 8 m 2 /g or more, preferably 10 m 2 /g or more.
藉由以上步驟而製造上述通式(1)所示之正極材。 The positive electrode material represented by the above formula (1) is produced by the above steps.
(非水電解質蓄電池) (non-aqueous electrolyte battery)
實施形態之非水電解質蓄電池，係具有包含正極、負極、隔膜、電解液之已知之電池構造。正極係具有活性物質、導電材及黏結劑。非水電解質電池之形態係無特別限定，例如可適用錢幣型、鈕扣型、囊袋型、角型、或是具有螺旋構造之筒型等各種之類型。此外，非水電解質電池之大小也為任意，可為大型，小型或薄型。 The nonaqueous electrolyte secondary battery of the embodiment has a known battery structure including a positive electrode, a negative electrode, a separator, and an electrolytic solution. The positive electrode has an active material, a conductive material, and a binder. The form of the nonaqueous electrolyte battery is not particularly limited, and for example, it can be applied to various types such as a coin type, a button type, a pouch type, an angle type, or a cylinder type having a spiral structure. Further, the size of the nonaqueous electrolyte battery is also arbitrary, and it can be large, small or thin.
活性物質可使用上述通式(1)所示之正極材。正極所使用之導電材係用以確保正極之電傳導性，可使用將碳黑、乙炔黑、石墨等之碳物質粉狀體之1種或2種以上混合者。黏結劑只要可發揮黏繫活性物質粒子及導電材之功用者則無特別限定。例如可使用聚四氟乙烯、聚偏二氟乙烯、氟橡膠、聚丙烯、聚乙烯、聚乙烯醇、聚丙烯酸、聚丙烯酸鈉、聚丙烯酸鋰等。分散該等活性物質、導電材、黏結劑之溶劑，可使用N-甲基-2-吡咯啶酮等之有機溶劑。該正極集電體可使用鋁箔等。 As the active material, a positive electrode material represented by the above formula (1) can be used. The conductive material used for the positive electrode is used to ensure the electrical conductivity of the positive electrode, and one or a mixture of two or more kinds of carbonaceous materials such as carbon black, acetylene black, and graphite may be used. The binder is not particularly limited as long as it can exhibit the functions of the binder active material particles and the conductive material. For example, polytetrafluoroethylene, polyvinylidene fluoride, fluororubber, polypropylene, polyethylene, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, lithium polyacrylate, or the like can be used. An organic solvent such as N-methyl-2-pyrrolidone can be used as the solvent for dispersing the active material, the conductive material, and the binder. As the positive electrode current collector, aluminum foil or the like can be used.
負極係將負極活性物質鹼金屬與一般電池同樣地成形為薄片狀，或是將成為薄片狀者壓著於鎳、不鏽鋼等之集電體網而形成。負極活性物質可使用鋰、鈉、鉀、銣、銫等之鹼金屬，進一步可使用該等鹼金屬之合金或化合物。 In the negative electrode, the negative electrode active material alkali metal is formed into a sheet shape in the same manner as a general battery, or a sheet-like material is pressed against a current collector mesh such as nickel or stainless steel. As the negative electrode active material, an alkali metal such as lithium, sodium, potassium, rubidium or cesium can be used, and an alloy or compound of such an alkali metal can be further used.
介於正極與負極之間存在之隔膜可由電氣絶緣性之多孔體而形成，例如可舉出聚乙烯、聚丙烯等之聚烯烴；聚酯、 聚對苯二甲酸乙二酯、聚醯亞胺等之聚合物製之膜或繊維不織布。材質可為單獨或使用複數種。此外，隔膜可為單層，也可為多層(複合化膜)。此外可含有陶瓷等之無機材料奈米粒子。此外，可在隔膜兩面塗佈聚偏二氟乙烯等之高分子化合物而使用。 The separator interposed between the positive electrode and the negative electrode may be formed of an electrically insulating porous body, and examples thereof include polyolefins such as polyethylene and polypropylene; and polyester; A film made of a polymer such as polyethylene terephthalate or polyimine or a non-woven fabric. Materials can be used individually or in multiples. Further, the separator may be a single layer or a multilayer (composite film). Further, it may contain inorganic material nano particles such as ceramics. Further, a polymer compound such as polyvinylidene fluoride may be applied to both surfaces of the separator to be used.
