TWI404257B - Lithium battery and manufacturing method thereof - Google Patents
Lithium battery and manufacturing method thereof Download PDFInfo
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- TWI404257B TWI404257B TW099125875A TW99125875A TWI404257B TW I404257 B TWI404257 B TW I404257B TW 099125875 A TW099125875 A TW 099125875A TW 99125875 A TW99125875 A TW 99125875A TW I404257 B TWI404257 B TW I404257B
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- 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
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Abstract
Description
本發明係一種鋰電池及其製造方法，特別是一種具有以微波加熱方式製造而得之正極活性物質層的鋰電池及其製造方法。The present invention relates to a lithium battery and a method of manufacturing the same, and more particularly to a lithium battery having a positive electrode active material layer produced by microwave heating and a method of manufacturing the same.
隨著可攜式電子產品日益受重視，其相關組件的性能也需隨之增強。故儲能材料也順應時代的趨勢，走向輕、薄、短、小的境界，其中鋰離子二次電池具能量密度高、循環壽命長、重量輕等優點而受青睞。目前世界各主要電池公司均積極開發體積更小、重量更輕、能量密度更高、具經濟、安全、環保性的二次電池。As portable electronic products become more and more important, the performance of their related components needs to be enhanced. Therefore, the energy storage materials are also in line with the trend of the times, moving towards a light, thin, short, and small realm. Among them, lithium ion secondary batteries are favored because of their high energy density, long cycle life, and light weight. At present, all major battery companies in the world are actively developing secondary batteries that are smaller, lighter in weight, higher in energy density, economical, safer and more environmentally friendly.
橄欖石結構(olivine structure)的磷酸鋰鐵(LiFePO4 )是一種稍微扭曲的六方最密堆積，其晶體則是由MO6 八面體、LiO6 八面體和PO4 四面體所構成的空間骨架。因為磷酸鋰鐵具有良好之電化學特徵、無環境污染、安全性較佳、原材料來源豐富、比容量高、循環性能及熱穩定性好且充放電效率高等優點，而被認為是極具應用潛力的鋰離子電池正極材料之一。Lithium iron phosphate (LiFePO 4 ) in the olivine structure is a slightly twisted hexagonal closest packing, and its crystal is a space composed of MO 6 octahedron, LiO 6 octahedron and PO 4 tetrahedron. skeleton. Because lithium iron phosphate has good electrochemical characteristics, no environmental pollution, better safety, rich raw material sources, high specific capacity, good cycle performance and thermal stability, and high charge and discharge efficiency, it is considered to have great application potential. One of the cathode materials for lithium ion batteries.
習知，橄欖石結構LiFePO4 的合成方法多以固相反應法進行，亦即將鋰鹽、鐵鹽、和磷酸銨鹽依比例進行研磨混合成粉末後，再進行熱處理。然而固態反應法需要高溫、長時間、且顆粒較大(50 um)會導致導電度變差。而一般熱處理系統主要係利用加熱源於腔體中，產生熱對流、輻射以及傳導，使加熱體升溫至所需溫度。而微波加熱之所以優於傳統加熱，在於微波加熱的熱能是在材料內部產生的，若我們處理的是介電損耗較小的材料，微波可以穿透整個材料，使得材料的每個部位都可以直接與電磁場作用，因此產生的熱能是均勻的分布在整個體積，而傳統的方式熱必須先經由輻射與對流到達材料的表面，再由傳導的方式將熱傳至材料內部，熱流的方向是由外至內，完全與微波加熱相反。對於大體積的材料處理，傳統加熱一定會有溫度分布不均勻的現象產生，為了避免這種現象對材料有不良的影響，通常是降低高溫爐的升溫梯度，但是卻增加了整個加熱製程的時間，因此微波加熱的體積性與均勻性是它的一個優勢所在。電磁能轉換為熱能可以說是瞬間且高效率的轉換機制，因此使用微波加熱可以節約能源、降低製程溫度、減少製程時間，而且得到的材料特性更優於傳統加熱。Conventionally, the synthesis method of the olivine structure LiFePO 4 is mostly carried out by a solid phase reaction method, that is, the lithium salt, the iron salt, and the ammonium phosphate salt are ground and mixed into a powder, and then heat-treated. However, the solid state reaction method requires high temperature, long time, and large particles (50 um) cause conductivity to deteriorate. In general, the heat treatment system mainly uses heating source in the cavity to generate heat convection, radiation and conduction, so that the heating body is heated to a desired temperature. The reason why microwave heating is better than traditional heating is that the heat energy of microwave heating is generated inside the material. If we process the material with less dielectric loss, the microwave can penetrate the whole material, so that every part of the material can be Directly interacting with the electromagnetic field, the heat generated is evenly distributed throughout the volume. In the traditional way, heat must first reach the surface of the material via radiation and convection, and then transfer heat to the inside of the material. The direction of heat flow is External to internal, completely opposite to microwave heating. For large-volume material treatment, the traditional heating must have a phenomenon of uneven temperature distribution. In order to avoid this phenomenon, the temperature gradient of the high-temperature furnace is usually lowered, but the heating process is increased. Therefore, the volume and uniformity of microwave heating is one of its advantages. The conversion of electromagnetic energy into thermal energy can be said to be an instantaneous and efficient conversion mechanism, so the use of microwave heating can save energy, reduce process temperature, reduce process time, and obtain better material properties than conventional heating.
參照美國專利案第5,910,382號，其標題為「一種鋰二次電池之正極材料，Cathode materials for secondary(rechargeable) lithium batteries」。該專利揭露一種以鋰化合物、二價的鐵化合物，及磷酸化合物在固態下依比例加以混合，繼而在鈍性氣氛下以650℃~800℃的高溫進行熱處理24小時，以製得磷酸鋰鐵粉末。然而製程所耗時間長，於業界應用上追求縮短量產時間有所違背，且所形成的磷酸鋰鐵粉末具有粒徑較大且分布不均勻之缺點，因此無法在高電流下進行充放電動作。U.S. Patent No. 5,910,382, entitled "Cathode materials for secondary (rechargeable) lithium batteries". The patent discloses a lithium compound, a divalent iron compound, and a phosphoric acid compound mixed in a solid state, and then heat-treated at a high temperature of 650 ° C to 800 ° C for 24 hours in a passive atmosphere to obtain lithium iron phosphate. powder. However, the process takes a long time, and it is contrary to the pursuit of shortening the mass production time in the industry application, and the formed lithium iron phosphate powder has the disadvantages of large particle size and uneven distribution, so it is impossible to perform charge and discharge operations under high current. .
