TW201438996A - Method for producing microparticles, method for producing positive electrode active material for lithium ion secondary cell, positive electrode active material, lithium ion secondary cell using same, and source emulsion for producing microparticles - Google Patents
Method for producing microparticles, method for producing positive electrode active material for lithium ion secondary cell, positive electrode active material, lithium ion secondary cell using same, and source emulsion for producing microparticles Download PDFInfo
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Abstract
Description
本發明有關於一種使用自噴嘴噴霧液體狀原料, 並使其於火焰中燃燒而製造微粒子之噴霧燃燒法之微粒子之製造方法及製造裝置。本發明特別有關於一種矽酸鐵鋰等之矽酸系之鋰離子二次電池用之正極活性物質之製造。 The invention relates to a liquid material which is sprayed from a nozzle, A method and a manufacturing apparatus for producing fine particles by a spray combustion method in which a fine particle is burned in a flame. In particular, the present invention relates to the production of a positive electrode active material for a lithium ion secondary battery of a tannic acid type such as lithium iron silicate.
近年,手機及筆記型電腦、數位相機、攝影機等行動電子設備之電源已廣泛使用小型且輕量之鋰離子二次電池。且,電動汽車之普及下,亦需求高功能且廉價之鋰離子電池。現在,鋰離子二次電池之正極活性物質一般乃使用鈷酸鋰(LiCoO2)。然而,鈷酸鋰含有資源上限制較大而高價且毒性亦強之鈷而成問題,且加熱至高溫將放出氧而可能起火而有安全性較低之問題。相對於此,在熱及化學之安定性上遠較鈷酸鋰優良且可由豐富之原料體系製得之新正極活性物質已有具備橄欖石構造之磷酸鐵鋰(LiFePO4)及矽酸鐵鋰(Li2FeSiO4)等備受矚目。然而,該等 材料原本導電性較低,結晶內部之Li離子擴散速度較慢,故須加工成具有數十~100nm之原粒子徑之微粒子。 In recent years, small and lightweight lithium ion secondary batteries have been widely used as power sources for mobile electronic devices such as mobile phones, notebook computers, digital cameras, and video cameras. Moreover, under the popularity of electric vehicles, lithium-ion batteries with high functionality and low cost are also required. Now, the positive electrode active material of a lithium ion secondary battery generally uses lithium cobaltate (LiCoO 2 ). However, lithium cobalt oxide is a problem in which cobalt having a large resource and high toxicity and high toxicity is contained, and heating to a high temperature releases oxygen and may cause fire and has a low safety. On the other hand, the new positive electrode active material which is superior in thermal and chemical stability to lithium cobalt oxide and which can be obtained from a rich raw material system has lithium iron phosphate (LiFePO 4 ) and lithium iron citrate having an olivine structure. (Li 2 FeSiO 4 ) and the like have attracted attention. However, these materials are originally low in conductivity, and the Li ion diffusion rate inside the crystal is slow, so it is processed into fine particles having a primary particle diameter of several tens to 100 nm.
上述奈米尺寸之微粒子之製造方法已提案有在諸如合成矽酸鐵鋰時,將含有矽氧烷與鋰或鐵之複數有機金屬化合物溶解於可燃性之有機溶劑中而作成之原料溶液導入噴燒器中,並自安裝於噴燒器先端之噴嘴加以噴霧而使其燃燒生成氧化矽及上述各金屬之金屬氧化物之核粒子,且藉前述核粒子之聚結成長而製成由氧化矽與複數金屬氧化物所構成之複合微粒子之技術(參照諸如專利文獻1)。 The method for producing the above-mentioned nano-sized fine particles has been proposed to introduce a raw material solution prepared by dissolving a plurality of organometallic compounds containing a halogenated alkane and lithium or iron in a combustible organic solvent, such as lithium iron citrate. In the burner, the nozzle is sprayed from a nozzle attached to the tip end of the burner to be burned to form cerium oxide and the core particles of the metal oxide of each of the above metals, and the cerium oxide is formed by the agglomeration of the core particles. A technique of composite fine particles composed of a plurality of metal oxides (refer to, for example, Patent Document 1).
然而,上述專利文獻所揭露之方法所製成之矽酸鹽系鋰離子電池用活性物質之粒徑甚小而電池特性良好,但原料需使用可溶於有機溶劑之鋰及其它金屬原料,該等原料則甚為昂貴,故難以降低所需之活性物質之製造成本。 However, the active material of the bismuth hydride-based lithium ion battery produced by the method disclosed in the above patent document has a small particle size and good battery characteristics, but the raw material needs to use lithium and other metal materials which are soluble in an organic solvent. Raw materials are very expensive, so it is difficult to reduce the manufacturing cost of the active materials required.
專利文獻1:日本專利特開2012-195134號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-195134
自安裝於噴燒器先端之噴嘴噴霧含有矽氧烷與鋰或鐵之複數有機金屬化合物溶解於可燃性之有機溶劑中而作成之原料溶液而使其燃燒之方法,雖其原料之燃燒性良好,而可製得微粒子,但原料昂貴,故有成本提高之問 題。另,使用將金屬鹽等溶解於水性溶媒中而製作之原料溶液時,與將複數之有機金屬化合物溶解於可燃性之有機溶劑中時相較,雖成本較低,但噴霧時之燃燒性較差,且將發生較大粒子之混入。 A method of spraying a raw material solution prepared by dissolving a plurality of organometallic compounds of lithium or iron in a flammable organic solvent and burning the same from a nozzle attached to the tip end of the burner, although the raw material has good combustion property. , but the particles can be made, but the raw materials are expensive, so there is a cost increase. question. Further, when a raw material solution prepared by dissolving a metal salt or the like in an aqueous solvent is used, the cost is low, but the flammability at the time of spraying is poor compared to when a plurality of organometallic compounds are dissolved in a flammable organic solvent. And the mixing of larger particles will occur.
本發明即有鑑於上述狀況,目的在提供一種可藉噴霧燃燒法而以較低成本製造粒徑小而特性良好之矽酸鹽系之鋰離子二次電池用活性物質之微粒子之製造方法、使用該方法之鋰離子二次電池及其原料乳劑。 In view of the above circumstances, it is an object of the present invention to provide a method for producing fine particles of a lithium ion secondary battery active material which can be produced by a spray combustion method and having a small particle size and a good property at a low cost. A lithium ion secondary battery of the method and a raw material emulsion thereof.
為達成前述目的,本發明具有以下之特徵。 To achieve the foregoing objects, the present invention has the following features.
(1)本發明為一種微粒子製造方法,其特徵在於包含以下步驟:製備原料乳劑之步驟,該原料乳劑係油包水型乳劑且於可燃性液體中以液滴形式分散有原料溶液,該原料溶液至少含有含矽微粒子與鋰源以及矽與鋰以外之原料金屬源;將前述原料乳劑噴霧成液滴狀之步驟;及,使前述液滴中之可燃性液體燃燒,而形成微粒子之步驟。 (1) The present invention is a method for producing fine particles, which comprises the steps of: preparing a raw material emulsion which is a water-in-oil emulsion and dispersing a raw material solution in the form of droplets in a flammable liquid, the raw material The solution contains at least a cerium-containing fine particle and a lithium source, and a raw material metal source other than cerium and lithium; a step of spraying the raw material emulsion into a droplet form; and a step of burning the flammable liquid in the liquid droplet to form fine particles.
(2)如(1)揭露之微粒子製造方法,其特徵在於當以鋰為Li,以矽為Si,進而以選自於由Fe、Mn、Ti、Cr、V、Ni、Co、Cu、Zn、Al、Ge、Zr、Mo、W所構成群組中之1種或2種以上的金屬元素為M,並以選自於由Ti、Cr、V、Zr、Mo、W、P、B所構成群組中之至少1種金屬元素為X時,前述微粒子之組成以通式表示為LiyMSi1-zXzO4、1≦y≦2、0≦z<0.4。 (2) The method for producing fine particles as disclosed in (1), characterized in that lithium is Li, lanthanum is Si, and further selected from the group consisting of Fe, Mn, Ti, Cr, V, Ni, Co, Cu, and Zn. One or two or more metal elements of the group consisting of Al, Ge, Zr, Mo, and W are M, and are selected from the group consisting of Ti, Cr, V, Zr, Mo, W, P, and B. When at least one metal element in the constituent group is X, the composition of the fine particles is expressed by the formula as Li y MSi 1-z X z O 4 , 1 ≦ y ≦ 2, and 0 ≦ z < 0.4.