實施形態之非水電解質電池中可使用藉由含有高分子化合物而成為凝膠狀之電解質，該高分子化合物係藉由有機溶媒膨潤並成為保持非水電解質之保持體。是因為藉由含有以有機溶媒膨潤之高分子化合物而可得高離子傳導率，並獲得優異充放電效率，同時可防止電池之漏液。在非水電解質含有高分子化合物時，高分子化合物之含有量較佳為0.1質量%以上、10質量%以下之範圍內。 In the nonaqueous electrolyte battery of the embodiment, an electrolyte which is gel-like by containing a polymer compound which is swollen by an organic solvent and which is a retainer for holding a nonaqueous electrolyte can be used. This is because high ion conductivity can be obtained by containing a polymer compound swollen with an organic solvent, and excellent charge and discharge efficiency can be obtained, and leakage of the battery can be prevented. When the nonaqueous electrolyte contains a polymer compound, the content of the polymer compound is preferably in the range of 0.1% by mass or more and 10% by mass or less.
此外，在隔膜兩面塗佈聚偏二氟乙烯等之高分子化合物而使用時，非水電解質與高分子化合物之質量比較佳在50：1至10：1之範圍內。藉由在該範圍內可得更高之充放電效率。 Further, when a polymer compound such as polyvinylidene fluoride is applied to both surfaces of the separator, the quality of the nonaqueous electrolyte and the polymer compound is preferably in the range of 50:1 to 10:1. A higher charge and discharge efficiency can be obtained in this range.
前述高分子化合物例如可舉出聚乙烯甲醛、聚環氧乙烷、及含有聚環氧乙烷交聯體等之醚系高分子化合物；聚甲基丙烯酸酯等之酯系高分子化合物；丙烯酸酯系高分子化合物；以及聚偏二氟乙烯、及偏二氟乙烯與六氟丙烯之共聚物等之偏二氟乙烯聚合物。高分子化合物可單獨使用1種，也可混合複數種使用。尤其從高溫保存時之膨潤防止效果之觀點來看，較佳為使用聚偏二氟乙烯等之氟系高分子化合物。 Examples of the polymer compound include polyethylene formaldehyde, polyethylene oxide, and an ether-based polymer compound containing a polyethylene oxide crosslinked product; an ester-based polymer compound such as polymethacrylate; and acrylic acid; An ester-based polymer compound; and a vinylidene fluoride polymer such as polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene. The polymer compound may be used singly or in combination of plural kinds. In particular, from the viewpoint of the swelling preventing effect at the time of high-temperature storage, a fluorine-based polymer compound such as polyvinylidene fluoride is preferably used.
電解液主要由有機溶媒與電解質鹽所構成，該有機溶媒係使用高電容率溶媒及低黏度溶媒。 The electrolyte mainly consists of an organic solvent and an electrolyte salt, which uses a high permittivity solvent and a low viscosity solvent.
前述高電容率溶媒除了碳酸伸乙酯、碳酸伸丙酯以 外，例如可舉出碳酸伸丁酯、γ-丁內酯、γ-戊內酯、四氫呋喃、1,4-二烷、N-甲基-2-吡咯啶酮、N-甲基-2-唑烷酮(N-methyl-2-Oxazolidinone)、環丁碸、2-甲基環丁碸等。 Examples of the high permittivity solvent other than ethyl carbonate and propylene carbonate include, for example, butyl carbonate, γ-butyrolactone, γ-valerolactone, tetrahydrofuran, and 1,4-diene. Alkane, N-methyl-2-pyrrolidone, N-methyl-2- N-methyl-2-Oxazolidinone, cyclobutyl hydrazine, 2-methylcyclobutyl hydrazine, and the like.
前述低黏度溶媒除了碳酸二甲酯、碳酸二乙酯、碳酸甲基乙酯以外，例如可舉出碳酸甲基丙酯、碳酸甲基異丙酯、碳酸乙基丙酯、碳酸二丙酯、碳酸甲基丁酯、碳酸二丁酯、二甲氧基乙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、丙酸甲酯、丙酸乙酯、甲酸甲酯、甲酸乙酯、丁酸甲酯、異丁酸甲酯等。 Examples of the low viscosity solvent other than dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate include methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, and dipropyl carbonate. Methyl butyl carbonate, dibutyl carbonate, dimethoxyethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, C Ethyl acetate, methyl formate, ethyl formate, methyl butyrate, methyl isobutyrate, and the like.
