TWI398981B - Lithium secondary battery anode material - Google Patents
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Description
本發明係關於成為鋰二次電池之鋰載體之負極材料。The present invention relates to a negative electrode material which becomes a lithium carrier of a lithium secondary battery.
作為非水電解質二次電池之使用鋰鹽之有機電解液之鋰二次電池係輕量且能源密度高，被期待作為從攜帶用小型電子機器的電源到近年來之混合動力車或電汽車等之動力用電源。當初，使用金屬鋰作為鋰二次電池之負極材料，但在金屬鋰充電時，鋰離子析出、成長成樹枝晶狀，對於安全性也有問題，因此使用沒有此問題之石墨等碳材被提案。A lithium secondary battery using an organic electrolyte of a lithium salt as a nonaqueous electrolyte secondary battery is lightweight and has a high energy density, and is expected to be used as a power source for portable electronic devices to hybrid vehicles or electric cars in recent years. Power supply. At the beginning, metallic lithium was used as a negative electrode material for a lithium secondary battery. However, when lithium metal is charged, lithium ions are precipitated and grown into a dendritic shape, which poses a problem in terms of safety. Therefore, a carbon material such as graphite having no such problem has been proposed.
石墨材係由於鋰離子之摻雜．脫離性(脫．***性)優良而充放電效率高，更且，充放電時之電位也與金屬鋰幾乎相等，有可得到高電壓之電池等優點。然而，石墨化度高，石墨結晶之六角網面構造高度發達之石墨材易與電解液產生反應，有充放電效率低下等電池輸出減少，且電池之充放電循環特性也低下之缺點。Graphite is due to the doping of lithium ions. The detachability (deintercalation) is excellent, and the charge and discharge efficiency is high. Further, the potential at the time of charge and discharge is almost equal to that of metallic lithium, and there is an advantage that a battery having a high voltage can be obtained. However, the degree of graphitization is high, and the graphite material having a highly developed hexagonal mesh structure of graphite crystals easily reacts with the electrolyte, and the battery output is reduced, such as low charge and discharge efficiency, and the charge and discharge cycle characteristics of the battery are also low.
亦即，石墨化度高之石墨材，在例如丙烯碳酸酯系電解液中結晶面間有由於電解液共插層而容易造成石墨層間剝離，分解等現象之缺點。In other words, in the graphite material having a high degree of graphitization, for example, in the propylene carbonate-based electrolytic solution, there is a disadvantage that the electrolyte layer is intercalated and the graphite layer is easily peeled off and decomposed.
為解決此缺點，在日本專利公開07－06911號公報中係提案藉由使用微細結晶無秩序配列之碳材料來防止石墨結晶之六角網面構造之破壞，維持良好之循環特性，但充放電循環在40次左右就有低下之傾向，並不充分。In order to solve this drawback, it is proposed in Japanese Patent Laid-Open Publication No. 07-06911 to prevent the destruction of the hexagonal mesh structure of graphite crystals by using a carbon material which is disorderly arranged in a fine crystal, and to maintain good cycle characteristics, but the charge and discharge cycle is There are tendencies of lowness around 40 times, which is not sufficient.
一般而言，為使鋰離子之摻雜．脫離速度快，使鋰離子之擴散路徑短是有效的，由於使形成負極材料之碳素材之粒子徑變小較佳，作為以中間相碳(mesophase carbon)小球體作為負極材料之提案，例如在日本專利公開07－272725號公報中，提案將中間相碳小球體粉碎，使其平均粒徑為3~10 μm，以10℃/hr以下之升溫速度升溫至600~700℃熱處理後，在1000~3000℃燒成之方法，但由於中間相碳小球體之粒徑大至3~10 μm，因此鋰離子之擴散路徑無法變很短，為使摻雜．脫離速度快、不是以得到高輸出。In general, to dope lithium ions. The detachment speed is fast, and the diffusion path of lithium ions is short, and since the particle diameter of the carbon material forming the negative electrode material is made smaller, it is proposed as a negative electrode material using mesophase carbon small spheres, for example, In Japanese Patent Publication No. 07-272725, it is proposed to pulverize a mesophase carbon small sphere so as to have an average particle diameter of 3 to 10 μm, and to increase the temperature to a temperature of 1000 ° C to 700 ° C at a temperature increase rate of 10 ° C / hr or less. The method of firing at ~3000 °C, but since the particle size of the mesophase carbon small sphere is as large as 3~10 μm, the diffusion path of lithium ions cannot be shortened for doping. The detachment speed is fast, not to get a high output.
又，作為混合動力車或電汽車等之動力用電源來使用時，例如在上坡起步時在短時間要求高輸出，鋰離子之摻雜．脫離速度快是必要的，但同時也要求良好之循環特性。Moreover, when used as a power source for a hybrid vehicle or an electric car, for example, when starting uphill, high output is required in a short time, and lithium ions are doped. Fast detachment is necessary, but it also requires good cycling characteristics.
因此，除了藉由以粒子徑小之碳材來形成負極材料，以謀求鋰離子之摻雜．脫離速度之高速化以外，使用石墨化度低，石墨結晶之六角網面構造不那麼發達之難石墨化碳材，以求得充放電循環特性之提高是必要的。Therefore, in addition to forming a negative electrode material by a carbon material having a small particle diameter, lithium ion doping is sought. In addition to the high speed of the detachment speed, it is necessary to use a graphitized carbon material having a low degree of graphitization and a graphite crystal having a hexagonal mesh structure which is not so developed, in order to obtain an improvement in charge and discharge cycle characteristics.