(3)如(1)揭露之微粒子製造方法,其特徵在於前述原料 乳劑中含有界面活性劑。 (3) The method for producing a microparticle according to (1), characterized in that the aforementioned raw material The emulsion contains a surfactant.
(4)如(3)揭露之微粒子製造方法,其特徵在於前述界面活性劑係HLB為3~6之非離子型界面活性劑。 (4) The method for producing fine particles disclosed in (3), characterized in that the surfactant is a nonionic surfactant having a HLB of 3 to 6.
(5)如(1)揭露之微粒子製造方法,其特徵在於分散於前述可燃性液體中之前述原料溶液的液滴的平均粒徑為0.5~10μm。 (5) The method for producing fine particles disclosed in (1), characterized in that the droplets of the raw material solution dispersed in the flammable liquid have an average particle diameter of 0.5 to 10 μm.
(6)如(1)揭露之微粒子製造方法,其特徵在於經噴霧之前述原料乳劑的液滴的平均粒徑為5~500μm。 (6) The method for producing fine particles disclosed in (1), characterized in that the droplets of the raw material emulsion sprayed have an average particle diameter of 5 to 500 μm.
(7)如(1)揭露之微粒子製造方法,其特徵在於前述含矽微粒子乃含有二氧化矽或矽酸鋰之微粒子。 (7) The method for producing a fine particle according to (1), characterized in that the ruthenium-containing fine particles are fine particles containing ruthenium dioxide or lithium niobate.
(8)如(1)揭露之微粒子製造方法,其特徵在於前述原料溶液含有鋰及選自於由鋰與矽以外之原料金屬之硝酸鹽、氫氧化物、鹽酸鹽、硫酸鹽、醋酸鹽、碳酸鹽所構成群組中之1種以上的原料。 (8) The method for producing a fine particle according to (1), wherein the raw material solution contains lithium and a nitrate, a hydroxide, a hydrochloride, a sulfate, or an acetate selected from a raw material metal other than lithium and cesium. One or more kinds of raw materials in the group consisting of carbonates.
(9)如(1)揭露之微粒子製造方法,其特徵在於前述可燃性液體含有1種以上之油性燃料。 (9) The method for producing fine particles disclosed in (1), characterized in that the flammable liquid contains one or more types of oily fuels.
(10)本發明為一種鋰離子二次電池用正極活性物質之製造方法,其特徵在於將以(1)~(9)中任一項之微粒子製造方法而製成之微粒子,與選自於由有機高分子材料、醣類、多價醇類、碳質材料所構成群組中之一種以上的碳源混合後,在鈍氣環境中進行燒成,使其變成具有橄欖石構造之矽酸過渡金屬鋰化合物。 (10) The present invention is a method for producing a positive electrode active material for a lithium ion secondary battery, characterized in that the fine particles produced by the method for producing fine particles according to any one of (1) to (9) are selected from After mixing one or more carbon sources of a group consisting of organic polymer materials, saccharides, polyvalent alcohols, and carbonaceous materials, the mixture is fired in an inert gas atmosphere to form a tannic acid having an olivine structure. Transition metal lithium compound.
(11)本發明為一種矽酸鹽系之鋰離子二次電池用正極活性物質,係使用(10)揭露之製造方法而製成。 (11) The present invention is a positive electrode active material for a lithium ion secondary battery of a citrate type, which is produced by the production method disclosed in (10).
(12)本發明為一種鋰離子二次電池,係使用(11)揭露之正極活性物質而製成。 (12) The present invention is a lithium ion secondary battery produced by using the positive electrode active material disclosed in (11).
(13)本發明為一種油包水型之微粒子製造用原料乳劑,其於可燃性液體中分散有至少含有含矽微粒子與鋰源以及矽與鋰以外之原料金屬源的原料溶液的液滴。 (13) The present invention relates to a water-in-oil type raw material emulsion for producing fine particles, in which a liquid droplet containing at least a raw material solution containing cerium fine particles and a lithium source and a raw material metal source other than cerium and lithium is dispersed in the flammable liquid.
依據本發明,可藉噴霧燃燒法而提供粒徑小且特性良好之矽酸鹽系之鋰離子二次電池用正極活性物質及可以較低成本加以製造之方法。並可提供使用上述物質與方法之鋰離子二次電池及微粒子製造用原料乳劑與微粒子製造裝置。 According to the present invention, a positive electrode active material for a lithium ion secondary battery of a citrate type having a small particle size and excellent properties can be provided by a spray combustion method, and a method which can be produced at a low cost. A lithium ion secondary battery and a raw material emulsion and fine particle production apparatus for producing fine particles using the above materials and methods can be provided.
11‧‧‧微粒子製造裝置 11‧‧‧Microparticle manufacturing equipment
13‧‧‧原料乳劑 13‧‧‧ Raw emulsion
15‧‧‧噴霧噴嘴 15‧‧‧ spray nozzle
17‧‧‧噴霧氣體 17‧‧‧ spray gas
19‧‧‧原料流 19‧‧‧Material flow
21‧‧‧液滴 21‧‧‧ droplets
23‧‧‧燃燒源 23‧‧‧Combustion source
25‧‧‧火焰 25‧‧‧flame
27‧‧‧微粒子 27‧‧‧Microparticles
31‧‧‧可燃性液體 31‧‧‧Combustible liquid
33‧‧‧原料溶液 33‧‧‧ raw material solution
35‧‧‧界面活性劑 35‧‧‧Interactive surfactant
37‧‧‧含矽微粒子 37‧‧‧ containing fine particles
41‧‧‧處理室 41‧‧‧Processing room
43‧‧‧微粒子回收裝置 43‧‧‧Microparticle recovery unit
45‧‧‧排放氣 45‧‧‧Exhaust gas
51‧‧‧核粒子 51‧‧‧nuclear particles
53‧‧‧原粒子 53‧‧‧Original particles
61‧‧‧微粒子製造裝置 61‧‧‧Microparticle manufacturing equipment
63‧‧‧勻合器 63‧‧‧Season
圖1顯示第1實施形態之微粒子製造裝置11之構造。 Fig. 1 shows the structure of the fine particle production apparatus 11 of the first embodiment.
圖2顯示原料乳劑13之構造。 Figure 2 shows the construction of the raw material emulsion 13.
圖3顯示原料流19中之液滴21之構造。 Figure 3 shows the construction of droplets 21 in feed stream 19.
圖4顯示微粒子製造裝置11與微粒子回收裝置43之構造。 4 shows the configuration of the microparticle manufacturing apparatus 11 and the microparticle recovery apparatus 43.
圖5說明藉由噴霧燃燒法之微粒子之生成。 Figure 5 illustrates the formation of microparticles by a spray combustion method.
圖6顯示第1實施形態之另一例之微粒子製造裝置61之構造。 Fig. 6 shows the structure of a fine particle producing apparatus 61 of another example of the first embodiment.
圖7為實施例1之原料乳劑之光學顯微鏡相片。 Figure 7 is an optical micrograph of the raw material emulsion of Example 1.
圖8為實施例1之正極活性物質之X射線繞射量測結果。 Fig. 8 is a graph showing the results of X-ray diffraction measurement of the positive electrode active material of Example 1.
圖9為實施例1之正極活性物質之掃描型電子顯微鏡相片。 Fig. 9 is a scanning electron micrograph of the positive electrode active material of Example 1.
圖10為實施例1及比較例之正極活性物質之充放電特性(實線:實施例1,虛線:比較例)。 Fig. 10 shows the charge and discharge characteristics of the positive electrode active material of Example 1 and Comparative Example (solid line: Example 1, broken line: comparative example).
以下基於圖示而詳細說明本發明之實施形態。 Hereinafter, embodiments of the present invention will be described in detail based on the drawings.