電解質鹽例如可舉出六氟化磷酸鋰(LiPF6)、四氟化硼酸鋰(LiBF4)、六氟化砷酸鋰(LiAsF6)、六氟化銻酸鋰(LiSbF6)、過氯酸鋰(LiClO4)及四氯化鋁酸鋰(LiAlCl4)等之無機鋰鹽；及三氟甲烷磺酸鋰(CF3SO3Li)、雙(三氟甲烷碸)醯亞胺鋰[(CF3SO2)2NLi]、雙(五氟乙烷碸)醯亞胺鋰[(C2F5SO2)2NLi]及鋰三(三氟甲烷碸)甲基金屬化合物[(CF3SO2)3CLi]等之全氟烷磺酸衍生物之鋰鹽。電解質鹽可單獨使用1種，也可混合複數種使用。 Examples of the electrolyte salt include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF 6 ), and perchloric acid. An inorganic lithium salt such as lithium acid (LiClO 4 ) and lithium aluminum tetrachloride (LiAlCl 4 ); and lithium trifluoromethanesulfonate (CF 3 SO 3 Li) or bis(trifluoromethanemethane) ruthenium hydride [ (CF 3 SO 2 ) 2 NLi], bis(pentafluoroethane oxime) quinone imide lithium [(C 2 F 5 SO 2 ) 2 NLi] and lithium tris(trifluoromethane hydrazide) methyl metal compound [(CF a lithium salt of a perfluoroalkanesulfonic acid derivative such as 3 SO 2 ) 3 CLi]. The electrolyte salt may be used singly or in combination of plural kinds.
此外，電解液中可含有各種添加劑，添加劑例如可舉出碳酸伸乙烯酯、碳酸乙烯伸乙酯、碳酸伸氟乙酯、亞硫酸伸乙酯、1,3-丙烷磺內酯、1,4-丁烷磺內酯、聯苯、環己烷苯、十氫化萘、三苯等。 Further, various additives may be contained in the electrolytic solution, and examples of the additives include vinyl carbonate, ethyl ethylene carbonate, fluoroethyl carbonate, ethyl sulfite, 1,3-propane sultone, and 1,4. - butane sultone, biphenyl, cyclohexane benzene, decalin, triphenyl, and the like.
以下藉由實施例、比較例進一步具體說明本發明，但本發明並不限於該等實施例。 Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.
(實施例1) (Example 1)
將表1所示濃度之Fe(NO3)3．9H2O水溶液2.5毫升、Al(NO3)3．9H2O水溶液2.5毫升、及3莫耳/升NH4F水溶液5毫升，緩緩滴入於50毫升乙醇中，藉此得沉澱物。過濾所得沉澱物，以乙醇洗淨，在80℃、真空下乾燥12小時，並如表1般獲得(NH4)3Fe(1-x)AlxF6所示前驅物1至3。 The concentration of Fe(NO 3 ) 3 shown in Table 1 will be obtained. 9H 2 O aqueous solution 2.5 ml, Al (NO 3 ) 3 . 2.5 ml of a 9H 2 O aqueous solution and 5 ml of a 3 m 2 /liter NH 4 F aqueous solution were slowly added dropwise to 50 ml of ethanol, whereby a precipitate was obtained. The resulting precipitate was filtered, washed with ethanol, dried under vacuum at 80 ° C for 12 hours, and obtained as a solvent of (NH 4 ) 3 Fe (1-x) Al x F 6 as shown in Table 1.
將所得前驅物1在氬環境下於250℃加熱2小時後，進一步在氬環境下於400℃加熱2小時，藉此得Fe0.9Al0.1F3。測定所得正極材之BET比表面積結果為11m2/g。另外，加熱時之昇溫速度為10℃/分。 The obtained precursor 1 was heated at 250 ° C for 2 hours in an argon atmosphere, and further heated at 400 ° C for 2 hours under an argon atmosphere, thereby obtaining Fe 0.9 Al 0.1 F 3 . The BET specific surface area of the obtained positive electrode material was measured and found to be 11 m 2 /g. Further, the temperature increase rate at the time of heating was 10 ° C / min.