參照美國專利案第6,528,033號，其標題為「一種製造鋰組成材料之方法，Method of making lithium-containing materials」。該專利揭露一種在鋰化合物、鐵化合物與磷酸化合物的混合物中添加有機物，使混合物中含有過量的碳以做為鐵金屬離子的還原劑，並在鈍性氣氛下以2℃/min速率升溫至750℃至950℃，利用熱碳還原反應製備磷酸鋰鐵。但是此方法會因大量有機物的添加，使得製作出的磷酸鋰鐵含有較高成分的碳，因為熱碳還原法中過多的碳會將鐵化合物還原成鐵金屬而損失許多比電容量。U.S. Patent No. 6,528,033, entitled "Method of making lithium-containing materials". The patent discloses an organic substance added to a mixture of a lithium compound, an iron compound and a phosphoric acid compound, which contains an excess amount of carbon as a reducing agent for iron metal ions, and is heated to a rate of 2 ° C / min in a passive atmosphere to Lithium iron phosphate was prepared by a hot carbon reduction reaction at 750 ° C to 950 ° C. However, this method results in the production of lithium iron phosphate containing a higher component of carbon due to the addition of a large amount of organic matter, because excessive carbon in the hot carbon reduction process reduces the iron compound to iron metal and loses a lot of specific capacity.
參照美國專利案第7,060,238號，其標題為「金屬磷酸鹽之製備，Synthesis of metal phosphates」。該專利揭示一種合成LiMnPO4 以及LiFePO4 之方法，其中更包含添加一金屬防止鐵氧化成三價鐵化合物，使製程過程中不需額外加入還原劑，也因此不會有碳殘留等問題。但此方式製得之鋰金屬正極材料，其導電率較低，且鋰電池具有較低電容量。Reference is made to U.S. Patent No. 7,060,238, entitled "Synthesis of metal phosphates." The patent discloses a method for synthesizing LiMnPO 4 and LiFePO 4 , which further comprises adding a metal to prevent oxidation of iron into a ferric iron compound, so that no additional reducing agent is added during the process, and thus there is no problem of carbon residue. However, the lithium metal positive electrode material obtained by this method has a low electrical conductivity and a lithium battery has a low electrical capacity.
參照美國專利案第6,962,666號與第7,344,659號專利，其標題均為「具有高表面導電率之電極材料，Electrode materials with high surface conductivity」。該等專利揭示一種以聚丙烯(polypropylene)作為碳材料並與Fe3 (PO4 )2 ‧8H2 O以及Li3 PO4 於350℃乾燥3小時。將乾燥完畢之混合物於700℃燒結7小時並製作成正極。於加入碳材料後，鋰電池之電容值由145 mAh/g增加為170 mAh/g並於五次充放電循環後依然保有80%之電容值。上述之鋰電池正極材料，皆係以高溫固相反應法製造，其製造過程需長時間消耗大量的能源，因而提高鋰電池的製作成本。Reference is made to U.S. Patent Nos. 6,962,666 and 7,344,659, the entire disclosures of which are entitled "Electrode materials with high surface conductivity". The patents disclose the use of polypropylene as a carbon material and drying with Fe 3 (PO 4 ) 2 ‧8H 2 O and Li 3 PO 4 at 350 ° C for 3 hours. The dried mixture was sintered at 700 ° C for 7 hours and made into a positive electrode. After adding carbon material, the capacitance of the lithium battery increased from 145 mAh/g to 170 mAh/g and still retained 80% of the capacitance after five charge and discharge cycles. The above-mentioned lithium battery positive electrode materials are all manufactured by a high-temperature solid phase reaction method, and the manufacturing process requires a large amount of energy for a long time, thereby increasing the manufacturing cost of the lithium battery.
有鑑於此，本發明將微波燒結法導入鋰電池的製造過程中，利用微波加熱的方式來製作鋰電池之正極活性物質層，不僅縮短了鋰電池的製造成本與製程時間，並且可改善鋰電池之循環特性與容量。In view of the above, the present invention introduces a microwave sintering method into a lithium battery manufacturing process, and uses a microwave heating method to fabricate a positive electrode active material layer of a lithium battery, which not only shortens the manufacturing cost and process time of the lithium battery, but also improves the circulation of the lithium battery. Features and capacity.
本發明之主要目的在提供一種鋰電池，該鋰電池之正極具有較佳粒徑大小、高循環特性與高容量，並符合現階段業界需求。本發明之另一目的在提供一種鋰電池製程方法，藉以取代目前正極材料活性物質層利用高溫固相法製作時需長時間於高溫之下合成之缺點。該方法之特徵係於低製程成本與時間，獲得具有較佳粒徑大小之該鋰電池之正極材料以提供具有高循環特性與高容量之鋰電池。The main object of the present invention is to provide a lithium battery, the positive electrode of which has better particle size, high cycle characteristics and high capacity, and meets the needs of the industry at this stage. Another object of the present invention is to provide a lithium battery process method, which can replace the shortcomings of the current active material layer of the positive electrode material which is synthesized under a high temperature solid phase method for a long time under high temperature. The method is characterized by low process cost and time to obtain a positive electrode material of the lithium battery having a preferred particle size to provide a lithium battery having high cycle characteristics and high capacity.
為達上述目的，本發明提出一種鋰電池，包含：正極、負極、隔離層以及電解質。其中，正極包含正極集電體與正極活性物質層，且正極活性物質層係披覆於正極集電體；負極包含負極集電體與負極活性物質層，且負極活性物質層係披覆於負極集電體；隔離層分離正極與負極於相對位置，以避免短路效應；而電解質係配置於正極與負極之間，使離子可於正極與負極間自由移動。此外，正極活性物質的製造過程中包含以微波源加熱微波吸收材料之步驟，而微波吸收材料係由0.5至15重量百分比(wt%)之氧化鐵、0.1至5重量百分比(wt%)之氧化鎳、0.1至5重量百分比(wt%)之氧化鈷、0.2至10重量百分比(wt%)之矽酸鋯、0.2至10重量百分比(wt%)之黏土、以及55至80重量百分比(wt%)之碳化矽所構成。To achieve the above object, the present invention provides a lithium battery comprising: a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode includes a positive electrode current collector and a positive electrode active material layer, and the positive electrode active material layer is coated on the positive electrode current collector; the negative electrode includes a negative electrode current collector and a negative electrode active material layer, and the negative electrode active material layer is coated on the negative electrode The current collector; the isolation layer separates the positive electrode from the negative electrode at a relative position to avoid a short circuit effect; and the electrolyte is disposed between the positive electrode and the negative electrode to allow ions to move freely between the positive electrode and the negative electrode. Further, the manufacturing process of the positive electrode active material includes a step of heating the microwave absorbing material with a microwave source, and the microwave absorbing material is oxidized by 0.5 to 15 weight percent (wt%) of iron oxide and 0.1 to 5 weight percent (wt%). Nickel, 0.1 to 5 weight percent (wt%) of cobalt oxide, 0.2 to 10 weight percent (wt%) of zirconium ruthenate, 0.2 to 10 weight percent (wt%) of clay, and 55 to 80 weight percent (wt% ) is composed of carbonized bismuth.