(第1實施形態) (First embodiment)
(微粒子製造裝置) (Microparticle manufacturing device)
圖1為說明第1實施形態之微粒子製造裝置11之模式圖。微粒子製造裝置11包含將供入原料乳劑13與噴霧氣體17而噴出含有原料乳劑13之液滴21之原料流19之噴霧噴嘴15,以及可使原料流19燃燒之燃燒源23。燃燒源23設成連接噴霧噴嘴15,可使原料流19及噴霧氣體17燃燒,而形成火焰25。 Fig. 1 is a schematic view showing the fine particle production apparatus 11 of the first embodiment. The microparticle production apparatus 11 includes a spray nozzle 15 that feeds the raw material emulsion 13 and the spray gas 17 to discharge the raw material stream 19 containing the liquid droplets 21 of the raw material emulsion 13, and a combustion source 23 that can burn the raw material stream 19. The combustion source 23 is connected to the spray nozzle 15, and the raw material stream 19 and the spray gas 17 can be burned to form the flame 25.
(原料乳劑) (raw emulsion)
由於藉微粒子製造裝置11製造矽酸鹽系鋰離子二次電池用正極活性物質,故原料乳劑13中至少含有鋰源、矽源及鋰與矽以外之其它原料金屬源。使原料乳劑13中含有鋰源、矽源及其等以外之原料金屬源,即可使製得之微粒子27含有鋰之氧化物、矽之氧化物及鋰與矽以外之金屬之氧化物,以及其等之多氧化物等,並使上述微粒子結晶以形成具有橄欖石構造之鋰過渡金屬矽酸鹽。舉例言之,使用鐵作為鋰、矽以外之原料金屬,並按各元素之化學計量成 分比例而依Li:Fe:Si=2:1:1配製原料乳劑13,即可製得具有橄欖石構造之矽酸鐵鋰(Li2FeSiO4)。 Since the positive electrode active material for a bismuth hydride-based lithium ion secondary battery is produced by the fine particle production apparatus 11, the raw material emulsion 13 contains at least a lithium source, a ruthenium source, and a raw material metal source other than lithium and ruthenium. The raw material emulsion 13 contains a raw material metal source other than a lithium source, a cerium source, and the like, so that the obtained fine particles 27 contain an oxide of lithium, an oxide of cerium, and an oxide of a metal other than lithium and cerium, and The oxide or the like is crystallized, and the fine particles are crystallized to form a lithium transition metal niobate having an olivine structure. For example, using iron as a raw material metal other than lithium or lanthanum, and preparing a raw material emulsion 13 according to a ratio of stoichiometric components of each element according to Li:Fe:Si=2:1:1, an olivine structure can be obtained. Lithium iron citrate (Li 2 FeSiO 4 ).
在此,本發明所製得之微粒子之組成若以鋰為Li,以矽為Si,進而以選自於由Fe、Mn、Ti、Cr、V、Ni、Co、Cu、Zn、Al、Ge、Zr、Mo、W所構成群組中之1種或2種以上的金屬元素為M,並以選自於由Ti、Cr、V、Zr、Mo、W、P、B所構成群組中之至少1種金屬元素為X時,前述微粒子之組成則可以通式表示為LiyMSi1-zXzO4、1≦y≦2、0≦z<0.4。尤其,X中含有過渡元素以外之P、B時,若為P,則使用之原料可使用磷酸(H3PO4)、磷酸二氫銨(NH4H2PO4)、磷酸銨((NH4)3PO4),若為B,則可使用硼酸(H3BO3)、五硼酸銨(NH4B5O8)及其等之水合物等。 Here, the composition of the microparticles obtained by the present invention is such that lithium is Li, yttrium is Si, and further selected from Fe, Mn, Ti, Cr, V, Ni, Co, Cu, Zn, Al, Ge. One or two or more metal elements of the group consisting of Zr, Mo, and W are M, and are selected from the group consisting of Ti, Cr, V, Zr, Mo, W, P, and B. When at least one of the metal elements is X, the composition of the fine particles may be expressed by Li y MSi 1-z X z O 4 , 1 ≦ y ≦ 2, and 0 ≦ z < 0.4. In particular, when P and P other than the transition element are contained in X, if it is P, phosphoric acid (H 3 PO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), ammonium phosphate ((NH) may be used as the raw material used. 4 ) 3 PO 4 ), and if B, a boric acid (H 3 BO 3 ), ammonium pentaborate (NH 4 B 5 O 8 ), a hydrate thereof, or the like can be used.
如圖2所示,原料乳劑13係油包水型乳劑且於可燃性液體31中以液滴形式分散有原料溶液33,該原料溶液33係至少含有含矽微粒子37與鋰離子以及鋰與矽以外之原料金屬離子。 As shown in FIG. 2, the raw material emulsion 13 is a water-in-oil emulsion, and a raw material solution 33 containing at least cerium-containing fine particles 37 and lithium ions and lithium and lanthanum is dispersed in the flammable liquid 31 as droplets. Metal ions other than the raw materials.
(可燃性液體) (flammable liquid)
可燃性液體31若為可燃性之液體即無特別之限制,但宜含有選自於由燈油、煤油、輕油、汽油、松節油、重油、己烷、辛烷、癸烷、十二烷、二甲苯、甲苯、二甲醚所構成群組中之1種以上的燃料。就價格及處理性之觀點而言,以燈油與輕油為尤佳,而可使用燈油與輕油之混合物。 The flammable liquid 31 is not particularly limited as long as it is a flammable liquid, but preferably contains a singly selected from the group consisting of kerosene, kerosene, light oil, gasoline, turpentine, heavy oil, hexane, octane, decane, dodecane, and One or more fuels in the group consisting of toluene, toluene, and dimethyl ether. In terms of price and handling, it is preferred to use kerosene and light oil, and a mixture of kerosene and light oil can be used.
(含矽微粒子) (containing strontium particles)
已分散於原料溶液33中之含矽微粒子37若為含矽之微 粒子則無特別之限定,但宜為含有二氧化矽(SiO2)或矽酸鋰(Li2SiO3)之微粒子。此則因含矽微粒子37中不含不應於正極活性物質中含有之其它金屬元素之故。 The cerium-containing fine particles 37 which have been dispersed in the raw material solution 33 are not particularly limited as long as they contain cerium-containing fine particles, but are preferably fine particles containing cerium oxide (SiO 2 ) or lithium niobate (Li 2 SiO 3 ). This is because the ruthenium-containing fine particles 37 do not contain other metal elements which should not be contained in the positive electrode active material.
含矽微粒子37之粒徑愈小,製得之微粒子粒徑愈小,甚至製得之正極活性物質之粒徑亦愈小,故較為適用。含矽微粒子37之原粒子之平均粒徑宜為50nm以下,20nm以下則更佳。含矽微粒子37之平均粒徑可藉電子顯微鏡之觀察或動態光散射法而加以求出。 The smaller the particle diameter of the cerium-containing fine particles 37, the smaller the particle size of the obtained fine particles, and the smaller the particle diameter of the obtained positive electrode active material, the more suitable it is. The average particle diameter of the primary particles of the cerium-containing fine particles 37 is preferably 50 nm or less, more preferably 20 nm or less. The average particle diameter of the cerium-containing fine particles 37 can be determined by observation by an electron microscope or dynamic light scattering method.
又,含矽微粒子37表面為親水性,故將分散於原料溶液33中而非可燃性液體31中。視含矽微粒子之種類不同,可形成乳劑可長時間安定化之皮克林乳液。 Further, since the surface of the cerium-containing fine particles 37 is hydrophilic, it is dispersed in the raw material solution 33 instead of the flammable liquid 31. Depending on the type of bismuth-containing microparticles, it is possible to form a Pickering emulsion in which the emulsion can be stabilized for a long period of time.