(比較例1) (Comparative Example 1)
將0.5莫耳/升之Fe(NO3)3．9H2O水溶液5毫升、及3莫耳/升NH4F水溶液5毫升，緩緩滴入50毫升乙醇中，藉此而得沉澱物。過濾所得沉澱物並以乙醇洗淨，在80℃、真空下乾燥12小時，並獲得(NH4)3FeF6所示之比較前驅物1。 Will be 0.5 mol / liter of Fe (NO 3 ) 3 . 5 ml of a 9H 2 O aqueous solution and 5 ml of a 3 mol/liter NH 4 F aqueous solution were slowly dropped into 50 ml of ethanol to obtain a precipitate. The resulting precipitate was filtered and washed with ethanol, dried under vacuum at 80 ° C for 12 hours, and a comparative precursor 1 of (NH 4 ) 3 FeF 6 was obtained.
將所得比較前驅物1在氬環境下於250℃加熱2小時後，進一步在氬環境下於400℃加熱2小時，藉此得FeF3。測定所得正極材之BET比表面積之結果為8m2/g。另外，加熱時之昇溫速度為10℃/分。 The obtained comparative precursor 1 was heated at 250 ° C for 2 hours in an argon atmosphere, and further heated at 400 ° C for 2 hours in an argon atmosphere, thereby obtaining FeF 3 . The BET specific surface area of the obtained positive electrode material was measured and found to be 8 m 2 /g. Further, the temperature increase rate at the time of heating was 10 ° C / min.
(比較例2) (Comparative Example 2)
將0.5莫耳/升之Al(NO3)3．9H2O水溶液5毫升、及3莫耳/升NH4F水溶液5毫升，緩緩滴入50毫升乙醇中，藉此得沉澱物。過濾所得沉澱物並以乙醇洗淨，在80℃、真空下乾燥12小時，而得(NH4)3AlF6所示之比較前驅物2。 5 ml of a 0.5 mol/L Al(NO3)3.9H2O aqueous solution and 5 ml of a 3 mol/liter NH4F aqueous solution were slowly dropped into 50 ml of ethanol to obtain a precipitate. The obtained precipitate was filtered, washed with ethanol, and dried under vacuum at 80 ° C for 12 hours to obtain a comparative precursor 2 of (NH 4 ) 3 AlF 6 .
對於前驅物1至3、比較前驅物1、2分別使用X射線繞射裝置而得X射線繞射圖形。第1圖表示前驅物1至3、比較前驅物1、2之各X射線繞射圖形。此外，對於實施例1之正極材及比較例1之正極材分別使用X射線繞射裝置而得X射線繞射圖形。第2圖表示實施例1之正極材、及比較例1之正極材之各X射線繞射圖形。 An X-ray diffraction pattern is obtained for each of the precursors 1 to 3 and the comparative precursors 1 and 2 using an X-ray diffraction device. Fig. 1 shows the X-ray diffraction patterns of the precursors 1 to 3 and the comparative precursors 1, 2. Further, an X-ray diffraction pattern was obtained by using an X-ray diffraction apparatus for each of the positive electrode material of Example 1 and the positive electrode material of Comparative Example 1. Fig. 2 is a view showing the X-ray diffraction patterns of the positive electrode material of Example 1 and the positive electrode material of Comparative Example 1.
如第1圖所示，各前驅物所觀察之繞射線可歸屬於空間群Fm-3m，可確認獲得(NH4)3Fe(1-x)AlxF6。 As shown in Fig. 1, the ray observed by each precursor can be attributed to the space group Fm-3m, and it can be confirmed that (NH 4 ) 3 Fe (1-x) Al x F 6 is obtained .
此外，如第2圖所示，將前驅物1及比較前驅物1在400℃以上之溫度、氬環境下加熱，藉此觀察到可歸屬於Fe(1-x)AlxF3(x=0、0.1)(空間群R-3c)之繞射線。 Further, as shown in Fig. 2, the precursor 1 and the comparative precursor 1 were heated at a temperature of 400 ° C or higher and an argon atmosphere, whereby it was observed that it was attributable to Fe (1-x) Al x F 3 (x = 0, 0.1) (space group R-3c) around the ray.