為達上述另一目的，本發明更提供一種鋰電池的製造方法，包含下列步驟：混合鋰化合物、磷酸化合物、M金屬的化合物、以及微波吸收材料而形成混合物；微波加熱上述混合物而形成正極活性物質；披覆正極活性物質於正極集電體，以形成正極；披覆負極活性物質於負極集電體，以形成負極；以隔離層分離正極與負極於相對位置，避免產生短路效應；以及配置電解質於正極與負極之間，使離子可於正極與負極間自由移動。前述微波吸收材料係由0.5至15重量百分比(wt%)之氧化鐵、0.1至5重量百分比(wt%)之氧化鎳、0.1至5重量百分比(wt%)之氧化鈷、0.2至10重量百分比(wt%)之矽酸鋯、0.2至10重量百分比(wt%)之黏土以及55至80重量百分比(wt%)之碳化矽所組成。In order to achieve the above other object, the present invention further provides a method for manufacturing a lithium battery, comprising the steps of: mixing a lithium compound, a phosphoric acid compound, a compound of an M metal, and a microwave absorbing material to form a mixture; and heating the mixture to form a positive electrode activity by microwave a material; coating the positive electrode active material on the positive electrode current collector to form a positive electrode; coating the negative electrode active material on the negative electrode current collector to form a negative electrode; separating the positive electrode and the negative electrode in a relative position by an isolation layer to avoid a short circuit effect; The electrolyte is between the positive electrode and the negative electrode to allow ions to move freely between the positive electrode and the negative electrode. The aforementioned microwave absorbing material is composed of 0.5 to 15% by weight (wt%) of iron oxide, 0.1 to 5% by weight (wt%) of nickel oxide, 0.1 to 5% by weight (wt%) of cobalt oxide, 0.2 to 10% by weight. (wt%) zirconium silicate, 0.2 to 10 weight percent (wt%) clay, and 55 to 80 weight percent (wt%) niobium carbide.
綜上所述，本發明具有以下之功效：In summary, the present invention has the following effects:
1. 由於本發明之微波燒結法除了利用微波本身加熱材料外，亦添加微波吸收體作為輔助加熱之用。有別於傳統加熱方式，微波加熱使材料由內到外同時受熱，故可得到較均勻的微結構。1. Since the microwave sintering method of the present invention uses a microwave absorber itself to heat the material, a microwave absorber is also added as an auxiliary heating. Different from the traditional heating method, microwave heating causes the material to be heated from the inside to the outside, so that a relatively uniform microstructure can be obtained.
2. 微波源於大功率條件下可提供較高之升溫速率，藉以達到節約能源、降低製程溫度、減少製程時間，而且得到之正極活性材料的特性更優於傳統加熱方式。2. Microwave source can provide higher heating rate under high power conditions, thereby saving energy, reducing process temperature and reducing process time, and the characteristics of the positive active material obtained are better than the traditional heating method.
3. 本發明係在惰性氣體之氣氛下熱處理，因此可以預防三價鐵離子與氧接觸而還原成二價鐵離子，以增加正極活性物質之特性。3. The present invention heat-treats under an inert gas atmosphere, thereby preventing the ferric ions from contacting with oxygen and reducing them to divalent iron ions to increase the characteristics of the positive electrode active material.
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉較佳實施例，作詳細說明如下。The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims.
雖然本發明可表現為不同形式之實施例，但附圖所示者及於下文中說明者係為本發明可之較佳實施例，並請了解本文所揭示者係考量為本發明之一範例，且並非意圖用以將本發明限制於圖式及/或所描述之特定實施例中。While the invention may be embodied in various forms, the embodiments illustrated in the drawings It is not intended to limit the invention to the drawings and/or the particular embodiments described.
請參照第1圖，為本發明鋰電池的結構示意圖，其揭示一種鋰電池100，包含：正極110、負極120、隔離層130以及電解質140。其中，正極100包含正極集電體112與正極活性物質層111，而正極活性物質層111係披覆於正極集電體112。負極120包含負極集電體122與負極活性物質層121，而負極活性物質層121係披覆於負極集電體122上。隔離層130係分離正極110與負極120於相對位置，以避免產生短路效應。電解質140係配置於正極110與負極120之間，使離子可於正極110與負極120間自由移動。Please refer to FIG. 1 , which is a schematic structural diagram of a lithium battery of the present invention. A lithium battery 100 includes a positive electrode 110 , a negative electrode 120 , a separator 130 , and an electrolyte 140 . The positive electrode 100 includes a positive electrode current collector 112 and a positive electrode active material layer 111 , and the positive electrode active material layer 111 is coated on the positive electrode current collector 112 . The negative electrode 120 includes the negative electrode current collector 122 and the negative electrode active material layer 121, and the negative electrode active material layer 121 is coated on the negative electrode current collector 122. The isolation layer 130 separates the positive electrode 110 from the negative electrode 120 in a relative position to avoid a short circuit effect. The electrolyte 140 is disposed between the positive electrode 110 and the negative electrode 120 to allow ions to move freely between the positive electrode 110 and the negative electrode 120.
正極活性物質層111係披覆於正極集電體112之兩面或單面，且正極集電體112之材質係選自鋁箔、鎳箔或不鏽鋼箔等金屬箔之一。The positive electrode active material layer 111 is coated on both surfaces or one surface of the positive electrode current collector 112, and the material of the positive electrode current collector 112 is selected from one of metal foils such as aluminum foil, nickel foil, or stainless steel foil.