(原料金屬) (raw material metal)
原料溶液33中,除含矽微粒子、鋰源以外,並含有鋰與矽以外之原料金屬源,但原料溶液33中含有之其它鋰與矽以外之原料金屬可單獨使用或複數組合而使用鐵(Fe)、錳(Mn)、鈦(Ti)、鉻(Cr)、釩(V)、鎳(Ni)、鈷(Co)、銅(Cu)、鋅(Zn)、鋁(Al)、鍺(Ge)、鋯(Zr)、鉬(Mo)、鎢(W)等。原料溶液33中除鋰以外,宜含有選自於由鋰與矽以外之原料金屬之硝酸鹽、氫氧化物、鹽酸鹽、硫酸鹽、醋酸鹽、碳酸鹽、檸檬酸鹽等所構成群組中之1種以上的原料。舉例言之,鋰源可使用硝酸鋰、氯化鋰、碳酸鋰等。使用鐵作為鋰、矽以外之原料金屬時,可使用硝酸鐵、氯化亞鐵、三氯化鐵等作為鐵源。 In the raw material solution 33, in addition to the ruthenium-containing fine particles and the lithium source, a raw material metal source other than lithium and ruthenium is contained, but the other lithium contained in the raw material solution 33 and the raw material metal other than ruthenium may be used singly or in combination of iron. Fe), manganese (Mn), titanium (Ti), chromium (Cr), vanadium (V), nickel (Ni), cobalt (Co), copper (Cu), zinc (Zn), aluminum (Al), antimony ( Ge), zirconium (Zr), molybdenum (Mo), tungsten (W), and the like. In addition to lithium, the raw material solution 33 preferably contains a group selected from the group consisting of nitrates, hydroxides, hydrochlorides, sulfates, acetates, carbonates, citrates, and the like of a raw material metal other than lithium and cesium. One or more kinds of raw materials. For example, lithium source, lithium chloride, lithium carbonate or the like can be used as the lithium source. When iron is used as a raw material metal other than lithium or ruthenium, iron nitrate, ferrous chloride, ferric chloride or the like can be used as the iron source.
(界面活性劑) (surfactant)
另,原料乳劑13為於可燃性液體31中以液滴形式分散原料溶液33之油包水型乳劑。為安定維持該狀態,宜添加有界面活性劑35。界面活性劑35可使親水基靠向原料溶液33,並使親油基靠向可燃性液體31,而使原料溶液33安定地分散於可燃性液體31中。未使用界面活性劑時,則如圖6所示之他例之微粒子製造裝置61般,於噴嘴前設置乳化機(勻合器63),在噴出後即朝噴霧噴嘴15供給原料乳劑13,而在保持油包水型乳劑之狀態下進行噴霧,即可形成液滴21。如此,即可使除含矽微粒子、鋰離子以外,並含有鋰與矽以外之原料金屬離子之原料溶液33於可燃性液體31中形成乳態,且即便不使用界面活性劑35亦可製作於可燃性液體31中以液滴形式分散有原料溶液33之油包水型乳劑的原料乳劑13。然後,則可原料乳劑13噴霧成液滴狀,而使液滴中之可燃性液體31燃燒,並形成微粒子27。 Further, the raw material emulsion 13 is a water-in-oil type emulsion in which the raw material solution 33 is dispersed as droplets in the flammable liquid 31. To maintain this state for stability, a surfactant 35 should be added. The surfactant 35 allows the hydrophilic group to abut against the raw material solution 33, and causes the oleophilic group to lean against the flammable liquid 31 to stably disperse the raw material solution 33 in the flammable liquid 31. When the surfactant is not used, an emulsifier (combiner 63) is placed in front of the nozzle as in the microparticle production apparatus 61 of the example shown in FIG. 6, and the raw material emulsion 13 is supplied to the spray nozzle 15 after the ejection. The droplets 21 are formed by spraying while maintaining the water-in-oil emulsion. In this manner, the raw material solution 33 containing metal ions other than lithium-containing fine particles and lithium ions and containing raw materials other than lithium and cerium can be formed into a milky state in the flammable liquid 31, and can be produced without using the surfactant 35. In the flammable liquid 31, the raw material emulsion 13 of the water-in-oil emulsion of the raw material solution 33 is dispersed as droplets. Then, the raw material emulsion 13 is sprayed into droplets to burn the flammable liquid 31 in the droplets, and the fine particles 27 are formed.
界面活性劑35宜使用HLB(親水親油均衡)為3~6之非離子型界面活性劑。HLB意指親水性親油性均衡。使用HLB為3~6之低HLB之界面活性劑,即可安定地形成親油基在外側、親水基在內側而包入水粒子之油包水型(W/O型、Water in oil型)之乳劑。在此,HLB若未滿3,則親水性較弱,難以形成W/O型之乳劑,HLB若超過6,則W/O之乳劑將不安定而易形成O/W型之乳劑,故不適用。因此,HLB之較佳範圍一如上述而為3~6。 As the surfactant 35, a nonionic surfactant having an HLB (hydrophilic-lipophilic balance) of 3 to 6 is preferably used. HLB means a hydrophilic lipophilic balance. By using a surfactant with a HLB of 3 to 6 low HLB, it is possible to form a water-in-oil type (W/O type, Water in oil type) in which the lipophilic group is on the outer side and the hydrophilic group is inside and the water particles are contained inside. Emulsion. Here, if the HLB is less than 3, the hydrophilicity is weak, and it is difficult to form a W/O type emulsion. If the HLB exceeds 6, the W/O emulsion will be unstable and easily form an O/W type emulsion, so Be applicable. Therefore, the preferred range of HLB is 3-6 as described above.
且,陽離子型及陰離子型之界面活性劑多於界面活性劑中含有碳與氫以外之金屬成分,故上述金屬成分可能混 入所製得之微粒子中成為雜質,或對裝置造成影響,因此宜使用非離子型界面活性劑作為界面活性劑35。界面活性劑35可使用山梨醇單油酸酯(商品名:花王出品RHEODOL SP-O10V)等之脂肪酸酯型非離子型界面活性劑等。 Moreover, since the cationic and anionic surfactants contain more metal components than carbon and hydrogen in the surfactant, the above metal components may be mixed. It is preferable to use a nonionic surfactant as the surfactant 35 because it becomes an impurity in the obtained fine particles or affects the device. As the surfactant 35, a fatty acid ester type nonionic surfactant such as sorbitol monooleate (trade name: Kao RHEODOL SP-O10V) can be used.
原料乳劑13宜為油包水型乳劑。若為油包水型乳劑,則原料乳劑13中之原料溶液33之液滴大小將小於噴霧水溶液所得之液滴,故可獲致粒徑較小之微粒子。即,直接以噴霧噴嘴15噴霧原料溶液33,亦難以獲致粒徑數μm之液滴,但可於乳劑內形成粒徑數μm之原料溶液之微細液滴。原料溶液33之液滴微細,故對原料溶液33之熱傳導較快,而可生成粒徑較小之微粒子。 The raw material emulsion 13 is preferably a water-in-oil type emulsion. In the case of a water-in-oil emulsion, the droplet size of the raw material solution 33 in the raw material emulsion 13 will be smaller than that of the sprayed aqueous solution, so that fine particles having a small particle size can be obtained. That is, the raw material solution 33 is directly sprayed by the spray nozzle 15, and it is also difficult to obtain droplets having a particle diameter of several μm, but fine droplets of the raw material solution having a particle diameter of several μm can be formed in the emulsion. Since the droplets of the raw material solution 33 are fine, the heat transfer to the raw material solution 33 is faster, and fine particles having a smaller particle diameter can be produced.
又,原料乳劑13為油包水型乳劑,故液滴表面之可燃性液體較易燃燒。且,原料溶液在油中係以較小之液滴形式分散,故可獲致粒徑較小之粒子。進而,控制油相及水相之比率,則可藉加熱原料溶液之液滴而使其分裂生成可燃性液體之微小液滴,故可促進原料乳劑之燃燒。 Further, since the raw material emulsion 13 is a water-in-oil type emulsion, the flammable liquid on the surface of the droplet is relatively easy to burn. Moreover, the raw material solution is dispersed in the oil as a smaller droplet, so that particles having a smaller particle size can be obtained. Further, by controlling the ratio of the oil phase and the water phase, the droplets of the raw material solution can be heated to be split into fine droplets of the flammable liquid, so that the combustion of the raw material emulsion can be promoted.
另,若為水包油型(O/W型、Oil in water型)之乳劑,則與火焰接觸之液滴表面為水相,故不易燃燒。且,原料溶液未以液滴形式分散,故加熱時可能生成粗粒。 Further, in the case of an oil-in-water type (O/W type, Oil in water type) emulsion, the surface of the droplet which is in contact with the flame is in an aqueous phase, so that it is not easily burned. Further, since the raw material solution is not dispersed in the form of droplets, coarse particles may be formed upon heating.