作為粒子徑小，石墨結晶化度小之碳材如碳黑，例如，爐黑之一次粒子徑(基本粒子徑)為10~100nm程度，因此在日本專利公開63－285872號公報中，提案鋰載體藉由X線繞射法所求得之d002為3.35~3.8埃、結晶大小Lc為10~250埃、La為15~250埃、比表面積為50m2 /g以上之碳黑所構成之非水溶劑二次電池，又，本申請人也對碳黑所構成之鋰二次電池之負極材料進行了數個提案(日本專利公開06－068867號公報、日本專利公開06－068868號公報、日本專利公開06－068869號公報)。As a carbon material having a small particle diameter and a small degree of crystallinity of graphite, such as carbon black, for example, the primary particle diameter (basic particle diameter) of the furnace black is about 10 to 100 nm. Therefore, in Japanese Patent Laid-Open Publication No. 63-285872, lithium is proposed. The carbon black obtained by the X-ray diffraction method has a d002 of 3.35 to 3.8 angstroms, a crystal size Lc of 10 to 250 angstroms, a La of 15 to 250 angstroms, and a specific surface area of 50 m 2 /g or more. In addition, the present applicant has also made several proposals for a negative electrode material of a lithium secondary battery composed of carbon black (Japanese Patent Publication No. 06-068867, Japanese Patent Publication No. 06-068868, Japan) Patent Publication No. 06-068869).
然而，碳黑係由多數的一次粒子不規則的分岔為鍊狀，形成在三次元方向融著、結合之複雜凝集體(結構)，鋰離子係通過此凝集體來移動，即使在一次粒子徑小之碳黑中也不一定可以有效對於擴散路徑的短縮化有作用。However, the carbon black is chain-like by the irregular branching of most primary particles, forming a complex agglomerate (structure) that is fused and combined in the three-dimensional direction, through which lithium ions move, even in primary particles. The carbon black with a small diameter may not be effective for the shortening of the diffusion path.
在碳黑的種類中，將碳化氫原料熱分解而得到之熱碳黑之粒子徑大，結構不發達，其特徵在於碳黑粒子之凝集構造小這點。藉由將熱碳黑作為鋰二次電池負極材料來使用而得到改善了輸出特性或循環特性之鋰二次電池被提案(日本專利特表平11－514491號公報)，但在此中循環特性之改善也不一定充分。這是由於，熱碳黑之粒子徑大，其分布幅度也廣，因此粒子徑不均一化，容易在局部產生電流集中，對於循環特性有造成不好的影響之故。In the type of carbon black, the thermal carbon black obtained by thermally decomposing the hydrocarbon raw material has a large particle diameter and is not developed in structure, and is characterized in that the aggregation structure of the carbon black particles is small. A lithium secondary battery having improved output characteristics or cycle characteristics by using hot carbon black as a negative electrode material for a lithium secondary battery has been proposed (Japanese Patent Laid-Open Publication No. Hei 11-514491), but the cycle characteristics therein. The improvement is not necessarily sufficient. This is because the hot carbon black has a large particle diameter and a wide distribution range. Therefore, the particle diameter is not uniform, and current concentration is likely to occur locally, which has a bad influence on the cycle characteristics.
另一方面，本申請人，確認到藉由使用早先開發之實質上具有單一粒子形態之碳微小球作為鋰離子二次電池之負極材料來使用，可得到更優良之電池性能，而進行了新的提案(日本專利公開2005－243410號公報)。On the other hand, the applicant has confirmed that by using a carbon microsphere having a single particle form which has been developed earlier as a negative electrode material of a lithium ion secondary battery, a more excellent battery performance can be obtained, and a new one is obtained. Proposal (Japanese Patent Publication No. 2005-243410).
然而，上述提案中之碳微小球由於係以氫氣作為載體氣體，在氫氣氛下與比較低溫下緩慢熱分解來製造之故，因此在碳微小球表面上殘留焦油狀之碳質物。為除去此焦油狀碳質物，在2000℃以上之溫度有必要進行後處理般的熱處理，由於石墨之結晶化進行，因此有容易發生與電解液之反應之缺點，有充放電效率低下、電池輸出損失之問題。However, since the carbon microspheres in the above proposal are produced by hydrogen gas as a carrier gas and slowly thermally decomposed under a hydrogen atmosphere at a relatively low temperature, a tar-like carbonaceous material remains on the surface of the carbon microspheres. In order to remove the tar-like carbonaceous material, it is necessary to carry out a post-treatment heat treatment at a temperature of 2000 ° C or higher. Since the crystallization of graphite proceeds, there is a disadvantage that the reaction with the electrolytic solution easily occurs, and the charge and discharge efficiency is low, and the battery output is low. The problem of loss.
本發明係以上述提案為基礎，為謀求其改良而做成之物，以提供：較鋰離子之摻雜．脫離速度還快，且充放電循環特性優良，適合作為從攜帶機器用電源到混合動力車或電汽車等之動力源之具有高輸出之鋰二次電池之負極材料為目的。The present invention is based on the above proposal and is made for improvement thereof to provide: doping with lithium ions. The detachment speed is fast, and the charge/discharge cycle characteristics are excellent, and it is suitable for use as a negative electrode material of a lithium secondary battery having a high output from a power source for carrying a machine to a power source such as a hybrid car or an electric car.
為達成上述目的之本發明之鋰二次電池用負極材料，其特徵在於：藉由電子顯微鏡來測定之算術平均粒子徑dn為150~1000nm，揮發分Vm為5.0%以下，藉由旋轉離心分離裝置(DCF)所測定之斯脫克斯模式徑Dst與其半值寬度△Dst之比△Dst/Dst為0.40~1.10，藉由X光繞射法來測定之結晶晶格面間隔(d002)為0.370nm以下之碳微小球所構成。The negative electrode material for a lithium secondary battery of the present invention which achieves the above object is characterized in that the arithmetic mean particle diameter dn measured by an electron microscope is 150 to 1000 nm, and the volatile matter Vm is 5.0% or less by spin centrifugation. The ratio (D002) of the crystal lattice spacing (d002) measured by the X-ray diffraction method is 0.40 to 1.10, which is determined by the device (DCF), and the ratio ΔDst/Dst of the half-value width ΔDst is 0.40 to 1.10. It consists of carbon microspheres of 0.370 nm or less.