此外，正極活性物質層111之組成式係為LixMyPO4 ，其製造過程中包含以微波源加熱微波吸收材料之步驟，其中，M為金屬，其係選自鈧、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、釔、鋯、鈮、鉬、鈹、鎂、鈣、鍶、硼、鋁、鍺、錫、鎵及其組合，其中又以鐵為最佳。x係介於0.8至1.2之間，而y則介於0.8至1.2之間。微波吸收材料係由0.5至15重量百分比(wt%)之氧化鐵、0.1至5重量百分比(wt%)之氧化鎳、0.1至5重量百分比(wt%)之氧化鈷、0.2至10重量百分比(wt%)之矽酸鋯、0.2至10重量百分比(wt%)之黏土、以及55至80重量百分比(wt%)之碳化矽所組成。In addition, the composition of the positive electrode active material layer 111 is LixMyPO 4 , and the manufacturing process includes the step of heating the microwave absorbing material by a microwave source, wherein M is a metal selected from the group consisting of ruthenium, titanium, vanadium, chromium, manganese, Iron, cobalt, nickel, copper, zinc, cerium, zirconium, hafnium, molybdenum, niobium, magnesium, calcium, strontium, boron, aluminum, antimony, tin, gallium and combinations thereof, among which iron is the best. The x series is between 0.8 and 1.2, and the y is between 0.8 and 1.2. The microwave absorbing material is composed of 0.5 to 15 weight percent (wt%) of iron oxide, 0.1 to 5 weight percent (wt%) of nickel oxide, 0.1 to 5 weight percent (wt%) of cobalt oxide, and 0.2 to 10 weight percent ( The wt%) zirconium silicate, 0.2 to 10 weight percent (wt%) clay, and 55 to 80 weight percent (wt%) niobium carbide.
此外，前述微波吸收材料可透過額外添加0.5至15重量百分比(wt%)之氧化錳、0.1至5重量百分比(wt%)之氧化鉻或0.1至5重量百分比(wt%)之氧化銅來增強微波的吸收能力。In addition, the aforementioned microwave absorbing material may be enhanced by additionally adding 0.5 to 15 weight percent (wt%) of manganese oxide, 0.1 to 5 weight percent (wt%) of chromium oxide or 0.1 to 5 weight percent (wt%) of copper oxide. Microwave absorption capacity.
負極集電體122之兩面或單面設有負極活性物質層121之構造，且負極集電體122係選自銅箔、鎳箔以及不鏽鋼箔等之一。The negative electrode current collector 122 has a structure in which the negative electrode active material layer 121 is provided on both sides or one surface, and the negative electrode current collector 122 is selected from one of copper foil, nickel foil, and stainless steel foil.
負極活性物質層121中包含可吸留或釋放鋰之各種負極材料中之1種或2種以上，例如，錫、銅、磷等，其吸留或釋放鋰之能力較大而可獲得高能量密度之故。The negative electrode active material layer 121 contains one or more of various negative electrode materials capable of occluding or releasing lithium, for example, tin, copper, phosphorus, etc., and has a large ability to occlude or release lithium to obtain high energy. The reason of density.
負極材料可為金屬之單體、合金、或化合物或者至少一部分具有上述之1種或2種以上材料。又本發明中，合金除了可以是2種以上之金屬元素所構成外，也可以是包含1種以上之金屬元素與1種以上之半金屬元素，又或者是包含1種以上之非金屬元素。其組織中有時共存著固溶體、共晶(共融混合物)、金屬間化合物或此等中之兩種以上之合金。The negative electrode material may be a monomer, an alloy, or a compound of a metal or at least a part thereof may have one or more of the above materials. Further, in the present invention, the alloy may be composed of two or more kinds of metal elements, or may contain one or more metal elements and one or more kinds of semimetal elements, or may contain one or more kinds of non-metal elements. A solid solution, a eutectic (eutectic mixture), an intermetallic compound, or an alloy of two or more of these may be present in the structure.
作為金屬之合金，例如，作為錫-銅-磷以外之第4構成元素，可列舉含有由矽、鎳、鐵(Fe)、鈷、錳、鋅(Zn)、銦(In)、銀(Ag)、鈦(Ti)、鍺(Ge)、鉍(Bi)、銻(Sb)以及鉻(Cr)之一。As a metal alloy, for example, the fourth constituent element other than tin-copper-phosphorus includes yttrium, nickel, iron (Fe), cobalt, manganese, zinc (Zn), indium (In), and silver (Ag). ), one of titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr).
作為可吸留及釋放鋰之負極材料，例如也可使用石墨、難石墨化性碳或易石墨化性碳等碳質材料，且此等碳質材料也可與上述之負極材料共用。碳質材料在鋰之吸留及釋放時帶來之結晶構造之變化非常少，例如，使其與上述之負極材料共用時，可獲得高能量密度，並可獲得優異之循環特性，更可發揮作為導電劑之機能，故相當理想。As the negative electrode material capable of occluding and releasing lithium, for example, a carbonaceous material such as graphite, non-graphitizable carbon or easily graphitizable carbon may be used, and these carbonaceous materials may be used in common with the above-described negative electrode material. The change in the crystal structure of the carbonaceous material during the storage and release of lithium is very small. For example, when it is used in combination with the above-mentioned negative electrode material, high energy density can be obtained, and excellent cycle characteristics can be obtained, and the cycle characteristics can be exhibited. As a function of the conductive agent, it is quite desirable.
負極活性物質層121也可包含導電劑、黏接劑或黏度調整劑等無助於充電之其他材料。作為導電劑，可列舉石墨纖維、金屬纖維或金屬粉末等。作為黏接劑，可列舉聚偏二氟乙烯等氟系高分子化合物、或苯乙烯丁二烯橡膠或乙烯丙二烯橡膠等之合成橡膠等。作為黏度調整劑，可列舉羧甲基纖維素等。The negative electrode active material layer 121 may also contain other materials that do not contribute to charging, such as a conductive agent, an adhesive, or a viscosity modifier. Examples of the conductive agent include graphite fibers, metal fibers, metal powders, and the like. Examples of the binder include a fluorine-based polymer compound such as polyvinylidene fluoride or a synthetic rubber such as styrene butadiene rubber or ethylene allene rubber. Examples of the viscosity adjuster include carboxymethyl cellulose and the like.
電解質140，其提供離子在正極(陰極)與負極(陽極)間之轉移。電解質140具有高離子傳導性以及絕緣性，以防在存放期間之自行放電。電解質140可為液體或固體，固態電解質較佳者含有聚合基質，其含有離子傳導性介質；液態電解質較佳者包含溶劑及鹼金屬鹽，其形成離子傳導性液體。Electrolyte 140, which provides for the transfer of ions between the positive (cathode) and negative (anode). The electrolyte 140 has high ion conductivity and insulation to prevent self-discharge during storage. The electrolyte 140 may be a liquid or a solid, and the solid electrolyte preferably contains a polymeric matrix containing an ionically conductive medium; preferably, the liquid electrolyte comprises a solvent and an alkali metal salt which forms an ion conductive liquid.