原料溶液33若分散於可燃性液體31中,粒徑等即無特別之限制,但原料乳劑13中之原料溶液33的液滴的平均粒徑宜為0.5~10μm。此因若為上述程度之平均粒徑,則燃燒時熱較易傳導至原料溶液33之液滴內部,而易於生成微粒子之故。原料溶液33之液滴之粒徑可藉界面活性劑之 濃度及種類、乳劑製作時之乳化方法、勻合器之轉數等而進行調整。 When the raw material solution 33 is dispersed in the flammable liquid 31, the particle size and the like are not particularly limited, but the average particle diameter of the droplets of the raw material solution 33 in the raw material emulsion 13 is preferably 0.5 to 10 μm. If the average particle diameter is the above-described degree, heat during combustion is more easily conducted to the inside of the liquid droplets of the raw material solution 33, and it is easy to generate fine particles. The particle size of the droplets of the raw material solution 33 can be made by the surfactant The concentration and type, the emulsification method at the time of preparation of the emulsion, the number of revolutions of the homogenizer, and the like are adjusted.
關於原料乳劑13中之原料溶液33之液滴粒徑,可以光學顯微鏡觀察原料溶液之液滴之粒徑而得知。 The droplet size of the raw material solution 33 in the raw material emulsion 13 can be known by observing the particle diameter of the droplets of the raw material solution by an optical microscope.
又,原料乳劑13中之原料溶液33與可燃性液體31之質量比宜為10:90~85:15。進而,兩者之質量比為40:60~80:20,甚至40:60~75:25則更佳。 Further, the mass ratio of the raw material solution 33 to the flammable liquid 31 in the raw material emulsion 13 is preferably from 10:90 to 85:15. Furthermore, the mass ratio of the two is 40:60~80:20, and even 40:60~75:25 is better.
另,為提昇原料乳劑13之燃燒性,亦可對原料乳劑13添加過氧化氫等氧化性液體。 Further, in order to improve the combustibility of the raw material emulsion 13, an oxidizing liquid such as hydrogen peroxide may be added to the raw material emulsion 13.
(噴霧噴嘴) (spray nozzle)
噴霧噴嘴15為雙流體噴霧噴嘴,可使供給之原料乳劑13液滴化,並加以噴出作為原料流19。原料乳劑13與噴霧氣體17將供入噴霧噴嘴15,並藉高速之噴霧氣體17之氣流將原料乳劑13沖碎成微細之液滴21。 The spray nozzle 15 is a two-fluid spray nozzle, and the supplied raw material emulsion 13 can be dropletized and ejected as a raw material stream 19. The raw material emulsion 13 and the spray gas 17 are supplied to the spray nozzle 15, and the raw material emulsion 13 is crushed into fine droplets 21 by a high-speed gas stream of the spray gas 17.
噴霧氣體17則可使用氮、氬、氧、空氣或其等之混合氣體。尤其,為使原料流19容易燃燒,噴霧氣體17宜使用氧。且,為提昇原料流19之可燃性,亦可就噴霧氣體17使用可燃性氣體與助燃性氣體之預混氣體。 As the spray gas 17, a mixed gas of nitrogen, argon, oxygen, air or the like can be used. In particular, in order to facilitate the combustion of the raw material stream 19, it is preferred to use oxygen as the spray gas 17. Further, in order to improve the flammability of the raw material stream 19, a premixed gas of a combustible gas and a combustion-supporting gas may be used as the spray gas 17.
(液滴) (droplet)
原料流19中含有原料乳劑13之液滴21。如圖3所示,液滴21微於可燃性液體31中以液滴形式分散有含矽微粒子與鋰離子以及鋰與矽以外之原料金屬離子的原料溶液33。 The raw material stream 19 contains droplets 21 of the raw material emulsion 13. As shown in FIG. 3, the droplets 21 are slightly dispersed in the flammable liquid 31 as a raw material solution 33 containing fine particles of cerium and lithium ions and metal ions other than lithium and cerium.
已噴霧之原料流19中之原料乳劑13的液滴21的平均粒徑宜為5~500μm,10~50μm則更佳。此則因若為上 述程度之大小,則噴霧原料乳劑13時易於使液滴21燃燒之故。 The droplets 21 of the raw material emulsion 13 in the sprayed raw material stream 19 preferably have an average particle diameter of 5 to 500 μm, more preferably 10 to 50 μm. This is because When the raw material emulsion 13 is sprayed, the droplets 21 are easily burned.
已噴霧之原料流19中之原料乳劑13之液滴21之粒徑可使用相位都卜勒雷射粒子分析儀評價已噴霧之液滴21而加以取得。相位都卜勒雷射粒子分析儀可使用液滴21通過2束雷射光之相交點時所取得之都卜勒頻率之相位差,而以非接觸方式求出液滴21之粒徑。 The particle size of the droplets 21 of the raw material emulsion 13 in the sprayed raw material stream 19 can be obtained by evaluating the sprayed droplets 21 using a phase Doppler laser particle analyzer. The phase Doppler laser particle analyzer can determine the particle diameter of the droplet 21 in a non-contact manner by using the phase difference of the Doppler frequency obtained when the droplet 21 passes through the intersection of the two beams of laser light.
如圖1所示,燃燒源23亦稱為導燃器,可使自噴霧噴嘴15噴出之原料流19燃燒。燃燒源23設置於噴霧噴嘴15前部,特別設在噴霧噴嘴15先端附近。已燃燒之原料流19將形成火焰25。原料流19中含有之液滴21則因火焰25而曝露於高溫下,將氧化並凝聚而形成微粒子27。 As shown in Fig. 1, the combustion source 23, also referred to as a pilot burner, allows the feedstock stream 19 ejected from the spray nozzle 15 to be combusted. The combustion source 23 is provided at the front of the spray nozzle 15, and is particularly provided near the tip end of the spray nozzle 15. The burned feed stream 19 will form a flame 25. The droplets 21 contained in the raw material stream 19 are exposed to a high temperature by the flame 25, and are oxidized and aggregated to form fine particles 27.
圖4顯示微粒子製造裝置11之微粒子回收裝置43之構造。微粒子製造裝置11之主要部分配置於處理室41中,連接處理室41而設有微粒子回收裝置43。 4 shows the configuration of the fine particle recovery device 43 of the microparticle manufacturing apparatus 11. The main part of the microparticle production apparatus 11 is disposed in the processing chamber 41, and is connected to the processing chamber 41 to be provided with the fine particle recovery device 43.
(第1實施形態之微粒子製造裝置之微粒子製造方法) (Method of Producing Fine Particles in Microparticle Production Apparatus According to First Embodiment)
以下,參照圖1說明使用第1實施形態之微粒子製造裝置11之微粒子製造方法。 Hereinafter, a method of producing fine particles using the fine particle production apparatus 11 of the first embodiment will be described with reference to Fig. 1 .
首先,朝噴霧噴嘴15供給原料乳劑13。噴霧噴嘴15為將供入噴霧氣體17之雙流體噴霧噴嘴,可使原料乳劑13液滴化而噴出原料流19。 First, the raw material emulsion 13 is supplied to the spray nozzle 15. The spray nozzle 15 is a two-fluid spray nozzle to which the spray gas 17 is supplied, and the raw material emulsion 13 can be dropletized to eject the raw material stream 19.
接著,原料流19將藉燃燒源23而燃燒,並形成火焰25。原料乳劑13之液滴21則於火焰25中形成微粒子27。 Next, the feed stream 19 will be burned by the combustion source 23 and form a flame 25. The droplets 21 of the raw material emulsion 13 form fine particles 27 in the flame 25.
然後,如圖4所示,微粒子製造裝置11中形成於火焰25中之微粒子27將通過設有微粒子製造裝置11之處理室41內,並為袋濾器或旋風分離機等微粒子回收裝置43所回收。 Then, as shown in Fig. 4, the fine particles 27 formed in the flame 25 in the fine particle manufacturing apparatus 11 pass through the processing chamber 41 provided with the fine particle manufacturing apparatus 11, and are recovered by the fine particle recovery means 43 such as a bag filter or a cyclone. .