藉由本發明，由粒子間凝集少之碳微小球來形成鋰二次電池之負極材料，藉由特定碳微小球之粒子性狀及結晶性狀，來提供鋰離子之摻雜．脫離速度快、且充放電循環特性優良之鋰二次電池。According to the present invention, the negative electrode material of the lithium secondary battery is formed by carbon microballoons which are less agglomerated between particles, and the doping of lithium ions is provided by the particle properties and crystallinity of the specific carbon microspheres. A lithium secondary battery having a high release speed and excellent charge and discharge cycle characteristics.
形成本發明之鋰二次電池用負極材料之碳微小球，作為該粒子性狀之藉由電子顯微鏡所測定之算術平均一次粒子徑dn為150~1000nm，揮發分Vm有在5.0%以下之必要，又，粒子之凝集性狀藉由旋轉離心分離裝置(DCF)所測定之斯脫克斯模式徑Dst與其半值寬度△Dst之比△Dst/Dst有必要在0.40~1.10。The carbon microspheres forming the negative electrode material for a lithium secondary battery of the present invention have an arithmetic mean primary particle diameter dn of 150 to 1000 nm measured by an electron microscope as the particle property, and the volatile matter Vm is required to be 5.0% or less. Further, the agglutination property of the particles is required to be 0.40 to 1.10 in the ratio ΔDst/Dst of the sigma mode diameter Dst measured by the rotary centrifugal separator (DCF) to the half value width ΔDst.
又，藉由電子顯微鏡所測定之算術平均一次粒子徑dn(以下，也僅記為平均粒子徑dn)若未滿150nm，則鋰離子之摻雜．脫離速度快，但由於比表面積大，因此對於電解液變的活性，其結果，電池之初期效率低下。又，初期效率係指以最初鋰離子摻雜在碳六角網面層間時的容量為初期充電容量A，以該鋰離子脫離時之容量作為初期放電容量B之情況，以B/A×100(%)來表示。Further, the arithmetic mean primary particle diameter dn (hereinafter, also referred to as the average particle diameter dn) measured by an electron microscope is doped with lithium ions if it is less than 150 nm. The detachment speed is fast, but since the specific surface area is large, the activity of the electrolyte becomes variable, and as a result, the initial efficiency of the battery is lowered. In addition, the initial efficiency means that the capacity when the first lithium ion is doped between the carbon hexagonal mesh layers is the initial charge capacity A, and the capacity at the time of the lithium ion release is the initial discharge capacity B, and B/A×100 ( %)To represent.
然後，隨著重複充放電循環，碳六角網面的破壞進行，循環特性(對於反覆充放電之電池容量的維持率)也惡化。Then, as the charge and discharge cycle is repeated, the destruction of the carbon hexagonal mesh surface progresses, and the cycle characteristics (maintenance rate of the battery capacity for reverse charge and discharge) also deteriorate.
然而，若算數平均一次粒子徑dn超過1000nm，則由於粒子徑大，鋰離子的擴散路徑不會變短，因此鋰離子之摻雜．脫離速度變慢，為得到高輸出是不適切的。However, if the arithmetic average primary particle diameter dn exceeds 1000 nm, the diffusion path of lithium ions does not become short due to the large particle diameter, so the lithium ion is doped. The detachment speed is slow, and it is not suitable for obtaining high output.
又，算術平均一次粒子徑dn，係將試料藉由超音波分散器在頻率28kHz以30秒鐘使其分散在氯仿中調製之分散液固定於碳支持膜，將此以電子顯微鏡在直接倍率10000倍、綜合倍率100000攝影，從所得到之照片來隨機計測1000個粒子直徑，以每14nm來區分做成直方圖而求得算術平均一次粒子之直徑。Further, the arithmetic mean primary particle diameter dn was fixed to the carbon support film by a dispersion prepared by dispersing the sample in chloroform at a frequency of 28 kHz for 30 seconds by an ultrasonic disperser, and this was directly magnified by an electron microscope at 10000. The magnification was 100,000, and the diameter of 1000 particles was randomly measured from the obtained photograph, and the histogram was divided into 14 nm to obtain the diameter of the arithmetic mean primary particle.
存在於碳微小球之表面之焦油分或表面官能基會將表面的活性位置埋住，因此使其殘存量少為必要，特別是原料碳化氫之未分解物的焦油狀物質有必要儘量排除。因此，將揮發分Vm規定在5.0%以下。又，揮發分Vm係根據JIS K6221－1986「橡膠用碳黑之試驗方法」來測定。The tar or surface functional groups present on the surface of the carbon microspheres will bury the active site on the surface, so that it is necessary to make the residual amount small, and in particular, the tar-like substance of the undecomposed material of the raw material hydrocarbon must be excluded as much as possible. Therefore, the volatile matter Vm is specified to be 5.0% or less. Further, the volatile matter Vm is measured in accordance with JIS K6221-1986 "Test Method for Carbon Black for Rubber".