固態聚合電解質，係包含由聚合有機或無機單體(或其局部聚合物)形成之電解質140可相容物質之固態聚合基質，及當與其他電解質140之成份組合使用時，其可導致固態電解質。適當固態聚合基質包括此技藝已知者並包括自有機聚合物、無機聚合物或固態基質形成單體並自固態基質形成單體之局部聚合物形成之固態基質。A solid state polyelectrolyte comprising a solid polymeric matrix comprising an electrolyte 140 compatible material formed by polymerizing an organic or inorganic monomer (or a localized polymer thereof) and, when used in combination with other electrolytes 140, can result in a solid electrolyte . Suitable solid state polymeric matrices include those known to those skilled in the art and include solid matrices formed from organic polymers, inorganic polymers or solid matrix forming monomers and forming localized monomers from the solid matrix.
聚合電解質基質係包含鹽，通常為無機鹽，其係藉由溶劑媒質均勻分散整個基質。溶劑較佳為加入電解質140之低分子量有機溶劑，其可用來溶劑化無機離子鹽。溶劑較佳為任何可相容相當非揮發性非質子相當極性溶劑，包括碳酸甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸乙基甲酯(EMC)、碳酸伸丁酯、γ-丁內酯、三甘醇二甲醚、四甘醇二甲醚、內酯類、酯類、二甲基亞碸、二氧戊環、環丁碸、及其混合物。較佳溶劑包括EC/DMC、EC/DEC、EC/DPC及EC/EMC。較佳的是，無機離子鹽為鋰或鈉鹽，例如，LiASF6 、LiPF6 、LiClO4 、LiB(C6 H5 )4 、LiAlCl4 、LiBr、及其混合物，以毒性低的鹽較佳。The polyelectrolyte matrix comprises a salt, typically an inorganic salt, which is uniformly dispersed throughout the matrix by a solvent medium. The solvent is preferably a low molecular weight organic solvent added to the electrolyte 140, which can be used to solvate the inorganic ion salt. The solvent is preferably any compatible, relatively nonvolatile, aprotic, relatively polar solvent, including methyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC). , butyl carbonate, γ-butyrolactone, triglyme, tetraglyme, lactones, esters, dimethyl hydrazine, dioxolane, cyclobutane, and mixture. Preferred solvents include EC/DMC, EC/DEC, EC/DPC, and EC/EMC. Preferably, the inorganic ion salt is a lithium or sodium salt, for example, LiASF 6 , LiPF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiAlCl 4 , LiBr, and mixtures thereof, preferably a salt having low toxicity. .
此外，隔離層130設置於電解質140中，或環繞電解質140。隔離層130容許離子移行過膜，而仍可提供電荷在電極間之物理分離，以防止短路。隔離層130亦可抑制在電池內因化學反應失控所發生之高溫，在溫度升高時，較佳地藉由本身的降解來提供高電阻以防止化學反應持續進行。在一較佳具體例中，電解質140之聚合基質可含有附加聚合物(隔離層130)或其最初聚合基質可作為隔離層130，提供陽極與陰極間之所需之物理隔離。Further, the isolation layer 130 is disposed in the electrolyte 140 or surrounds the electrolyte 140. The isolation layer 130 allows ions to migrate through the film while still providing physical separation of charges between the electrodes to prevent short circuits. The spacer layer 130 can also suppress the high temperature which occurs in the battery due to the uncontrolled chemical reaction, and when the temperature rises, it is preferable to provide high resistance by itself to prevent the chemical reaction from continuing. In a preferred embodiment, the polymeric matrix of electrolyte 140 may contain additional polymer (isolation layer 130) or its original polymeric matrix as separator layer 130, providing the desired physical isolation between the anode and cathode.
隔離層130通常為聚合物並自含有共聚合物之組合物製備。較佳組合物為75至92%亞乙烯氟與8至25%六氟丙烯共聚合物(市面上可獲自Atochem North America公司名稱為Kynar FLEX)及有機溶劑塑化劑。該共聚合物組合物對製備電極膜元件亦佳，因為確保後續層壓界面可相容性。塑化溶劑為共同用作電解質鹽之溶劑之各種有機化合物之例如，碳酸丙烯酯或碳酸乙烯酯，以及此等化合物之混合物。以較高沸點塑化劑化合物如酞酸二丁酯、酞酸二甲酯、酞酸二乙酯、及磷酸參丁氧乙酯較佳。無機填料附加物如發烟氧化鋁或矽烷化發烟矽石可用以強化分離物膜之物理強度與熔融黏度，並在有些組合物內，增加電解質140溶液吸收之後續準位。The barrier layer 130 is typically a polymer and is prepared from a composition comprising a copolymer. Preferred compositions are 75 to 92% vinylidene fluoride and 8 to 25% hexafluoropropylene copolymer (commercially available from Atochem North America under the name Kynar FLEX) and an organic solvent plasticizer. The copolymer composition is also preferred for the preparation of electrode film elements because of the subsequent laminate interface compatibility. The plasticizing solvent is, for example, propylene carbonate or ethylene carbonate, and a mixture of such compounds, of various organic compounds which are used together as a solvent for the electrolyte salt. It is preferred to use a higher boiling plasticizer compound such as dibutyl phthalate, dimethyl phthalate, diethyl decanoate, and butyl oxybutylate. Inorganic filler addenda such as fumed alumina or decaneated fumed vermiculite may be used to enhance the physical strength and melt viscosity of the separator membrane and, in some compositions, increase the subsequent level of electrolyte 140 solution absorption.
請參考第2圖，為本發明之鋰電池的製造方法流程圖，包含下列步驟：Please refer to FIG. 2 , which is a flow chart of a method for manufacturing a lithium battery of the present invention, comprising the following steps:
步驟510：形成正極合劑。Step 510: Forming a positive electrode mixture.
將正極活性物質與導電劑以及黏著劑混合而調製成正極合劑。The positive electrode active material is mixed with a conductive agent and an adhesive to prepare a positive electrode mixture.
步驟520：形成正極合劑漿料。Step 520: Forming a positive electrode mixture slurry.
將正極合劑分散於溶劑中而成膏狀之正極合劑漿料。The positive electrode mixture is dispersed in a solvent to form a paste positive electrode mixture slurry.
步驟530：形成正極110。Step 530: Forming the positive electrode 110.
將正極合劑漿料被覆於金屬箔正極集電體112之二面使其乾燥後，壓縮成型而形成正極110。The positive electrode mixture slurry is coated on both sides of the metal foil positive electrode current collector 112, dried, and then compression-molded to form a positive electrode 110.
步驟610：形成負極合劑。Step 610: Forming a negative electrode mixture.
將負極活性物質與導電劑以及黏著劑混合而調製成負極合劑。The negative electrode active material is mixed with a conductive agent and an adhesive to prepare a negative electrode mixture.
步驟620：形成負極合劑漿料。Step 620: Forming a negative electrode mixture slurry.
