JP4401185B2 - Manufacturing method and manufacturing apparatus for electrode material for secondary battery - Google Patents

Manufacturing method and manufacturing apparatus for electrode material for secondary battery Download PDF

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JP4401185B2
JP4401185B2 JP2004031226A JP2004031226A JP4401185B2 JP 4401185 B2 JP4401185 B2 JP 4401185B2 JP 2004031226 A JP2004031226 A JP 2004031226A JP 2004031226 A JP2004031226 A JP 2004031226A JP 4401185 B2 JP4401185 B2 JP 4401185B2
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raw material
granulated raw
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graphite
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JP2005222867A (en
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哲史 久保田
直樹 的場
真吾 朝田
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Kansai Coke and Chemicals Co Ltd
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    • YGENERAL 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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Description

本発明は、球状化黒鉛粒子よりなる二次電池用の電極材料を製造する方法および装置に関するものである。   The present invention relates to a method and an apparatus for producing an electrode material for a secondary battery comprising spheroidized graphite particles.

最近、電子機器等の小型化に伴い、電源となる電池も小型化が求められており、特に電池の高容量化の観点からリチウムイオン二次電池が注目されている。リチウムイオン二次電池の中でも、負極に炭素材料を用いたものは、大容量が得られ、且つ、安全で高電圧が得られるといった点でも有用である。   Recently, with the miniaturization of electronic devices and the like, a battery serving as a power source is also required to be miniaturized. In particular, a lithium ion secondary battery has attracted attention from the viewpoint of increasing the capacity of the battery. Among lithium ion secondary batteries, those using a carbon material for the negative electrode are also useful in that a large capacity can be obtained and a safe and high voltage can be obtained.

ところで、電池用に用いられる炭素材料としては、天然黒鉛や人造黒鉛があり、電極を成形する際には、粉砕した天然黒鉛や人造黒鉛と溶媒およびバインダー(結着材)を混合してスラリーとしたものを対象物に塗布するのが一般的である。しかし、黒鉛の形状が鱗片状であると、スラリーの流動性が悪くなって塗布作業性が著しく損なわれるという問題があった。   By the way, as carbon materials used for batteries, there are natural graphite and artificial graphite. When forming an electrode, a mixture of pulverized natural graphite or artificial graphite, a solvent and a binder (binder) is mixed with a slurry. It is common to apply what has been applied to an object. However, when the shape of the graphite is scaly, the fluidity of the slurry is deteriorated, and there is a problem that the coating workability is remarkably impaired.

そこで、本発明者らは、こうした問題点の改善を期して研究を重ねた結果、鱗片状の天然黒鉛を粉砕してから再凝集させて球状化することによって、鱗片状黒鉛の利点を維持しながらスラリー特性を高めると共に、大きな放電電流値での放電容量の低下も抑えられる技術を開発し、先に提案している(例えば、特許文献1参照)。
特開平11−263612号公報
Thus, as a result of repeated research aimed at improving these problems, the present inventors maintained the advantages of scaly graphite by pulverizing and re-aggregating scaly natural graphite. However, a technique that improves slurry characteristics and suppresses a decrease in discharge capacity at a large discharge current value has been developed and proposed previously (see, for example, Patent Document 1).
JP-A-11-263612

しかしながら、鱗片状黒鉛の粉砕、球状化を効果的に行うための手法に課題が残されている。即ち、上述した提案方式による場合には、二次電池を充放電させる際のサイクル特性の向上に寄与する球状化黒鉛粒子の丸さ度合い(球状化度合い)を示す指標であるピーク強度比を、気体の吹込み時間を長くすることで高めることは、一応は可能であるものの、その上限値が低く改良の余地が残されていた。   However, a problem remains in the technique for effectively crushing and spheroidizing the flake graphite. That is, in the case of the proposed method described above, the peak intensity ratio, which is an index indicating the degree of roundness (degree of spheroidization) of the spheroidized graphite particles that contributes to the improvement of cycle characteristics when charging and discharging the secondary battery, Although it is possible to increase by increasing the gas blowing time, the upper limit value is low and there is room for improvement.