又，本發明之碳微小球，其次粒子凝集形態藉由旋轉離心分離裝置(DCF)所測定之斯脫克斯模式徑Dst與其半值寬度△Dst之比△Dst/Dst為0.40~1.10。若一次粒子凝集體的大小分部廣，則電流在負極內流動時發生局部的電流集中，所以其分布必須狹窄。另一方面，一次粒子凝集體的大小分布若過於狹窄則在電極形成時之塗工性低下。因此，在本發明中，由於使一次粒子凝集體的分布寬度設定在一定範圍內，而將△Dst/Dst之值規定為0.4~1.10。又，斯托克斯模式徑Dst以150~1500nm程度為佳。Further, in the carbon microsphere of the present invention, the ratio of the strish mode diameter Dst measured by the rotary centrifugal separator (DCF) to the half value width ΔDst ΔDst/Dst is 0.40 to 1.10. If the size of the primary particle aggregate is wide, the local current concentration occurs when the current flows in the negative electrode, so the distribution must be narrow. On the other hand, if the size distribution of the primary particle aggregate is too narrow, the workability at the time of electrode formation is lowered. Therefore, in the present invention, since the distribution width of the primary particle aggregates is set within a certain range, the value of ΔDst/Dst is set to 0.4 to 1.10. Further, the Stokes mode diameter Dst is preferably about 150 to 1500 nm.
斯托克斯模式徑Dst與以其半值寬度△Dst之值係藉由下述方法來測定。The Stokes mode diameter Dst and the value of its half-value width ΔDst are determined by the following method.
將乾燥之碳微小球與包含少量界面活性劑之20vol%乙醇水溶液混合，作成碳濃度0.1kg/m3 之分散液，將此以超音波來使其充分分散來作為試料。將旋轉離心分離裝置(英國Joyes Lobel公司製)設定為100s－1 之回轉數，將旋轉液(2wt%甘油水溶液，25℃)添加0.015dm3 後，注入0.001dm3 之緩衝液(20vol%乙醇溶液，25℃)。接著，將溫度25℃之碳分散液0.0005 dm3 以注射器加入後，開始離心沉降，同時使記錄器動作來作成如第1圖所示之分布曲線(橫軸：以注射器添加碳分散液後之經過時間，縱軸：隨著碳試料之離心沉降而變化之特定點的吸光度)。從此分布曲線來讀取各時間T，代入下述所示數式1來算出對應各時間之斯托克斯相當徑。The dried carbon microspheres were mixed with a 20 vol% aqueous ethanol solution containing a small amount of a surfactant to prepare a dispersion having a carbon concentration of 0.1 kg/m 3 , and this was sufficiently dispersed as a sample by ultrasonic waves. The rotary centrifugal separator (manufactured by Joyes Lobel Co., Ltd., UK) was set to a number of revolutions of 100 s -1 , and a rotating liquid (2 wt% glycerin aqueous solution, 25 ° C) was added to 0.015 dm 3 , and then a buffer of 0.001 dm 3 (20 vol% ethanol) was injected. Solution, 25 ° C). Next, after adding a carbon dispersion of 0.0005 dm 3 at a temperature of 25 ° C as a syringe, centrifugal sedimentation was started, and the recorder was operated to prepare a distribution curve as shown in Fig. 1 (horizontal axis: after adding a carbon dispersion by a syringe) Elapsed time, vertical axis: absorbance at a specific point as a function of centrifugal sedimentation of the carbon sample). The time T is read from the distribution curve, and the following equation 1 is substituted to calculate the Stokes equivalent diameter for each time.
在上述數式1中η為旋轉液之黏度(0.935×10－3 Pa．s)，N為旋轉回轉速度(100 s－1 )、r1 為碳分散液注入點的半徑(0.0456m)、r2 為到吸光度測定點之半徑(0.0482m)、ρcb 為碳之密度(kg/m3 )、ρ1 為旋轉液的密度(1.00178kg/m3 )。In the above formula 1, η is the viscosity of the rotary liquid (0.935 × 10 -3 Pa.s), N is the rotational rotation speed (100 s -1 ), and r 1 is the radius of the carbon dispersion injection point (0.0456 m), r 2 is the radius to the absorbance measurement point (0.0482 m), ρ cb is the density of carbon (kg/m 3 ), and ρ 1 is the density of the rotary liquid (1.00178 kg/m 3 ).
在如此所得到之斯托克斯相當徑與吸光度之分布曲線(第2圖)中，將最大頻度的斯托克斯相當徑作為斯托克斯模式徑Dst、可得到相對於最大頻度之50%之頻度之大小2點之斯托克斯相當徑的差(半值寬度)作為△Dst(nm)。In the Stokes equivalent diameter and absorbance distribution curve (Fig. 2) thus obtained, the Stokes equivalent diameter of the maximum frequency is taken as the Stokes mode diameter Dst, and 50 with respect to the maximum frequency can be obtained. The difference between the frequency of % and the Stokes equivalent diameter at 2 points (half-value width) is ΔDst (nm).
形成本發明之鋰二次電池用負極材料之碳微小球，除了這些粒子性狀以外，還必須為具備藉由x光繞射法來測定之結晶晶格面間隔(d002)在0.370nm以下之結晶性狀。In addition to these particle properties, the carbon microspheres forming the negative electrode material for a lithium secondary battery of the present invention must have crystals having a crystal lattice spacing (d002) of 0.370 nm or less as measured by x-ray diffraction. Traits.
在結晶晶格面間隔(d002)超過0.370nm之結晶性狀，由於非晶質比率高，因此摻雜鋰離子之位置顯著降低，在碳六角網面層無法***充分量之鋰離子，電池容量低下。但是，(d002)以在0.368以下為佳。In the crystalline form in which the crystal lattice spacing (d002) exceeds 0.370 nm, since the amorphous ratio is high, the position of doping lithium ions is remarkably lowered, and a sufficient amount of lithium ions cannot be inserted in the carbon hexagonal mesh layer, and the battery capacity is low. . However, (d002) is preferably 0.368 or less.