以SEM觀察前驅物1及實施例1之正極材。第3圖係前驅物1及實施例1之正極材之SEM像(倍率×10,000)。第4圖係實施例1之正極材之SEM像(倍率×20,000)。前驅物1之粒子尺寸為200至500nm程度並具有平滑面。另一方面，燒製前驅物1所得之實施例1之正極材之試料中，NH4F脫離之結果而在表面觀察到大量細孔之生成。 The precursor materials of the precursor 1 and the example 1 were observed by SEM. Fig. 3 is an SEM image (magnification × 10,000) of the positive electrode material of the precursor 1 and the first embodiment. Fig. 4 is a SEM image (magnification × 20,000) of the positive electrode material of Example 1. The precursor 1 has a particle size of about 200 to 500 nm and has a smooth surface. On the other hand, in the sample of the positive electrode material of Example 1 obtained by firing the precursor 1, as a result of the detachment of NH 4 F, a large amount of pores were observed on the surface.
以SEM觀察比較前驅物1及比較例1之正極材。第5圖係比較前驅物1及比較例1之正極材之SEM像(倍率×10,000)。比較前驅物1之粒子徑係與前驅物1幾乎相同，但燒製比較前驅 物1所得之比較例1之正極材中觀測到多少有凝集。 The positive electrode materials of the precursor 1 and the comparative example 1 were compared by SEM observation. Fig. 5 is a comparison of SEM images (magnification × 10,000) of the positive electrode materials of the precursor 1 and the comparative example 1. The particle diameter of the precursor 1 is almost the same as that of the precursor 1, but the firing is compared with the precursor. How much agglutination was observed in the positive electrode material of Comparative Example 1 obtained in the material 1.
(循環特性評價) (cycle characteristics evaluation)
使用實施例1及比較例1之正極材，而製作錢幣型之非水電解質電池。第6圖係表示循環特性評價所使用之錢幣型之非水電解質電池之構造的示意剖面圖。評價用之電池100係將正極12與負極14係透過隔膜15而積層者。正極12、負極14及隔膜15皆為圓板狀，而收容於以金屬製之外裝部品11及外裝部品13所劃分之空間內。外裝部品11、13之內部係充滿有機系電解質，外裝部品11、13之周緣部係透過密封墊片17密封藉此成為密閉。另外，在外裝部品13與負極14之間配置金屬製之彈簧18與隔片19。 Using the positive electrode materials of Example 1 and Comparative Example 1, a coin-type nonaqueous electrolyte battery was produced. Fig. 6 is a schematic cross-sectional view showing the structure of a coin-type nonaqueous electrolyte battery used for evaluation of cycle characteristics. The battery 100 for evaluation is a laminate in which the positive electrode 12 and the negative electrode 14 are passed through the separator 15 to be laminated. Each of the positive electrode 12, the negative electrode 14, and the separator 15 has a disk shape and is housed in a space defined by the metal exterior part 11 and the exterior part 13. The inside of the exterior parts 11 and 13 is filled with an organic electrolyte, and the peripheral portions of the exterior parts 11 and 13 are sealed by the sealing gasket 17 to be sealed. Further, a metal spring 18 and a spacer 19 are disposed between the exterior member 13 and the negative electrode 14.
使用實施例1之正極材之正極係用以下方式製作。首先將實施例1之正極材與乙炔黑、及石墨混合，藉由球磨機進行粉碎複合化處理。藉此使實施例1之正極材之平均粒徑成為約80nm(參照第7圖)。正極材、乙炔黑、石墨之混合比係以重量比為正極材：乙炔黑：石墨=70：15：5。進一步加入作為黏結劑之聚丙烯酸，並使用N-甲基吡咯啶酮而製作漿體。複合化試料與黏結劑之混合比係以重量比為複合材料：黏結劑=85：5。將所得漿體塗佈於鋁集電體並以80℃乾燥12小時以上，而製作正極。 The positive electrode of the positive electrode material of Example 1 was produced in the following manner. First, the positive electrode material of Example 1 was mixed with acetylene black and graphite, and pulverized and composited by a ball mill. Thus, the average particle diameter of the positive electrode material of Example 1 was about 80 nm (see Fig. 7). The mixing ratio of the positive electrode material, acetylene black, and graphite is based on the weight ratio of the positive electrode material: acetylene black: graphite = 70:15:5. Further, polyacrylic acid as a binder was added, and a slurry was prepared using N-methylpyrrolidone. The mixing ratio of the composite sample and the binder is a composite ratio by weight: binder = 85:5. The obtained slurry was applied to an aluminum current collector and dried at 80 ° C for 12 hours or more to prepare a positive electrode.