本発明は、この様な問題点に鑑みてなされたものであり、ピーク強度比をより高めることができる球状化黒鉛粒子よりなる二次電池用の電極材料を製造する方法および装置を提供することを目的とする。   The present invention has been made in view of such problems, and provides a method and apparatus for producing an electrode material for a secondary battery made of spheroidized graphite particles capable of further increasing the peak intensity ratio. With the goal.

本発明の請求項1の二次電池用電極材料の製造方法は、少なくとも鱗片状黒鉛を含む造粒原料を、該造粒原料が循環するように構成された循環容器内に供給し、かつ該造粒原料の循環域の途中に向けてその周囲の複数箇所からその途中部分に造粒用気体を吹付け、該鱗片状黒鉛を凝集させて二次電池用電極材料を製造する際に、上記造粒用気体の吹付けを、上記造粒原料の循環域に対し、該造粒原料の移動方向に沿った2以上の位置で行うことを特徴とする。   The method for producing an electrode material for a secondary battery according to claim 1 of the present invention supplies a granulated raw material containing at least scaly graphite into a circulation container configured to circulate the granulated raw material, and When producing an electrode material for a secondary battery by spraying a granulating gas from a plurality of surrounding locations toward the middle of the circulation region of the granulated raw material and aggregating the scaly graphite. The granulating gas is sprayed at two or more positions along the moving direction of the granulated raw material with respect to the circulation region of the granulated raw material.

本発明の請求項2の二次電池用電極材料の製造装置は、少なくとも鱗片状黒鉛を含む造粒原料が循環するように構成された循環容器と、該循環容器の内部に上記造粒原料を供給する供給手段と、該造粒原料の循環域であって造粒原料の移動方向に沿った2以上の位置に対して、各位置の周囲の複数箇所から造粒用気体を吹付ける気体吹付手段とを具備することを特徴とする。   An apparatus for producing an electrode material for a secondary battery according to claim 2 of the present invention comprises a circulation container configured to circulate a granulation raw material containing at least scaly graphite, and the granulation raw material in the circulation container. Supplying means for supplying, and gas blowing for blowing a granulating gas from a plurality of locations around each position to two or more positions along the moving direction of the granulated raw material in the circulation region of the granulated raw material Means.

請求項1および2の発明による場合には、造粒用気体の吹付け位置が増加することにより、造粒原料の衝突範囲又は単位時間当たりにおける造粒原料の衝突箇所(1回循環する間における造粒原料の衝突箇所)が増える。これにより、単位時間当たりにおける造粒原料の衝突回数が増加し、球状化黒鉛粒子の丸さ度合いを表すピーク強度比がより高められる。また、従来よりも短い時間で一定のピーク強度比に到達させることが可能となることにより、製造効率の増大が図れる。   In the case of the inventions of claims 1 and 2, by increasing the spraying position of the granulating gas, the collision range of the granulated raw material or the collision point of the granulated raw material per unit time (during one circulation) The number of granulated raw material collision points) increases. Thereby, the frequency | count of collision of the granulation raw material per unit time increases, and the peak intensity ratio showing the roundness degree of spheroidized graphite particle | grains is raised more. In addition, since it becomes possible to reach a certain peak intensity ratio in a shorter time than in the past, the production efficiency can be increased.

以下に、本発明の実施形態を具体的に説明する。   Embodiments of the present invention will be specifically described below.

図1は本実施形態に係る二次電池用電極材料の製造装置を示す正面図、図2は吹込みノズルの周辺を示す平面図である。   FIG. 1 is a front view showing an apparatus for producing an electrode material for a secondary battery according to this embodiment, and FIG. 2 is a plan view showing the periphery of a blowing nozzle.

この製造装置は、循環容器1と、循環容器1内に、少なくとも鱗片状黒鉛を含む造粒原料を供給するフィーダー2と、循環容器1の側壁に取付けられた複数、本実施形態では6個の吹付け用ノズル3と、循環容器1の上部に設けられた分級機4と、循環容器1の底部に設けられた吹き上げ用ノズル5とを備える。   The manufacturing apparatus includes a circulation container 1, a feeder 2 for supplying a granulated raw material containing at least scaly graphite in the circulation container 1, and a plurality of, six in this embodiment, attached to the side wall of the circulation container 1. The nozzle 3 for spraying, the classifier 4 provided in the upper part of the circulation container 1, and the nozzle 5 for blowing provided in the bottom part of the circulation container 1 are provided.