藉由X光繞射法來測定之結晶晶格面間隔係如下述來測定。The crystal lattice spacing measured by the X-ray diffraction method was measured as follows.
使用經石墨單色器單色化後之CuK α線，藉由反射式反射儀法，來測定廣角X光繞射曲線，使用學振法來求得。The wide-angle X-ray diffraction curve was measured by a reflection reflectance method using a CuK α line monochromated by a graphite monochromator, and was obtained by a vibration method.
形成本發明之鋰二次電池用負極材料之碳微小球，可將碳化氫氣體與除了氫氣之外的載體氣體一起用外熱式的加熱爐熱分解而製造。又，在算數平均一次粒子徑dn為450nm以上的情況，也可在外熱式反應爐之後段部分再度***原料氣體來製造。The carbon microspheres forming the negative electrode material for a lithium secondary battery of the present invention can be produced by thermally decomposing a hydrocarbon gas together with a carrier gas other than hydrogen in an external heating type heating furnace. Further, in the case where the arithmetic mean primary particle diameter dn is 450 nm or more, the raw material gas may be reinserted in the subsequent portion of the external thermal reactor to be produced.
例如，第3圖係將本發明之為製造碳微小球之裝置之全體構成舉例說明之圖。在第3圖中，11為充填原料氣體(例如甲烷氣體)之氣體筒、12為充填了載體氣體(例如氮氣)之氣體筒、13為流量計。14為貯藏液體碳化氫原料之原料槽，例如甲苯等以液狀來貯藏。15為將液體碳化氫原料預熱用的裝置，藉由預熱，來將液體原料氣體汽化。For example, Fig. 3 is a view showing an example of the overall configuration of the apparatus for producing carbon microballoons of the present invention. In Fig. 3, 11 is a gas cylinder filled with a material gas (for example, methane gas), 12 is a gas cylinder filled with a carrier gas (for example, nitrogen gas), and 13 is a flow meter. 14 is a raw material tank for storing a liquid hydrocarbon raw material, for example, toluene or the like is stored in a liquid state. 15 is a device for preheating a liquid hydrocarbon raw material, which is vaporized by preheating.
加熱爐17為將原料之碳化氫氣體熱分解轉化為碳微小球用之加熱爐，例如為內徑145mm、長度1500mm之不透明石英管，在其外側設置外熱加熱用之熱發生源18。作為外熱方式，可應用高頻誘導加熱方式、電熱加熱方式、甚至是流過燃燒氣體之方式。加熱爐17內係預先藉由真空泵浦22來使其脫氧或是置換非活性氣體。The heating furnace 17 is a heating furnace for thermally decomposing and converting a hydrocarbon gas of a raw material into carbon microballoons, for example, an opaque quartz tube having an inner diameter of 145 mm and a length of 1500 mm, and a heat generating source 18 for external heat heating is provided outside the furnace. As an external heat method, a high frequency induction heating method, an electric heating method, or even a method of flowing a combustion gas can be applied. The inside of the heating furnace 17 is deoxidized or replaced with an inert gas by the vacuum pump 22 in advance.
在加熱爐17內，為了控制混合氣體之流速，使反應管徑不同之例如模來石製、碳化矽製等耐熱性管可內插。又，藉由任意變更原料氣體11、載體氣體12之流量也可做到同樣的效果。在製造算數平均一次粒子徑之粒子徑超過450nm之碳微小球之情況，在加熱器出口後將原料氣體加入。爐內溫度係藉由熱電偶或是放射溫度計來檢出而控制到溫度調節器19所定的溫度。In the heating furnace 17, in order to control the flow rate of the mixed gas, heat-resistant tubes such as a mold-made stone or a carbonized tantalum, which have different reaction tube diameters, can be interposed. Further, the same effect can be obtained by arbitrarily changing the flow rates of the material gas 11 and the carrier gas 12. In the case of producing a carbon microball having an average primary particle diameter whose particle diameter exceeds 450 nm, the raw material gas is added after the heater outlet. The temperature in the furnace is detected by a thermocouple or a radiation thermometer and controlled to the temperature set by the temperature regulator 19.
將包含熱分解後之碳微小球之分解氣體以冷卻管20冷卻後，在收集室23將碳微小球分離收集後，經由水槽24在燃燒裝置25使分解氣體完全燃燒後排出系統外。After the decomposition gas containing the thermally decomposed carbon microballoons is cooled by the cooling pipe 20, the carbon microballoons are separated and collected in the collection chamber 23, and then the decomposition gas is completely burned in the combustion device 25 via the water tank 24, and then discharged outside the system.
此碳微小球係將作為原料之碳化氫汽化，與除了氫氣以外之載體氣體一起送入外熱式之加熱爐，藉由將碳化氫氣體熱分解來製造。This carbon microballoon vaporizes the hydrocarbon as a raw material, and sends it to an external heat type furnace together with a carrier gas other than hydrogen, and is produced by thermally decomposing the hydrocarbon gas.
碳化氫氣體，可使用甲烷、乙烷、丙烷、丁烷、乙烯、丙烯、丁二烯等脂肪族碳化氫，苯、甲苯、二甲苯等單環式芳香族碳化氫，萘、蒽等多環式芳香族碳化氫，以及天然氣、民用煤氣、液化天然氣、液化石油氣等，原料碳化氫在常溫為液體或固體之情況，加熱汽化，以氣體狀使用。As the hydrocarbon gas, an aliphatic hydrocarbon such as methane, ethane, propane, butane, ethylene, propylene or butadiene, a monocyclic aromatic hydrocarbon such as benzene, toluene or xylene, or a polycyclic ring such as naphthalene or anthracene can be used. Aromatic hydrocarbons, as well as natural gas, civil gas, liquefied natural gas, liquefied petroleum gas, etc., when the raw material hydrocarbon is liquid or solid at normal temperature, it is heated and vaporized and used as a gas.