除了使用比較例1之正極材以外，以與使用實施例1之正極材之正極相同方式製作使用比較例1之正極材之正極。球磨機後之比較例1之正極材之平均粒徑也觀察到部分凝集，但概略為100至200nm(參照第8圖)。 A positive electrode using the positive electrode material of Comparative Example 1 was produced in the same manner as the positive electrode of the positive electrode material of Example 1 except that the positive electrode material of Comparative Example 1 was used. A partial agglomeration was also observed in the average particle diameter of the positive electrode material of Comparative Example 1 after the ball mill, but it was roughly 100 to 200 nm (refer to Fig. 8).
以鋰金屬為負極，厚度25微米之聚丙烯製隔膜、電解液、及以上述手法製作之正極，而製作錢幣電池。作為電解液， 係使用在將碳酸伸乙酯(以下簡稱為EC)、碳酸二乙酯(以下簡稱為DEC)分別以體積比1：1混合之溶媒中將LiPF6以1莫耳/升之比例溶解者。 A coin battery is prepared by using a lithium separator as a negative electrode, a polypropylene separator having a thickness of 25 μm, an electrolytic solution, and a positive electrode produced by the above method. As the electrolytic solution, LiPF 6 was used at a molar ratio of 1 mol/liter in a solvent in which ethylene carbonate (hereinafter abbreviated as EC) and diethyl carbonate (hereinafter abbreviated as DEC) were mixed at a volume ratio of 1:1. Proportion dissolved.
對於裝設使用實施例1之正極材之正極的非水電解質電池、及裝設使用比較例1之正極材之正極的非水電解質電池進行電池特性評價。電池特性評價係在室溫下以電壓範圍為1.0V至4.5V、40mA/g之定電流進行充放電試驗。 The battery characteristics were evaluated for a nonaqueous electrolyte battery equipped with the positive electrode of the positive electrode material of Example 1 and a nonaqueous electrolyte battery equipped with the positive electrode of Comparative Example 1. The battery characteristics were evaluated by performing a charge and discharge test at a constant current of a voltage range of 1.0 V to 4.5 V and 40 mA/g at room temperature.
表2中整理初期放電容量與10循環後之放電容量維持率。使用實施例1之正極材時，係以電化學為惰性之Al取代而使初期放電容量減少，但10循環後之放電容量維持率為75%。另一方面，使用比較例1之正極材時，10循環後之放電容量維持率為70%，與使用比較例1之正極材時相比，明顯可知使用實施例1之正極材時會改善循環特性。 Table 2 shows the initial discharge capacity and the discharge capacity retention rate after 10 cycles. When the positive electrode material of Example 1 was used, the initial discharge capacity was decreased by electrochemically inert Al substitution, but the discharge capacity retention rate after 10 cycles was 75%. On the other hand, when the positive electrode material of Comparative Example 1 was used, the discharge capacity retention rate after 10 cycles was 70%, and it was apparent that the use of the positive electrode material of Example 1 improved the cycle as compared with the case of using the positive electrode material of Comparative Example 1. characteristic.
(實施例2) (Example 2)
使用0.4莫耳/升之Fe(NO3)3．9H2O水溶液2.5毫升、0.1莫耳/升之Al(NO3)3．9H2O水溶液2.5毫升、及3莫耳/升NH4F水溶液5毫升，以與實施例1同樣方式合成氟化銨前驅物，並藉由燒製而合成Fe0.8Al0.2F3。測定所得正極材之BET比表面積之結果為15m2/g。另外，燒製時之昇溫速度為1℃/分。 Use 0.4 mol/L Fe(NO 3 ) 3 . 9H 2 O aqueous solution 2.5 ml, 0.1 mol / liter of Al (NO 3 ) 3 . 2.5 ml of a 9H 2 O aqueous solution and 5 ml of a 3 mol/L NH 4 F aqueous solution were used to synthesize an ammonium fluoride precursor in the same manner as in Example 1, and Fe 0.8 Al 0.2 F 3 was synthesized by firing. The BET specific surface area of the obtained positive electrode material was measured and found to be 15 m 2 /g. Further, the temperature increase rate at the time of firing was 1 ° C / min.