循環容器1は、天井および底面が塞がれた筒状のもので、軸心を上下方向にして配されており、上下方向を縦長にして構成されている。側面の高さ方向の途中には、上記フィーダー2が設けられている。このフィーダー2は、筒状をしたものを斜めに向けて配設されていて、その下端部が循環容器1の側面を貫通した状態に設けられており、上部には開閉弁が備わっている。このフィーダー2の開閉弁を開けると、所定の一定量に調整された混合粉が循環容器1内に一点鎖線にて示すように供給される。また、このフィーダー2は、本実施形態では取出し口としても用いられている。   The circulation container 1 has a cylindrical shape in which the ceiling and the bottom are closed, and is arranged with the axis centering in the vertical direction, and is configured with the vertical direction being vertically long. The feeder 2 is provided in the middle of the side surface in the height direction. The feeder 2 is disposed in a cylindrical shape so as to be inclined, and its lower end is provided in a state of penetrating the side surface of the circulation container 1, and an open / close valve is provided at the top. When the opening / closing valve of the feeder 2 is opened, a predetermined amount of the mixed powder is supplied into the circulation container 1 as indicated by a one-dot chain line. In addition, the feeder 2 is also used as an outlet in the present embodiment.

循環容器1内に供給された造粒原料は、吹き上げ用ノズル5からの吹き上げ用気体と、吹付け用ノズル3からの造粒用気体とにより、上下方向に対流して循環せしめられる。その循環は、例えば循環容器1の軸心に沿って上昇し、天井近くで外側に広がり、側面に沿って下降して底面近くで軸心に向かうように行われる。以降、造粒原料は同様の循環経路で循環する。   The granulation raw material supplied into the circulation container 1 is circulated by convection in the vertical direction by the blowing gas from the blowing nozzle 5 and the granulating gas from the blowing nozzle 3. The circulation is performed, for example, so as to rise along the axial center of the circulation container 1, spread outward near the ceiling, and descend along the side surface toward the axial center near the bottom surface. Thereafter, the granulated raw material is circulated through a similar circulation path.

上記吹き上げ用ノズル5は、上述の循環用に用いられる他、排出時にも用いられる。排出時においては、ノズル5は、造粒原料を吹き上げてフィーダー2から外部に造粒原料を取出すように用いられる。   The blowing nozzle 5 is used not only for the circulation described above but also for discharging. At the time of discharge, the nozzle 5 is used to blow up the granulated raw material and take out the granulated raw material from the feeder 2 to the outside.

上記分級機4は、循環容器1の上部に設けられていて、造粒原料と気体を分離し、気体を循環容器1の外部に排出するように構成されている。   The classifier 4 is provided in the upper part of the circulation container 1 and is configured to separate the granulated raw material and gas and discharge the gas to the outside of the circulation container 1.

上記吹付け用ノズル3は、上述の循環用に用いられる他、造粒原料を構成する鱗片状黒鉛を凝集させる機能を有するもので、3個1組としてその2組を上下方向に位置をずらせて配設されている。   The spray nozzle 3 has a function of aggregating the scaly graphite constituting the granulated raw material, in addition to being used for the circulation described above, and the two sets are shifted in the vertical direction as one set of three. Arranged.