將負極合劑分散於溶劑中而成膏狀之負極合劑漿料。The negative electrode mixture is dispersed in a solvent to form a paste-like negative electrode mixture slurry.
步驟630：形成負極120。Step 630: Forming the anode 120.
將負極合劑漿料塗布於負極集電體122二面使其乾燥後，壓縮成型而形成負極120。The negative electrode mixture slurry is applied to both sides of the negative electrode current collector 122 to be dried, and then compression-molded to form a negative electrode 120.
步驟710：配置一隔離層130。Step 710: Configure an isolation layer 130.
將隔離層130捲繞於正極110與負極120中，並將正極110與負極120以及隔離層130收容於電池罐之內部。The separator 130 is wound around the positive electrode 110 and the negative electrode 120, and the positive electrode 110 and the negative electrode 120 and the separator 130 are housed inside the battery can.
步驟720：配置一電解質140。Step 720: Configuring an electrolyte 140.
將電解質140注入電池罐之內部，使其含浸隔離層130。The electrolyte 140 is injected into the interior of the battery can to be impregnated with the barrier layer 130.
步驟730：形成一鋰電池110。Step 730: Form a lithium battery 110.
經由上述步驟而完成鋰電池100。The lithium battery 100 is completed through the above steps.
此外，於上述形成正極合劑之步驟中，包含下列步驟：混合鋰化合物、磷酸化合物、金屬的化合物以及微波吸收材料而形成混合物；以及微波加熱該混合物而形成正極活性物質。此外，於微波加熱該混合物前可先對該混合物球磨。Further, in the step of forming the positive electrode mixture described above, the method comprises the steps of: mixing a lithium compound, a phosphoric acid compound, a metal compound, and a microwave absorbing material to form a mixture; and heating the mixture by microwave to form a positive electrode active material. Additionally, the mixture may be ball milled prior to heating the mixture in the microwave.
請參照第3圖，為本發明之正極製造方法流程圖，茲將本發明之正極的製造方法詳述如下：Referring to FIG. 3, which is a flow chart of a method for producing a positive electrode of the present invention, the method for producing the positive electrode of the present invention will be described in detail as follows:
步驟531：形成混合物。Step 531: Form a mixture.
混合鋰化合物、磷酸化合物、包含金屬M的化合物、碳源以及微波吸收材料而得到混合物。A mixture of a lithium compound, a phosphoric acid compound, a compound containing a metal M, a carbon source, and a microwave absorbing material is obtained.
步驟532：球磨混合物。Step 532: Ball milling the mixture.
將步驟531所得之混合物球磨20分鐘至2小時。The mixture obtained in the step 531 was ball milled for 20 minutes to 2 hours.
步驟533：通入惰性氣體。Step 533: Passing an inert gas.
將球磨後之混合物置入微波源的腔體中，並通入惰性氣體以防止二價鐵氧化，惰性氣體係選自：氮氣(N2 )、氬氣(Ar)、一氧化碳(CO)、二氧化碳(CO2 )及其組合。The ball milled mixture is placed in a cavity of a microwave source, and an inert gas is introduced to prevent oxidation of the ferrous iron. The inert gas system is selected from the group consisting of nitrogen (N 2 ), argon (Ar), carbon monoxide (CO), and carbon dioxide. (CO 2 ) and combinations thereof.
步驟534：以一微波加熱源加熱。Step 534: Heating with a microwave heating source.
微波吸收材料吸收微波加熱源所產生的微波能量而發熱，進而加熱球磨後之混合物。The microwave absorbing material absorbs the microwave energy generated by the microwave heating source to generate heat, thereby heating the ball milled mixture.
步驟535：形成正極活性物質。Step 535: Forming a positive active material.
將加熱後之混合物冷卻至室溫而形成正極活性物質。The heated mixture was cooled to room temperature to form a positive electrode active material.
步驟534中之微波吸收材料係由0.5至15重量百分比(wt%)之氧化鐵、0.1至5重量百分比(wt%)之氧化鎳、0.1至5重量百分比(wt%)之氧化鈷、0.2至10重量百分比(wt%)之矽酸鋯、0.2至10重量百分比(wt%)之黏土以及55至80重量百分比(wt%)之碳化矽所組成。The microwave absorbing material in step 534 is from 0.5 to 15 weight percent (wt%) of iron oxide, 0.1 to 5 weight percent (wt%) of nickel oxide, 0.1 to 5 weight percent (wt%) of cobalt oxide, 0.2 to 10 wt% (wt%) of zirconium silicate, 0.2 to 10 wt% (wt%) of clay, and 55 to 80 wt% (wt%) of niobium carbide.
此外，若是將上述微波吸收材料再添加0.5至15重量百分比(wt%)之氧化錳或0.1至5重量百分比(wt%)之氧化鉻抑或0.1至5重量百分比(wt%)之氧化銅，則可得到具有更佳微波吸收能力之微波吸收材料。Further, if the above microwave absorbing material is further added with 0.5 to 15 weight percent (wt%) of manganese oxide or 0.1 to 5 weight percent (wt%) of chromium oxide or 0.1 to 5 weight percent (wt%) of copper oxide, A microwave absorbing material having better microwave absorbing ability can be obtained.
步驟531之金屬M係選自：鈧、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、釔、鋯、鈮、鉬、鈹、鎂、鈣、鍶、硼、鋁、鍺、錫、鎵及其組合，其中又以鐵為最佳。The metal M of step 531 is selected from the group consisting of ruthenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, lanthanum, zirconium, hafnium, molybdenum, niobium, magnesium, calcium, strontium, boron, aluminum, lanthanum. Tin, gallium and combinations thereof, among which iron is the best.
承上，鐵化合物係選自於下列所構成之群組：硫酸鐵、硝酸鐵、氯化鐵以及醋酸鐵之一。The iron compound is selected from the group consisting of iron sulfate, iron nitrate, iron chloride, and iron acetate.
較佳地，該鋰化合物係選自於：氫氧化鋰、氟化鋰、碳酸鋰、氯化鋰、溴化鋰、氧化鋰、硝酸鋰、醋酸鋰、磷酸鋰、磷酸氫鋰、磷酸二氫鋰、磷酸銨鋰、磷酸二銨鋰及其組合所構成之群組。Preferably, the lithium compound is selected from the group consisting of lithium hydroxide, lithium fluoride, lithium carbonate, lithium chloride, lithium bromide, lithium oxide, lithium nitrate, lithium acetate, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, A group consisting of lithium ammonium phosphate, lithium diammonium phosphate, and combinations thereof.