圖5說明藉由噴霧燃燒法之微粒子之生成。自噴霧噴嘴15噴霧原料乳劑13,而形成粒徑為數μm~數百μm之液滴21之噴霧(原料流19),再於火焰25中加熱液滴21而生成微粒子27。於火焰25中將燃燒液滴21之可燃性液體31,並使原料溶液33之溶媒蒸發,且以含矽微粒子37為晶核,而使原料乳劑中含有之鋰、矽、鋰與矽以外之原料金屬藉燃燒反應而氧化形成核粒子51(晶核生成)。進而,在火焰25中,核粒子51將聚結、凝聚,而形成粒徑為數~100nm程度之原粒子53(氧化、凝聚)。生成於處理室41內之核粒子51及原粒子53等微粒子27將為微粒子回收裝置43所回收。含有微粒子27之氣流在以微粒子回收裝置43回收微粒子27後,則排出為排放氣45。 Figure 5 illustrates the formation of microparticles by a spray combustion method. The raw material emulsion 13 is sprayed from the spray nozzle 15 to form a spray (feed material stream 19) having droplets 21 having a particle diameter of several μm to several hundreds μm, and the liquid droplets 21 are heated in the flame 25 to generate fine particles 27. The flammable liquid 31 of the liquid droplets 21 is burned in the flame 25, and the solvent of the raw material solution 33 is evaporated, and the cerium-containing fine particles 37 are used as crystal nucleus, and lithium, cesium, lithium, and cerium are contained in the raw material emulsion. The raw material metal is oxidized by a combustion reaction to form core particles 51 (crystal nucleation). Further, in the flame 25, the core particles 51 are coalesced and aggregated to form the original particles 53 (oxidation, agglomeration) having a particle diameter of about several to 100 nm. The fine particles 27 such as the core particles 51 and the primary particles 53 generated in the processing chamber 41 are collected by the fine particle recovery device 43. The gas stream containing the fine particles 27 is discharged as the exhaust gas 45 after the fine particles 27 are recovered by the fine particle recovery device 43.
(第1實施形態之效果) (Effects of the first embodiment)
第1實施形態之微粒子製造裝置11使用油包水型之原料乳劑13,且可燃性液體31露出於液滴21表面,故可藉燃燒源23而輕易燃燒形成火焰25。且,原料乳劑13中含有微細液滴狀之原料溶液33,故不致生成粗粒。又,與使用水溶媒時不同,可快速加熱至液滴21內部,故可自液滴21均勻生成微細之微粒子27,而不致混入粗粒。 In the fine particle production apparatus 11 of the first embodiment, the water-in-oil type raw material emulsion 13 is used, and the combustible liquid 31 is exposed on the surface of the liquid droplet 21, so that the flame 25 can be easily burned by the combustion source 23. Further, since the raw material emulsion 13 contains the raw material solution 33 in the form of fine droplets, coarse particles are not formed. Further, unlike the case of using an aqueous solvent, it can be rapidly heated to the inside of the liquid droplet 21, so that the fine fine particles 27 can be uniformly formed from the liquid droplets 21 without being mixed into the coarse particles.
又,原料乳劑13中,除低成本之水溶性之鋰源以 外,並可使用鋰與矽以外之原料金屬源,故可抑制原料成本。尤其,即便使用界面活性劑時,亦可較使用可溶於可燃性液體之鋰源及可溶於可燃性液體之原料金屬源時更為抑制原料成本。 Further, in the raw material emulsion 13, in addition to the low-cost water-soluble lithium source, In addition, metal sources of raw materials other than lithium and tantalum can be used, so that the cost of raw materials can be suppressed. In particular, even when a surfactant is used, the raw material cost can be more suppressed than when a lithium source which is soluble in a flammable liquid and a raw material metal source which is soluble in a flammable liquid are used.
(噴燒器) (burner)
又,第1實施形態之微粒子製造裝置11及微粒子製造裝置61中,亦可設有用於形成將供入原料流19之火焰之環狀噴燒器。環狀噴燒器於已供入可燃性氣體與助燃性氣體之氣體導入管之環狀部分設有複數焰口。其次,可朝藉環狀噴燒器而形成之火焰供給原料流19。若可形成將供入原料流19之火焰,則噴燒器不限於環狀噴燒器,亦可使用焰口單一之噴燒器等。可燃性氣體並無特別之限制,可使用碳氫氣及氫氣等。且,助燃性氣體雖無特別之限定,但可使用空氣及氧等。 Further, in the fine particle production apparatus 11 and the fine particle production apparatus 61 of the first embodiment, a ring-shaped burner for forming a flame to be supplied into the raw material stream 19 may be provided. The annular burner is provided with a plurality of flame ports in an annular portion of the gas introduction pipe to which the flammable gas and the combustion-supporting gas have been supplied. Second, the feed stream 19 can be supplied to the flame formed by the annular burner. If a flame to be supplied to the raw material stream 19 can be formed, the burner is not limited to the annular burner, and a single burner such as a flame outlet can be used. The flammable gas is not particularly limited, and carbon hydrogen, hydrogen, or the like can be used. Further, although the combustion-supporting gas is not particularly limited, air, oxygen, or the like can be used.
(噴霧控制氣體噴出部) (spray control gas ejection unit)
又,第1實施形態之微粒子製造裝置11及微粒子製造裝置61中,亦可設有設在噴霧噴嘴15周圍而可自先端噴出噴霧控制氣體之噴嘴罩套。噴嘴罩套乃多層管構造之罩套。噴嘴罩套之功能在於自噴燒器之輻射熱保護噴霧噴嘴15之先端部而避免噴霧噴嘴15之阻塞,以及自噴嘴罩套先端流出噴霧控制氣體以形成覆蓋已噴霧之原料流19之氣流,並控制原料流19之指向性及流速。噴霧控制氣體可使用氮、氬、氧、空氣或其等之混合氣體。如上所述,控制原料流19之指向性及流速,即可增加朝火焰25中供給之原料流19 之比例而有效率地生成微粒子27,並控制火焰25中之原料之滯留時間,以控制粒徑。 Further, in the fine particle production apparatus 11 and the fine particle production apparatus 61 of the first embodiment, a nozzle cover which is provided around the spray nozzle 15 and which can spray a spray control gas from the tip end may be provided. The nozzle cover is a cover of a multi-layer tube construction. The function of the nozzle cover is to protect the tip end of the spray nozzle 15 from the radiant heat of the burner to avoid clogging of the spray nozzle 15, and to flow the spray control gas from the tip end of the nozzle cover to form a gas flow covering the sprayed material stream 19, and to control The directivity and flow rate of the feed stream 19. The spray control gas may use a mixed gas of nitrogen, argon, oxygen, air or the like. As described above, by controlling the directivity and flow rate of the feed stream 19, the feed stream 19 fed to the flame 25 can be increased. The fine particles 27 are efficiently produced in proportion and the residence time of the raw materials in the flame 25 is controlled to control the particle diameter.
(正極活性物質之製造方法) (Method for producing positive electrode active material)
就藉噴霧燃燒法而製得之矽酸鹽系鋰離子二次電池用活性物質之前驅物之微粒子進行結晶化處理,即可製得非水電解質二次電池之正極活性物質。尤其,將前驅物粒子與碳源混合後,宜於鈍氣充填環境下加以燒成。舉例言之,若為矽酸鐵鋰,則鐵成分在前驅物粒子內主要以3價之狀態存在,但在適當之還原環境下加以燒成,即可將鐵成分改變成2價,其結果,即可製得作為具有橄欖石構造之鋰離子二次電池用活性物質而作用之矽酸鐵鋰之結晶。 The positive electrode active material of the nonaqueous electrolyte secondary battery can be obtained by crystallization treatment of the fine particles of the precursor of the active material for the lithium ion secondary battery obtained by the spray combustion method. In particular, after mixing the precursor particles with the carbon source, it is preferably calcined in an atmosphere of a passive gas filling. For example, in the case of lithium iron ruthenate, the iron component is mainly present in the precursor particle in the form of a trivalent state, but when it is calcined in an appropriate reducing environment, the iron component can be changed to a divalent value, and as a result, Then, a crystal of lithium iron citrate which functions as an active material for a lithium ion secondary battery having an olivine structure can be obtained.