各ノズル3は、図3に示すように循環容器1の側壁に取付けられている。具体的には、循環容器1の側壁の外側に設けられた筒状の取付け部1aに、外側からノズル3を挿入し、ノズル3の外周に形成された鍔部3aを取付け部1aの端面に当接させることで取付け部1aにセットし、そのセット状態のノズル3の外側から固定具10を取付けている。固定具10は、円リング状の押さえ部10aの外周縁に側方に突出した外挿部10bが形成されたもので、外挿部10bの内周面には、筒状の取付け部1aの外周面に形成された雄ねじに螺合する雌ねじが形成されている。よって、固定具10を所定方向に回転させると、外挿部10bが取付け部1aに深く入っていき、押さえ部10aの内面が鍔部3aを押さえ、ノズル3が循環容器1の側壁に取付けられる。なお、図3中の11は、取付け部1aと鍔部3aとの間に挟まれたパッキンである。   Each nozzle 3 is attached to the side wall of the circulation container 1 as shown in FIG. Specifically, the nozzle 3 is inserted from the outside into a cylindrical mounting portion 1a provided outside the side wall of the circulation container 1, and the flange portion 3a formed on the outer periphery of the nozzle 3 is used as an end surface of the mounting portion 1a. The fixture 10 is attached from the outside of the nozzle 3 in the set state by being brought into contact with the attachment portion 1a. The fixing tool 10 is formed with an outer insertion portion 10b projecting laterally on the outer peripheral edge of a circular ring-shaped pressing portion 10a. On the inner peripheral surface of the outer insertion portion 10b, a cylindrical mounting portion 1a is provided. A female screw that is screwed into a male screw formed on the outer peripheral surface is formed. Therefore, when the fixture 10 is rotated in a predetermined direction, the extrapolated portion 10b goes deep into the mounting portion 1a, the inner surface of the pressing portion 10a presses the flange portion 3a, and the nozzle 3 is mounted on the side wall of the circulation container 1. . In addition, 11 in FIG. 3 is the packing pinched | interposed between the attaching part 1a and the collar part 3a.

各組のノズル3のそれぞれは、循環容器1の軸心に沿って造粒原料が上昇する環状域に向けて配置されており、これらのノズル3からのジェット気体は、環状域の中心に向けて吹付けられ、衝突域を形成するようになっている。本実施形態では、3個1組のノズル3が、上下方向に離隔した状態で2組設けられているので、上記衝突域が上下方向に2つ形成される。上記気体としては、例えば空気、窒素、或いは水蒸気などが用いられる。   Each of the nozzles 3 in each group is arranged toward the annular region where the granulated raw material rises along the axis of the circulation container 1, and the jet gas from these nozzles 3 is directed toward the center of the annular region. It is sprayed to form a collision zone. In the present embodiment, two sets of three nozzles 3 are provided in a state of being separated in the vertical direction, so that two collision areas are formed in the vertical direction. For example, air, nitrogen, or water vapor is used as the gas.

このように構成された本実施形態に係る製造装置により造粒処理される造粒原料としては、上述した鱗片状黒鉛のみからなるもの、或いは、鱗片状黒鉛と微細粒子との混合粉などが用いられる。微細粒子としては、本願出願人による特願2002−269096号で記述したものが用いられる。ここでは、前者の鱗片状黒鉛のみを造粒原料として用いる場合を例に挙げて説明する。   As the granulation raw material to be granulated by the production apparatus according to the present embodiment configured as described above, the above-described one composed only of flaky graphite or a mixed powder of flaky graphite and fine particles is used. It is done. As the fine particles, those described in Japanese Patent Application No. 2002-269096 by the applicant of the present application are used. Here, the case where only the former scaly graphite is used as a granulation raw material will be described as an example.

鱗片状黒鉛としては、鱗片状の天然黒鉛や人造黒鉛を使用することができ、例えば、鱗片状天然黒鉛は、一般に85%から99%を上まわる純度で入手できるのでそのまま用いれば良い。必要に応じて、公知の方法でさらに純度を高めることも好ましい。原料となる黒鉛の粒度は種々のものがあるが、球状化前の鱗片状黒鉛(原料)は、平均粒子径が10〜200μm程度のものを用いるのが好ましい。   As the flaky graphite, flaky natural graphite or artificial graphite can be used. For example, flaky natural graphite can be used as it is because it is generally available in a purity exceeding 85% to 99%. If necessary, it is also preferred to further increase the purity by a known method. There are various particle sizes of graphite as a raw material, but it is preferable to use scaly graphite (raw material) having an average particle diameter of about 10 to 200 μm before spheroidization.

造粒原料は、以下のように造粒される。   The granulated raw material is granulated as follows.

フィーダー2の開閉弁を開けて造粒原料を循環容器1内へ供給する。このとき、吹き上げ用ノズル5と吹付け用ノズル3から気体を予め吹出しておき、気体が前記循環経路に沿って移動するようにしておくことが好ましい。即ち、循環容器1の底部に造粒原料が貯まる量を少なくすることができ、造粒原料の循環をスムーズに行うことが可能となるためである。   The on-off valve of the feeder 2 is opened to supply the granulated raw material into the circulation container 1. At this time, it is preferable that gas is blown in advance from the blowing nozzle 5 and the blowing nozzle 3 so that the gas moves along the circulation path. That is, the amount of the granulated material stored in the bottom of the circulation container 1 can be reduced, and the granulated material can be circulated smoothly.