較佳地，該磷酸化合物係選自於下列所構成之群組：磷酸氫二銨、磷酸二氫銨、磷酸三銨、五氧化二磷、磷酸、磷酸鋰、磷酸氫鋰、磷酸二氫鋰、磷酸銨鋰以及磷酸二銨鋰之一。另外，本發明之正極亦可包含黏合劑及可導電物質。Preferably, the phosphate compound is selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, phosphorus pentoxide, phosphoric acid, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate. One of lithium ammonium phosphate and lithium diammonium phosphate. In addition, the positive electrode of the present invention may also contain a binder and a conductive material.
本發明所用之導電物質係包括碳黑、石墨、粉狀鎳、金屬顆粒、傳導性聚合物(例如，具有雙鍵之共軛網絡特性如聚吡咯及聚乙炔)、及其混合物。另外，上述之黏合劑係含聚合物質與可萃取塑化劑，適合形成黏合多孔複合物。較佳黏合劑包括鹵化烴聚合物(例如聚(偏二氯乙烯)及聚((二氯-1，4-伸苯基)乙烯)、氟化脲烷、氟化環氧化物、氟化丙烯酸類、鹵化烴聚合物之共聚合物、環氧化物、乙烯丙烯胺三單體(EPDM)、聚亞乙烯二氟化物(PVDF)、六氟丙烯(HFP)、乙烯丙烯酸共聚合物(EAA)、乙烯醋酸乙烯酯共聚合物(EVA)、EAA/EVA共聚合物、PVDF/HFP共聚合物、及其混合物。The conductive materials used in the present invention include carbon black, graphite, powdered nickel, metal particles, conductive polymers (for example, conjugated network characteristics having double bonds such as polypyrrole and polyacetylene), and mixtures thereof. Further, the above-mentioned binder is a polymerizable substance and an extractable plasticizer, and is suitable for forming a porous composite. Preferred binders include halogenated hydrocarbon polymers (eg, poly(vinylidene chloride) and poly((dichloro-1,4-phenylene) ethylene), fluorinated urethanes, fluorinated epoxides, fluorinated acrylic acid a copolymer of a halogenated hydrocarbon polymer, an epoxide, an ethylene propylene amine trimonomer (EPDM), a polyethylene difluoride (PVDF), a hexafluoropropylene (HFP), an ethylene acrylic acid copolymer (EAA) , ethylene vinyl acetate copolymer (EVA), EAA/EVA copolymer, PVDF/HFP copolymer, and mixtures thereof.
此外，於步驟534中，微波加熱球磨後之混合物的製程條件為：In addition, in step 534, the process conditions of the mixture after microwave heating of the ball mill are:
(1)微波之頻率係介於0.3 GHz至30 GHz之間。(1) The frequency of the microwave is between 0.3 GHz and 30 GHz.
(2)微波加熱過程之功率係介於400 W至1200 W之間。(2) The power of the microwave heating process is between 400 W and 1200 W.
(3)微波加熱過程之升溫速率係介於60℃/min至120℃/min之間。(3) The heating rate of the microwave heating process is between 60 ° C / min and 120 ° C / min.
(4)微波加熱過程之持溫溫度係介於750℃至850℃之間。(4) The temperature holding temperature of the microwave heating process is between 750 ° C and 850 ° C.
(5)微波加熱過程之持溫時間係介於2分鐘至30分鐘之間。(5) The holding time of the microwave heating process is between 2 minutes and 30 minutes.
本發明之微波吸收材料係用以吸收微波，並將微波能量轉為熱能，隨微波能量之強弱及多寡，可將材料加熱至450℃至1500℃。The microwave absorbing material of the present invention is used for absorbing microwaves and converting microwave energy into heat energy, and the material can be heated to 450 ° C to 1500 ° C depending on the strength and the amount of microwave energy.
在此鋰電池100中，施行充電時，由正極110釋放鋰離子，經由電解質140而將負極120所含之鋰析出至可吸留及釋放鋰之負極材料。再繼續充電時，在開路電壓低於過充電電壓之狀態下，開始將鋰金屬析出至可吸留及釋放鋰之負極材料之表面。接著，施行放電時，首先，由負極120熔解釋出鋰金屬成為鋰離子，藉著電解質140將其吸留於正極110。再繼續放電時，由可吸留及釋放負極120中之鋰之負極材料釋放鋰離子，藉著電解質140將其吸留於正極110。In the lithium battery 100, when charging is performed, lithium ions are released from the positive electrode 110, and lithium contained in the negative electrode 120 is deposited through the electrolyte 140 to a negative electrode material capable of occluding and releasing lithium. When charging is continued, the lithium metal is precipitated on the surface of the negative electrode material capable of occluding and releasing lithium in a state where the open circuit voltage is lower than the overcharge voltage. Next, when discharge is performed, first, lithium metal is melted by the negative electrode 120 to become lithium ions, and is stored in the positive electrode 110 by the electrolyte 140. When the discharge is continued, lithium ions are released from the anode material which can occlude and release lithium in the anode 120, and are occluded to the cathode 110 by the electrolyte 140.
<實施例1><Example 1>
本實施例係在製造具有橄欖石結構之正極活性物質。首先將0.5莫耳Fe2 O3 79.85克、0.5莫耳Li2 CO3 36.95克以及1莫耳(NH4 )2 HPO4 132.06克混合，形成一混合物。再將混和物與氧化鋯球重量以20：1加入乙醇溶液中，並置於球磨機中球磨一小時。球磨後之混合物溶液置於氮氣環境中以120℃烘烤6小時，乾燥後即得一粉末狀的起始物。將該粉末狀的起始物置於氧化鋁坩堝中，再將此坩堝置於功率為750 W頻率為2.45 GHz之微波燒結爐中，而升溫度率設定為60℃/min，並再通氮氣下以750℃熱處理2至10分鐘，繼而得到磷酸鋰鐵粉末，亦即本發明之正極活性物質。This embodiment is to manufacture a positive active material having an olivine structure. First, 0.5 moles of Fe 2 O 3 79.85 grams, 0.5 moles of Li 2 CO 3 36.95 grams, and 1 mole of (NH 4 ) 2 HPO 4 132.06 grams were mixed to form a mixture. The weight of the mixture and the zirconia balls were then added to the ethanol solution at 20:1 and ball milled in a ball mill for one hour. The ball-milled mixture solution was baked at 120 ° C for 6 hours in a nitrogen atmosphere, and after drying, a powdery starting material was obtained. The powdered starting material was placed in an alumina crucible, and the crucible was placed in a microwave sintering furnace with a power of 750 W at a frequency of 2.45 GHz, and the temperature rise rate was set to 60 ° C / min, and then under nitrogen. The heat treatment is carried out at 750 ° C for 2 to 10 minutes, followed by obtaining lithium iron phosphate powder, that is, the positive electrode active material of the present invention.