鈍氣可使用氮氣、氬氣、氖氣、氦氣、二氧化碳氣體等。且,為提高生成物之導電性,亦可於碳氫氣體充填環境中進行加熱處理。用於提高熱處理後之生成物之導電性之碳源則可使用聚乙烯醇、聚乙烯吡咯烷酮、羧甲基纖維素等有機高分子材料、葡萄糖、蔗糖等醣類、丙三醇、乙二醇等多價醇類、碳黑、石墨粉等碳質物質等。但若為可藉加熱處理而生成具有還原性之碳源之物質,則不限於上述物質。 As the inert gas, nitrogen gas, argon gas, helium gas, helium gas, carbon dioxide gas or the like can be used. Further, in order to improve the conductivity of the product, heat treatment may be performed in a hydrocarbon gas filling environment. As the carbon source for improving the conductivity of the product after the heat treatment, an organic polymer material such as polyvinyl alcohol, polyvinylpyrrolidone or carboxymethyl cellulose, a sugar such as glucose or sucrose, glycerin or ethylene glycol can be used. Carbonaceous materials such as polyvalent alcohols, carbon black, and graphite powder. However, if it is a substance which can generate a reducing carbon source by heat processing, it is not limited to the above.
宜以同一燒成步驟進行前驅物粒子之結晶化與藉碳而進行之塗覆或擔持處理。在熱處理條件為溫度300~900℃與處理時間0.5~10小時之組合下可適當製得所需之結晶性及粒徑之燒成物。高溫及長時間之熱處理所致過大之熱負載則可能導致生成粗大之單晶,故應予以避免, 宜在可製得所需之結晶性或微結晶性之正極活性物質之程度之加熱條件下,採用可儘可能抑制微晶之大小之熱處理條件。熱處理之溫度宜為400~800℃程度。 It is preferred to carry out the crystallization of the precursor particles and the coating or carrying treatment by carbon in the same baking step. The heat-treated condition is a combination of a temperature of 300 to 900 ° C and a treatment time of 0.5 to 10 hours, and a desired fired product of crystallinity and particle diameter can be suitably obtained. Excessive heat loading due to high temperature and prolonged heat treatment may result in the formation of coarse single crystals and should be avoided. It is preferred to use heat treatment conditions capable of suppressing the size of the crystallites as much as possible under the heating conditions to which the desired crystalline or microcrystalline positive electrode active material can be obtained. The temperature of the heat treatment is preferably about 400 to 800 °C.
另,製得之正極活性物質在燒成步驟中凝聚後,亦可藉研缽、球磨機或其它磨碎方式加以處理,而再形成粉末狀。 Further, after the obtained positive electrode active material is agglomerated in the firing step, it may be treated by a mortar, a ball mill or other grinding method to form a powder.
以下,以實施例具體說明本發明。 Hereinafter, the present invention will be specifically described by way of examples.
<實施例1> <Example 1>
將硝酸鋰(LiNO3)與九水合硝酸鐵(Fe(NO3)3.9H2O)溶解於純水中,進而加入氧化矽微粒子(AEROSIL 300(日本AEROSIL出品),平均一次粒徑7nm)而製成原料溶液。且,準備燈油作為可燃性液體。然後,使用花王製RHEODOL SP-O10V(山梨醇單油酸酯,HLB值為4.3)作為界面活性劑,並依原料溶液:可燃性液體:界面活性劑之重量比為65:33.5:1.5之比例加以置入設有金屬製之攪拌葉之勻合器中,依1萬rpm攪拌10分鐘,而製成油包水型之原料乳劑。另,就鋰源、鐵源及矽源則使原料乳劑中之Li、Fe、Si為Li2FeSiO4之化學計量比之2:1:1。且,原料乳劑中之濃度則設成使原料乳劑1kg所生成之Li2FeSiO4為0.5mol。 Lithium nitrate (LiNO 3 ) and iron nitrate nonahydrate (Fe(NO 3 ) 3 .9H 2 O) were dissolved in pure water, and then cerium oxide microparticles (AEROSIL 300 (produced by Japan AEROSIL) with an average primary particle diameter of 7 nm) were added. And the raw material solution is prepared. Further, varnish is prepared as a flammable liquid. Then, using Kao RHEODOL SP-O10V (sorbitol monooleate, HLB value of 4.3) as a surfactant, and according to the ratio of the raw material solution: flammable liquid: surfactant ratio of 65:33.5:1.5 The mixture was placed in a homogenizer equipped with a metal stirring blade, and stirred at 10,000 rpm for 10 minutes to prepare a water-in-oil type raw material emulsion. Further, in the lithium source, the iron source, and the rhodium source, Li, Fe, and Si in the raw material emulsion are 2:1:1 of the stoichiometric ratio of Li 2 FeSiO 4 . Further, the concentration in the raw material emulsion was set such that Li 2 FeSiO 4 produced by 1 kg of the raw material emulsion was 0.5 mol.
圖7為實施例1之原料乳劑藉光學顯微鏡加以觀察所得之相片。可觀察原料乳劑中之原料溶液之液滴,粒徑(液滴徑)為1.5μm程度。 Fig. 7 is a photograph of the raw material emulsion of Example 1 observed by an optical microscope. The droplets of the raw material solution in the raw material emulsion were observed, and the particle diameter (droplet diameter) was about 1.5 μm.
已使用圖1所示之微粒子製造裝置11而以上述原 料乳劑製成微粒子。首先,自雙流體噴霧噴嘴(噴霧噴嘴15)噴霧原料乳劑。噴霧所使用之氣體為氧氣。已噴霧之原料噴霧(原料流19)則藉燃燒源23而燃燒形成火焰25。其結果,已製得微粒子27。已生成之微粒子則為袋濾器所回收。 The microparticle manufacturing apparatus 11 shown in Fig. 1 has been used in the above-mentioned original The emulsion is made into fine particles. First, the raw material emulsion is sprayed from the two-fluid spray nozzle (spray nozzle 15). The gas used for the spray is oxygen. The sprayed raw material spray (feedstream 19) is combusted by combustion source 23 to form flame 25. As a result, the fine particles 27 have been produced. The generated microparticles are recovered by the bag filter.
於5wt%聚乙烯醇水溶液中依乾重比10:1分散微粒子與聚乙烯醇,並於水分蒸發後,在N2氣體環境下,進行製得之微粒子於650℃下之8小時燒成。燒成中將發生聚乙烯醇之碳化與過渡金屬之還原,並發生矽酸鐵鋰之生成與結晶化。就製得之凝聚體進行磨碎處理,即製得正極活性物質。 To 5wt% aqueous solution of polyvinyl alcohol by dry weight ratio of 10: The fine particles obtained in 8 hours at 650 ℃ baking the fine particles and a dispersion of polyvinyl alcohol, and after evaporation, under N 2 gas atmosphere, for. During the calcination, carbonization of the polyvinyl alcohol and reduction of the transition metal occur, and formation and crystallization of lithium iron citrate occur. The obtained agglomerates are subjected to a grinding treatment to obtain a positive electrode active material.
圖8為碳塗層後之正極活性物質進行X射線繞射量測後之結果。圖8之橫軸上之黑點代表橄欖石型之矽酸鐵鋰(Li2FeSiO4)所致之波峰出現之處。實施例1中,已知可製得橄欖石型之矽酸鐵鋰(Li2FeSiO4)之結晶。 Fig. 8 shows the results of X-ray diffraction measurement of the positive electrode active material after carbon coating. The black dots on the horizontal axis of Fig. 8 represent the occurrence of the peaks caused by the olivine-type lithium iron silicate (Li 2 FeSiO 4 ). In Example 1, it is known that a crystal of olivine-type lithium iron citrate (Li 2 FeSiO 4 ) can be obtained.
圖9為以掃描型電子顯微鏡觀察碳塗層後之正極活性物質之結果,已觀察到粒徑為50~200nm程度之微粒子。且,藉BET法測定正極活性物質之比表面積,結果則為16.2m2/g。 Fig. 9 shows the results of observing the positive electrode active material after the carbon coating with a scanning electron microscope. Microparticles having a particle diameter of about 50 to 200 nm have been observed. Further, the specific surface area of the positive electrode active material was measured by the BET method, and as a result, it was 16.2 m 2 /g.