(比較例3) (Comparative Example 3)
與實施例1同樣方式合成前驅物，並將所得前驅物在氬環境下以400℃加熱2小時，藉此獲得Fe0.9Al0.1F3。測定所得正極材之BET比表面積之結果為7m2/g。另外，加熱時之昇溫速度為1℃/分。 The precursor was synthesized in the same manner as in Example 1, and the obtained precursor was heated at 400 ° C for 2 hours under an argon atmosphere, whereby Fe 0.9 Al 0.1 F 3 was obtained . The BET specific surface area of the obtained positive electrode material was measured and found to be 7 m 2 /g. Further, the rate of temperature rise during heating was 1 ° C / min.
(比較例4) (Comparative Example 4)
與比較例1同樣方式合成前驅物，並將所得前驅物在氬環境下以400℃加熱2小時，藉此獲得FeF3。測定所得正極材之BET比表面積之結果為7m2/g。另外，加熱時之昇溫速度為1℃/分。 The precursor was synthesized in the same manner as in Comparative Example 1, and the obtained precursor was heated at 400 ° C for 2 hours under an argon atmosphere, whereby FeF 3 was obtained. The BET specific surface area of the obtained positive electrode material was measured and found to be 7 m 2 /g. Further, the rate of temperature rise during heating was 1 ° C / min.
對於實施例2、比較例3、4之正極材，分別使用X射線繞射裝置而得X射線繞射圖形。第9圖表示實施例2、比較例3、4之各X射線繞射圖形。 For the positive electrode materials of Example 2 and Comparative Examples 3 and 4, an X-ray diffraction pattern was obtained using an X-ray diffraction device. Fig. 9 shows the X-ray diffraction patterns of Example 2 and Comparative Examples 3 and 4.
使用實施例2、比較例3、4之正極材，並與實施例1同樣方式製作正極、及裝入該正極之錢幣型之非水電解質電池，在室溫下以電壓範圍1.0V至4.5V、40mA/g之定電流進行充放電試驗。 Using the positive electrode materials of Example 2 and Comparative Examples 3 and 4, a positive electrode and a coin-type nonaqueous electrolyte battery charged in the positive electrode were produced in the same manner as in Example 1, and the voltage range was 1.0 V to 4.5 V at room temperature. A constant current of 40 mA/g was used for the charge and discharge test.
表3統整初期放電容量與10循環後之放電容量維持率。使用實施例2之正極材時，因以電化學為惰性之Al取代的量較比較例多，故初期放電容量減少，但10循環後之放電容量維持率為99%。另一方面，使用比較例3、4之正極材時，10循環後之放電容量維持率依序分別為47%、45%，與使用比較例之正極材時相比，使用實施例2之正極材時明顯循環特性有改善，表示以低溫與高溫之2階段而燒製之手法係較為優異。 Table 3 summarizes the initial discharge capacity and the discharge capacity retention rate after 10 cycles. When the positive electrode material of Example 2 was used, since the amount of Al which was electrochemically inert was more than that of the comparative example, the initial discharge capacity was decreased, but the discharge capacity retention rate after 10 cycles was 99%. On the other hand, when the positive electrode materials of Comparative Examples 3 and 4 were used, the discharge capacity retention ratio after 10 cycles was 47% and 45%, respectively, and the positive electrode of Example 2 was used as compared with the case of using the positive electrode material of the comparative example. The apparent cycle characteristics of the material are improved, indicating that the method of firing at two stages of low temperature and high temperature is superior.
本發明可利用於非水電解質電池之正極材。 The present invention can be utilized as a positive electrode material for a nonaqueous electrolyte battery.
11‧‧‧外裝部品 11‧‧‧ Exterior parts
12‧‧‧正極 12‧‧‧ positive
13‧‧‧外裝部品 13‧‧‧External parts
14‧‧‧負極 14‧‧‧negative
15‧‧‧隔膜 15‧‧‧Separator
17‧‧‧密封墊片 17‧‧‧Sealing gasket
18‧‧‧彈簧 18‧‧‧ Spring
19‧‧‧隔片 19‧‧‧ spacer
100‧‧‧電池 100‧‧‧Battery
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