載體氣體可使用氫氣以外之在碳化氫氣體熱分解時安定且不反應之非活性氣體，例如，氮、氬、氦、氖、氙、氪等氣體。As the carrier gas, an inert gas other than hydrogen which is stable and does not react when the hydrocarbon gas is thermally decomposed can be used, for example, a gas such as nitrogen, argon, helium, neon, xenon or krypton.
在此情況，若使用氫氣作為載體氣體，則碳化氫氣體的熱分解反應被抑制，因此生成得率也低下，生產效率變差。更且，在碳微小球表面上，由於一直為氫氣氣氛，因此在碳化過程中脫氫反應的進行也被妨礙，結果成為表面凹凸多的碳微小球。碳化氫高分子化之未分解之分解過程中容易殘留焦油狀的碳，由於熱處理變的必要，也更使生產效率差。In this case, when hydrogen gas is used as the carrier gas, the thermal decomposition reaction of the hydrocarbon gas is suppressed, so that the production yield is also lowered, and the production efficiency is deteriorated. Further, since the hydrogen gas atmosphere is always on the surface of the carbon microspheres, the progress of the dehydrogenation reaction during the carbonization is also hindered, and as a result, the carbon microspheres having a large number of surface irregularities are formed. In the undecomposed decomposition process of the hydrocarbonization of the hydrocarbon, tar-like carbon tends to remain, and the heat treatment becomes necessary, and the production efficiency is also inferior.
藉由將原料碳化氫氣體與載體氣體一起供給於加熱爐來進行熱分解而製造，藉由調整、控制熱分解時的溫度、通過爐內之碳化氫氣體的速度、碳化氫氣體與載體氣體的比率(原料濃度)、從反應爐之後段部分之再度***原料氣體之方法的有無等，來控制碳微小球之算數平均一次粒子徑dn、揮發分Vm、斯托克斯模式徑Dst、半寬幅度△Dst以及晶格面間隔(d002)等。It is produced by thermally decomposing a raw material hydrocarbon gas together with a carrier gas in a heating furnace, by adjusting and controlling the temperature at the time of thermal decomposition, the velocity of the hydrocarbon gas passing through the furnace, the hydrocarbon gas and the carrier gas. The ratio (raw material concentration), the presence or absence of the method of reinserting the raw material gas from the subsequent portion of the reactor, etc., to control the arithmetic mean primary particle diameter dn, the volatile matter Vm, the Stokes mode diameter Dst, and the half width of the carbon microspheres. The amplitude ΔDst and the lattice spacing (d002) and the like.
例如，可藉由將熱分解時的溫度控制在1000~1400℃，通過爐內之碳化氫氣體之線速度在0.02~4.0m/sec，原料濃度在10~50vol%來製造。又，並不限定於前述製造方法，只要是滿足專利申請範圍特性之碳微小球即可，更可使用新的製造方法。For example, it can be produced by controlling the temperature at the time of thermal decomposition at 1000 to 1400 ° C, the linear velocity of the hydrocarbon gas in the furnace at 0.02 to 4.0 m/sec, and the raw material concentration at 10 to 50 vol%. Moreover, it is not limited to the above-described manufacturing method, and a carbon microsphere which satisfies the characteristics of the patent application range can be used, and a new manufacturing method can be used.
以下，對比本發明之實施例與比較例來具體說明。又，這些實施例係表示本發明之一實施形態，但本發明並不限定於這些實施例。Hereinafter, the embodiments and comparative examples of the present invention will be specifically described. Further, these embodiments show an embodiment of the present invention, but the present invention is not limited to these embodiments.
在作為第3圖所示之加熱爐之內徑為145mm，長度為1500mm之加熱爐中，使用甲烷氣體、丙烷氣體、丁烷氣體作為原料碳化氫，氮氣作為載體氣體，改變原料氣體濃度、熱分解溫度、氣體流速(線速度)等進行2小時熱分解、製造碳微小球。In the heating furnace having an inner diameter of 145 mm and a length of 1500 mm as shown in Fig. 3, methane gas, propane gas, and butane gas are used as raw materials for hydrogen carbide, and nitrogen is used as a carrier gas to change the concentration and heat of the raw material gas. The decomposition temperature, the gas flow rate (linear velocity), and the like were thermally decomposed for 2 hours to produce carbon microballoons.
作為原料碳化氫，對於甲苯吹入氮氣使其沸騰而汽化之甲苯氣體作為原料來使用。As the raw material hydrocarbon, toluene gas which is boiled by blowing nitrogen gas into toluene to be vaporized is used as a raw material.
將實施例2所得到之碳微小球在非活性氣體500℃熱處理2小時。The carbon microspheres obtained in Example 2 were heat-treated at 500 ° C for 2 hours in an inert gas.
將使甲苯汽化之甲苯氣體作為原料，且載體氣體使用氫氣。Toluene gas in which toluene is vaporized is used as a raw material, and hydrogen is used as a carrier gas.
使用市售的熱碳黑MT。A commercially available hot carbon black MT was used.
將市售之硬質碳黑粉碎進行粒度調整之粉末作為試料。Commercially available hard carbon black was pulverized and subjected to particle size adjustment as a sample.
對於這些碳微小球，藉由電子顯微鏡所測定算數平均粒子徑dn、揮發分Vm、藉由旋轉離心分離裝置(DCF)之斯托克斯模式徑Dst及其半值寬度△Dst，又，藉由X光繞設法測定結晶晶格面間隔(d002)。將此結果示於表1。For these carbon microspheres, the arithmetic mean particle diameter dn, the volatile matter Vm, the Stokes mode diameter Dst of the rotary centrifugal separation device (DCF), and the half value width ΔDst thereof are measured by an electron microscope. The crystal lattice spacing (d002) was determined by X-ray winding. The results are shown in Table 1.