(電池特性之評價) (Evaluation of battery characteristics)
對實施例1中製得之正極活性物質依10重量%混合導電助劑(碳黑),進而依乾重比90:10之比例混合混合粉末與黏結劑之聚偏二氟乙烯(PVdF)之N-甲基-2-吡咯烷酮(NMP)溶液後,再使用自轉公轉式攪拌機加以充份混拌,而製成陽極漿料。 The conductive active agent (carbon black) was mixed with 10% by weight of the positive electrode active material prepared in Example 1, and the mixed powder and the polyvinylidene fluoride (PVdF) of the binder were mixed at a ratio of dry weight to 90:10. After the N-methyl-2-pyrrolidone (NMP) solution, it was mixed with a self-rotating revolution mixer to prepare an anode slurry.
對厚20μm之鋁箔集電器依50g/m2之塗刷量塗布陽極漿料,並在120℃下予以乾燥30分鐘。然後,藉滾壓機施予輥軋加工,並加以模切成直徑16mm之圓盤狀而製成正極。 The anode slurry was applied to a 20 μm thick aluminum foil current collector at a coating amount of 50 g/m 2 and dried at 120 ° C for 30 minutes. Then, it was subjected to rolling processing by a roll press, and die-cut into a disk shape having a diameter of 16 mm to prepare a positive electrode.
該等正極在80℃下經過8小時之真空乾燥後,則於露點-60℃以下之氬置換之套手工作箱內,就負極使用金屬鋰,並就電解液使用依體積比1:1之比例混合碳酸伸乙酯及二乙基碳酸鹽而成之混合溶媒中溶解1M之濃度之LiPF6而成之溶液,且就分隔部使用厚20μm之聚烯性微孔質膜,而製成直徑20mm×厚1.6mm之2016型之鈕扣式電池。 After the positive electrode is vacuum dried at 80 ° C for 8 hours, the metal is used for the negative electrode in the argon replacement working chamber with a dew point of -60 ° C or less, and the volume ratio of the electrolyte is 1:1. A solution obtained by dissolving a concentration of 1 M of LiPF6 in a mixed solvent of ethyl carbonate and diethyl carbonate, and using a 20 μm thick polyene microporous membrane for the partition to make a diameter of 20 mm. × 2016 type button battery with a thickness of 1.6mm.
接著,就前述之鈕扣式鋰二次電池實施正極活性物質之電極特性之試驗評價如下。 Next, the test for evaluating the electrode characteristics of the positive electrode active material in the above-described button type lithium secondary battery was evaluated as follows.
在試驗溫度25℃,0.1C之電流率下,藉CC-CV法進行充電至4.5V(對Li/Li+),然後待電流率降至0.01C後停止充電。其後,在0.1C之比率下,藉CC法進行放電至1.5V(與前述相同),而測定初次放電容量。 At a test temperature of 25 ° C and a current rate of 0.1 C, the battery was charged to 4.5 V (for Li/Li + ) by the CC-CV method, and then the charging was stopped after the current rate dropped to 0.01 C. Thereafter, the discharge was carried out to 1.5 V by the CC method at the ratio of 0.1 C (the same as described above), and the initial discharge capacity was measured.
圖10顯示使用實施例1之正極活性物質及作為比較例而於可燃性之有機溶媒中溶解有機金屬化合物而成之原料溶液而製成之正極活性物質之充放電曲線。(a)為充電曲線,(b)為放電曲線。實線所示之實施例1之正極活性物質之初次放電容量為101mAh/g。相對於此,使用虛線所示之作為比較例而於可燃性之有機溶媒中溶解有機金屬化合物而成之原料溶液(環烷酸鋰、2-乙基己酸鐵、八甲基環四矽 氧烷、2乙基己酸)而製成之正極活性物質之初次放電容量為100mAh/g。如上所述,本發明所製得之活性物質可獲致與使用可燃性之有機溶劑中溶解有機金屬化合物而成之原料溶液而製成之活性物質同等良好之電池特性。 Fig. 10 is a graph showing a charge and discharge curve of a positive electrode active material prepared by dissolving a raw material active material of Example 1 and a raw material solution obtained by dissolving an organic metal compound in a flammable organic solvent as a comparative example. (a) is the charging curve and (b) is the discharge curve. The initial discharge capacity of the positive electrode active material of Example 1 shown by the solid line was 101 mAh/g. On the other hand, a raw material solution (lithium naphthenate, iron 2-ethylhexanoate, octamethylcyclotetramethylene) obtained by dissolving an organometallic compound in a flammable organic solvent as a comparative example shown by a broken line is used. The initial discharge capacity of the positive electrode active material prepared by using oxyalkylene or 2-ethylhexanoic acid was 100 mAh/g. As described above, the active material obtained by the present invention can attain the same battery characteristics as those of the active material prepared by dissolving the organic metal compound in a flammable organic solvent.
使用油包水型乳劑之實施例之原料之成本與使用可溶於溶劑中之原料時相較,可大幅降低至1/3~1/10。 The cost of the raw materials of the examples using the water-in-oil emulsion can be greatly reduced to 1/3 to 1/10 as compared with the case of using the raw materials soluble in the solvent.
舉例言之,可溶於溶劑中之金屬原料乃脂肪酸及苛性鹼反應後,再加入金屬鹽之水溶液而進行複分解,或在高溫下加熱處理脂肪酸與金屬化合物,使其等直接反應而製成。其因製造設備規模較大或反應時間較長,而導致原料成本提高。且,由於使金屬鹽等金屬化合物與其它物質反應而製成,故成本明顯高於金屬鹽。 For example, the metal raw material soluble in the solvent is reacted with a fatty acid and a caustic alkali, and then an aqueous solution of the metal salt is added to perform metathesis, or the fatty acid and the metal compound are heat-treated at a high temperature, and the like is directly reacted. The raw material cost is increased due to the large scale of the manufacturing equipment or the long reaction time. Further, since a metal compound such as a metal salt is reacted with other substances, the cost is remarkably higher than that of the metal salt.
相對於此,使用本發明之油包水型乳劑之原料之成本,由於可使用金屬鹽等較低價之原料,故成本低於可溶於溶劑之原料。 On the other hand, the cost of using the raw material of the water-in-oil type emulsion of the present invention is lower than that of a material which is soluble in a solvent because a relatively low-priced raw material such as a metal salt can be used.
如上所述,燒成將使用低成本之水溶性之原料而作成之油包水型之原料乳劑噴霧而製得之微粒子,即可製得粒徑甚小且電池特性亦良好之矽酸鐵鋰。進而,加以使用則可製造鋰離子二次電池用正極活性物質及使用該物質之二次電池。 As described above, by firing fine particles obtained by spraying a water-in-oil type raw material emulsion prepared by using a low-cost water-soluble raw material, lithium iron citrate having a small particle diameter and good battery characteristics can be obtained. . Further, when used, a positive electrode active material for a lithium ion secondary battery and a secondary battery using the same can be produced.
以上,已參照附圖而說明本發明之較佳實施形態,但本發明不受限於上述例示。本技術範疇之從業人士當可在本案所揭露之技術思想範疇內,構思各種變更例或修正例,其等亦應當理解為包含於本發明之技術範圍內。 The preferred embodiments of the present invention have been described above with reference to the drawings, but the present invention is not limited by the above description. Those skilled in the art can devise various modifications and alterations within the scope of the technical idea disclosed in the present invention, and the scope of the invention is also understood to be included in the technical scope of the present invention.
11‧‧‧微粒子製造裝置 11‧‧‧Microparticle manufacturing equipment
13‧‧‧原料乳劑 13‧‧‧ Raw emulsion
15‧‧‧噴霧噴嘴 15‧‧‧ spray nozzle
17‧‧‧噴霧氣體 17‧‧‧ spray gas
19‧‧‧原料流 19‧‧‧Material flow
21‧‧‧液滴 21‧‧‧ droplets
23‧‧‧燃燒源 23‧‧‧Combustion source
25‧‧‧火焰 25‧‧‧flame
27‧‧‧微粒子 27‧‧‧Microparticles
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