本發明之具有橄欖石結構之正極製作方法的實施例2與該實施例1製法大致相同，其差異處在於將Fe2 O3 置換成0.5莫耳Mn2 O3 78.94克，其餘與該實施例1相同，藉以得到一磷酸鋰錳粉末。The second embodiment of the method for producing a positive electrode having an olivine structure of the present invention is substantially the same as the method of the first embodiment, except that Fe 2 O 3 is replaced with 0.5 mol of Mn 2 O 3 78.94 g, and the rest and the embodiment. 1 is the same, thereby obtaining lithium manganese monophosphate powder.
本發明之具有橄欖石結構之正極製作方法的實施例3與該實施例1製法大致相同，其差異處係為於該混合化合物中，添加0.5莫耳碳6.00克，其餘與該實施例1相同，藉以得到一含碳之磷酸鋰鐵粉末。The third embodiment of the method for producing a positive electrode having an olivine structure of the present invention is substantially the same as the method of the first embodiment, and the difference is that 6.00 g of 0.5 mol carbon is added to the mixed compound, and the rest is the same as in the first embodiment. In order to obtain a carbon-containing lithium iron phosphate powder.
請參照第2圖，本發明之鋰電池其製程步驟簡單說明如下：Referring to FIG. 2, the process steps of the lithium battery of the present invention are briefly described as follows:
將該實施例1所製得之磷酸鋰鐵粉末與碳黑及聚二氟乙烯(polyvinylidene difluoride，PVDF)黏合劑，依比例(83：10：7)混合均勻後，被覆於10 um鋁箔上，經120℃烘乾6小時後，藉以得到一磷酸鋰鐵活性物質層，並形成該正極110。以及藉著厚25 μm之微多孔性聚乙烯膜(東燃化學製；E25MMS) 構成之隔離層130依照負極120、隔離層130及正極110之順序疊層後，多數捲繞。接著，混合40重量百分比之4-氟-1,3-二噁茂烷-2-酮(FEC)、45重量百分比之碳酸二甲酯(DMC)、15重量百分比之電解質鹽LiPF6 而調製電解質140。並將正極110與負極120收容於電池罐之內部後，將電解質140注入電池罐之內部，使其含浸隔離層130，以形成該鋰電池100，再藉由充放電測試機測試其充放電性質。The lithium iron phosphate powder obtained in the first embodiment and the carbon black and polyvinylidene difluoride (PVDF) binder were uniformly mixed in a ratio (83:10:7), and then coated on a 10 um aluminum foil. After drying at 120 ° C for 6 hours, a lithium iron monophosphate active material layer was obtained, and the positive electrode 110 was formed. Further, the separator 130 made of a microporous polyethylene film (manufactured by Tosoh Chemical Co., Ltd.; E25MMS) having a thickness of 25 μm is laminated in the order of the negative electrode 120, the separator 130, and the positive electrode 110, and is mostly wound. Next, 40 parts by weight of 4-fluoro-1,3-dioxan-2-one (FEC), 45 weight percent of dimethyl carbonate (DMC), and 15 weight percent of electrolyte salt LiPF 6 were mixed to prepare an electrolyte. 140. After the positive electrode 110 and the negative electrode 120 are housed inside the battery can, the electrolyte 140 is injected into the interior of the battery can to be impregnated with the isolation layer 130 to form the lithium battery 100, and then tested for charge and discharge properties by a charge and discharge tester. .
綜上所述，本發明之功效係為：In summary, the efficacy of the present invention is:
1.由於本發明之微波燒結法除了利用微波本身加熱材料本身外，亦使用微波吸收體作為輔助加熱正極活性物質，藉由該加熱之方式將有別於習知加熱技術，不僅能藉由功率之控制改變其升溫時間，也能對材料的整體均勻加熱。1. Since the microwave sintering method of the present invention uses the microwave itself to heat the material itself, the microwave absorber is also used as an auxiliary heating positive electrode active material, and the heating method is different from the conventional heating technology, and can be used not only by power The control changes the temperature rise time and also uniformly heats the entire material.
2.微波加熱源於大功率條件下操作將產生較高之升溫速率，藉以達到節約能源、降低製程溫度、減少製程時間，而且得到之該LixMyPO4 正極材料活性層的特性更優於習知加熱技術。2. The operation of the microwave heating source under high power conditions will result in a higher heating rate, thereby achieving energy saving, lowering the process temperature, and reducing the processing time, and obtaining the characteristics of the active layer of the LixMyPO 4 positive electrode material is better than the conventional heating. technology.
3.本發明係於惰性氣體的氣氛中進行熱處理，可以預防二價鐵離子與氧接觸而氧化成三價鐵離子。3. The present invention is heat-treated in an inert gas atmosphere to prevent oxidation of divalent iron ions to ferric ions by contact with oxygen.
雖然本發明已以前述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與修改。如上述的解釋，都可以作各型式的修正與變化，而不會破壞此發明的精神。因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, it is not intended to limit the scope of the invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. As explained above, various modifications and variations can be made without departing from the spirit of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.
100‧‧‧鋰電池100‧‧‧Lithium battery
110‧‧‧正極110‧‧‧ positive
111‧‧‧正極活性物質層111‧‧‧positive active material layer
112‧‧‧正極集電體112‧‧‧ positive current collector
120‧‧‧負極120‧‧‧negative
121‧‧‧負極活性物質層121‧‧‧Negative active material layer
122‧‧‧負極集電體122‧‧‧Negative current collector
130‧‧‧隔離層130‧‧‧Isolation
140‧‧‧電解質140‧‧‧ Electrolytes
為了讓本發明之上述和其他目的、特徵、和優點能更明顯，下文特舉本發明較佳實施例，並配合所附圖示，作詳細說明如下：The above and other objects, features, and advantages of the present invention will become more apparent from the <RTIgt;
第1圖為本發明之鋰電池的示意圖。Figure 1 is a schematic view of a lithium battery of the present invention.
第2圖為本發明之鋰電池製造方法流程圖。Fig. 2 is a flow chart showing a method of manufacturing a lithium battery of the present invention.
第3圖為本發明之正極製造方法流程圖。Fig. 3 is a flow chart showing a method of manufacturing a positive electrode of the present invention.
100．．．鋰電池100. . . lithium battery
110．．．正極110. . . positive electrode
111．．．正極活性物質層111. . . Positive active material layer
112．．．正極集電體112. . . Positive current collector
120．．．負極120. . . negative electrode
121．．．負極活性物質層121. . . Negative electrode active material layer
122．．．負極集電體122. . . Negative current collector
130．．．隔離層130. . . Isolation layer
140．．．電解質140. . . Electrolyte
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