接著，將這些碳小球作為負極材料，以下述方法來組裝鋰二次電池，評價其電池特性。其結果示於表2。Next, these carbon beads were used as a negative electrode material, and a lithium secondary battery was assembled by the following method, and the battery characteristics were evaluated. The results are shown in Table 2.
在碳微小球中，添加固形分10重量%之溶解於N－甲基－2－吡咯烷酮之聚氟化乙烯叉(PVDF)，混練製作碳糊料，將此碳糊料塗布於厚度為18 μm之壓延銅箔上，乾燥後以滾輪壓滾來壓製。從此薄片切出直徑約16mm之圓形作為負極，以金屬鋰作為正極及參照極，製作三極式之測試電池，測定初期效率、可逆容量、比率特性。In a carbon microsphere, a solid content of 10% by weight of a polyvinyl fluoride fork (PVDF) dissolved in N-methyl-2-pyrrolidone was added, and a carbon paste was kneaded, and the carbon paste was applied to a thickness of 18 μm. The rolled copper foil was dried, and then pressed by a roller to be pressed. From this sheet, a circular shape having a diameter of about 16 mm was cut out as a negative electrode, and metal lithium was used as a positive electrode and a reference electrode to prepare a three-electrode test cell, and initial efficiency, reversible capacity, and ratio characteristics were measured.
．初期效率對於鋰參照極以一定電流充電(摻雜鋰離子)至0.002V，以一定電流放電(使鋰離子脫離)至1.2V，測定初次充電電量與放電電量。. The initial efficiency was charged to a lithium reference electrode at a constant current (doped with lithium ions) to 0.002 V, and discharged at a constant current (to dissociate lithium ions) to 1.2 V, and the initial charge amount and discharge amount were measured.
由下式求得初期料率(%)：初期效率(%)＝(初次放電電量/初次充電電量)×100The initial material rate (%) is obtained from the following formula: initial efficiency (%) = (first discharge capacity / initial charge) × 100
．可逆容量接下來，以同樣條件重複進行充放電，將第10次循環之可放電電量藉由下式來算出可逆容量：可逆容量(mAh/g)＝第10次循環之放電電量. Reversible capacity Next, charging and discharging were repeated under the same conditions, and the reversible capacity was calculated from the dischargeable electric quantity of the 10th cycle by the following formula: reversible capacity (mAh/g) = discharge amount of the 10th cycle
．比率特性以可維持作為二次電池之充放電能力(以放電容量100mAh/g為下限)之最小充放電循環時間來評價比率特性(min)。. The ratio characteristic was evaluated as a ratio characteristic (min) by maintaining a minimum charge and discharge cycle time as a charge and discharge capability of the secondary battery (with a discharge capacity of 100 mAh/g as a lower limit).
又，循環特性係以試驗簡易形鈕釦形電池來求得。Further, the cycle characteristics were obtained by testing a simple button-shaped battery.
在每個所得到之碳試料中，添加固形分10重量%之溶解於N－甲基－2－吡咯烷酮之聚氟化乙烯叉(PVDF)，混練製作碳糊料。將此碳糊料塗布於厚度為18 μm之壓延銅箔上，乾燥後以滾輪壓滾來壓製。從此薄片切出直徑約16mm之圓形作為負極電極。To each of the obtained carbon samples, a solid content of 10% by weight of a polyvinyl fluoride fork (PVDF) dissolved in N-methyl-2-pyrrolidone was added, and a carbon paste was kneaded. This carbon paste was applied onto a rolled copper foil having a thickness of 18 μm, dried, and pressed by a roller to be pressed. A circular shape having a diameter of about 16 mm was cut out from the sheet as a negative electrode.
正極係使用鈷酸鋰LiCoO2 ，在鈷酸鋰LiCoO2 粉末中添加5重量%之聚氟化乙烯叉(PVDF)粉末，添加5重量%之導電劑Ketjen Black EC，使用N－甲基吡咯烷酮混合調製懸浮液，將其均一塗布於鋁箔上，藉由乾燥來製作電極薄片。從此薄片來切出16mm之圓形作成正極電極。Lithium cobaltate LiCoO 2 was used for the positive electrode, 5% by weight of polyvinyl fluoride fork (PVDF) powder was added to the lithium cobaltate LiCoO 2 powder, and 5% by weight of a conductive agent Ketjen Black EC was added, and mixed with N-methylpyrrolidone. The suspension was prepared, uniformly coated on an aluminum foil, and dried to prepare an electrode sheet. From this sheet, a 16 mm circular shape was cut out to form a positive electrode.
使用前述負極電極及正極電極，使用在乙烯碳酸酯與二甲基碳酸酯之混合溶劑(體積比1：1混合)將LiPF6 以1莫耳/公升之濃度來溶解之物作為電解液，在分隔板上使用聚丙烯之不織布作成簡易型鈕釦型電池。Using the above-mentioned negative electrode and positive electrode, a solution in which LiPF 6 is dissolved at a concentration of 1 mol/liter in a mixed solvent of ethylene carbonate and dimethyl carbonate (mixed in a volume ratio of 1:1) is used as an electrolytic solution. A non-woven fabric of polypropylene is used as a simple button type battery on the partition plate.
．循環特性之測定在25℃之恆溫下，在端子電壓之放電下限電壓為3.0V，充電上限電壓為4.2V之電位範圍以0.5mA/cm2 之定電流下進行充放電試驗。循環特性係對於第1次之碳負極材料之平均每單位重量之放電容量之第500次放電容量之比率，循環特性(%)＝初期放電容量(mAh/g)/500循環時間點之放電容量(mAh/g)×100來評價。. Measurement of cycle characteristics At a constant temperature of 25 ° C, a charge and discharge test was performed at a constant current of a terminal voltage of 3.0 V and a charge upper limit voltage of 4.2 V at a constant current of 0.5 mA/cm 2 . The cycle characteristic is the ratio of the 500th discharge capacity per unit weight of the discharge capacity of the first carbon negative electrode material, cycle characteristic (%) = initial discharge capacity (mAh/g) / discharge capacity at 500 cycle time points (mAh/g) × 100 was evaluated.
由以上結果來看，在實施例中鋰二次電池之比率特性、可逆電池容量、初期效率及循環特性皆可說是良好的程度。又，在算數平均一次粒子徑dn略小之實施例1、7中，初期效率略為低下，在算數平均一次粒子徑dn較大之實施例2，比率特性較低，更且，在凝集體之粒度分布△Dst/Dst較廣之實施例2、9，循環特性較為低下。From the above results, the ratio characteristics, the reversible battery capacity, the initial efficiency, and the cycle characteristics of the lithium secondary battery in the examples can be said to be good. Further, in the first and seventh embodiments in which the arithmetic mean primary particle diameter dn is slightly small, the initial efficiency is slightly lowered, and in the second embodiment in which the arithmetic mean primary particle diameter dn is large, the ratio characteristics are low, and further, in the aggregate. In the examples 2 and 9, which have a wide particle size distribution ΔDst/Dst, the cycle characteristics are relatively low.
在比較例1、2凝集體之粒度分布△Dst/Dst大，循環特性惡化。在比較例3由於算數平均一次粒子徑dn小而初期效率低下，在比較例4由於算數平均一次粒子徑dn大而比率特性惡化。在氫氣載體合成碳微小球之比較例5，揮發分Vm高，初期效率惡化。在使用市售之熱碳黑MT之比較例6，凝集體之粒度分布△Dst/Dst大，循環特性惡化，又，在使用市售之硬質碳黑之比較例7，粒徑大比率特性惡化。In Comparative Examples 1 and 2, the particle size distribution ΔDst/Dst of the aggregate was large, and the cycle characteristics were deteriorated. In Comparative Example 3, since the arithmetic average primary particle diameter dn was small and the initial efficiency was low, in Comparative Example 4, the ratio averaged primary particle diameter dn was large and the ratio characteristics were deteriorated. In Comparative Example 5 in which carbon microspheres were synthesized in a hydrogen carrier, the volatile matter Vm was high and the initial efficiency was deteriorated. In Comparative Example 6 using a commercially available hot carbon black MT, the particle size distribution ΔDst/Dst of the aggregate was large, and the cycle characteristics were deteriorated. Further, in Comparative Example 7 using commercially available hard carbon black, the particle size ratio characteristic deteriorated. .
藉由使用本發明之負極材料所構成之鋰二次電池，作為可從攜帶機器用之各種電源到混合動力車或電汽車之動力源來使用，具有高輸出之鋰二次電池是極為有用的。A lithium secondary battery comprising the negative electrode material of the present invention can be used as a power source for a hybrid vehicle or an electric vehicle from various power sources for carrying a machine, and a lithium secondary battery having a high output is extremely useful. .
11．．．充填原料氣體之氣體筒11. . . Gas cylinder filled with raw material gas
12．．．充填了載體氣體之氣體筒12. . . Gas cylinder filled with carrier gas
13．．．流量計13. . . Flow meter
14．．．貯藏液體碳化氫原料之原料槽14. . . Raw material tank for storing liquid hydrocarbon raw materials
15．．．將液體碳化氫原料預熱用的裝置15. . . Device for preheating liquid hydrocarbon raw material
17．．．加熱爐17. . . Heating furnace
18．．．熱發生源18. . . Heat generation source
19．．．溫度調節器19. . . temperature regulator
20．．．冷卻管20. . . Cooling tube
23．．．收集室twenty three. . . Collection room
24．．．水槽twenty four. . . sink
25．．．燃燒裝置25. . . Combustion device
第1圖係表示測定斯脫克斯模式徑Dst時之追加了碳微小球分散液後之經過時間與碳微小球之離心沉降所造成之吸光度的變化之分布曲線。Fig. 1 is a graph showing the distribution of the change in the absorbance caused by the centrifugal sedimentation of the carbon microspheres when the carbon microsphere dispersion was added when the Snex mode diameter Dst was measured.
第2圖係表示測定斯脫克斯模式徑Dst時所得到之斯脫克斯相當徑與吸光度之關係之分布曲線。Fig. 2 is a graph showing the distribution of the relationship between the Stokes equivalent diameter and the absorbance obtained when the Snex mode diameter Dst is measured.
第3圖係舉例表示為製造本發明之碳微小球用之裝置之全體構成之說明圖。Fig. 3 is an explanatory view showing an overall configuration of an apparatus for producing a carbon microsphere of the present invention.
11．．．充填原料氣體之氣體筒11. . . Gas cylinder filled with raw material gas
12．．．充填了載體氣體之氣體筒12. . . Gas cylinder filled with carrier gas
13．．．流量計13. . . Flow meter
14．．．貯藏液體碳化氫原料之原料槽14. . . Raw material tank for storing liquid hydrocarbon raw materials
15．．．將液體碳化氫原料預熱用的裝置15. . . Device for preheating liquid hydrocarbon raw material
17．．．加熱爐17. . . Heating furnace
18．．．熱發生源18. . . Heat generation source
19．．．溫度調節器19. . . temperature regulator
20．．．冷卻管20. . . Cooling tube
23．．．收集室twenty three. . . Collection room
24．．．水槽twenty four. . . sink
25．．．燃燒裝置25. . . Combustion device
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