循環容器1内へ供給された造粒原料は、循環する気体を介して気体と同様に循環経路上を移動していく。その移動の途中において、まず下側の3個1組のノズル3により形成される衝突域を通過するとき、造粒原料が衝突して凝集し球状化する。その後、上側の3個1組のノズル3により形成される衝突域を通過するとき、前同様に鱗片状黒鉛が衝突して凝集される。その後、循環経路上を移動して、再度、2組のノズル3により凝集が繰り返され、徐々に球状化した黒鉛の円形度が高くなり、ピーク強度比が向上していく。このとき、分級機4を介して気体は循環容器1の外部に排出され、加えて、分級限界以下の微粉も分級機4を介して循環容器1の外部に排出される。   The granulated raw material supplied into the circulation container 1 moves on the circulation path like the gas through the circulating gas. In the middle of the movement, first, when passing through a collision zone formed by a set of three nozzles 3 on the lower side, the granulated raw material collides and aggregates and spheroidizes. Then, when passing through the collision area formed by the upper set of three nozzles 3, the scaly graphite collides and aggregates as before. After that, it moves on the circulation path, and agglomeration is repeated again by the two sets of nozzles 3, and the degree of circularity of the gradually spheroidized graphite is increased, and the peak intensity ratio is improved. At this time, the gas is discharged to the outside of the circulation container 1 through the classifier 4, and in addition, fine powder below the classification limit is also discharged to the outside of the circulation container 1 through the classifier 4.

しかる後、例えば30分或いはそれよりも長い時間だけ経過した後、吹き上げ用ノズル5と吹付け用ノズル3からの気体の吹出しを停止する。これにより、球状化黒鉛粒子が循環容器1の底部に貯まる。その後、フィーダー2の開閉弁をそれまでの閉状態から開状態にし、吹き上げ用ノズル5からの気体の吹出しを行ってフィーダー2から造粒原料を取出して回収する。なお、回収された球状化黒鉛粒子は、プレス等により二次電池の電極に形成される。   Thereafter, for example, after a lapse of 30 minutes or longer, gas blowing from the blowing nozzle 5 and the blowing nozzle 3 is stopped. Thereby, the spheroidized graphite particles are stored at the bottom of the circulation container 1. Thereafter, the open / close valve of the feeder 2 is changed from the closed state to the open state, the gas is blown out from the blowing nozzle 5, and the granulated raw material is taken out from the feeder 2 and collected. The recovered spheroidized graphite particles are formed on the electrode of the secondary battery by pressing or the like.

なお、ノズル3から気体を吹付ける際のノズル吐出圧、吹付け気体量、循環容器の内圧などは、円滑な衝突と流動が達成できるほぼ一定値に設定され、処理時間を適宜に設定することにより鱗片状黒鉛を球状化する。例えば、ノズル吐出圧は0.01〜0.50MPa程度、吹付けガス量は0.2〜10.0Nm3/min程度、循環容器の内圧は−10〜30kPa程度、処理時間は30分以上とすればよい。また、循環容器1内の温度は0〜60℃程度とすれば良い。 Note that the nozzle discharge pressure, the amount of blowing gas, the internal pressure of the circulation container, etc. when the gas is blown from the nozzle 3 are set to substantially constant values that can achieve smooth collision and flow, and the processing time is set appropriately. To spheroidize the flake graphite. For example, the nozzle discharge pressure may be about 0.01 to 0.50 MPa, the amount of blowing gas may be about 0.2 to 10.0 Nm 3 / min, the internal pressure of the circulation container may be about −10 to 30 kPa, and the processing time may be 30 minutes or more. Moreover, what is necessary is just to let the temperature in the circulation container 1 be about 0-60 degreeC.

図4は、処理時間を10分、20分、30分、40分、50分で変化させた状態におけるピーク強度比の変化を調査した結果(黒丸印)を示すグラフである。なお、この図には、従来の方法により20分、30分、35分、40分、50分、60分で処理した結果(白丸印)も併せて示している。また、表1にも同様の結果を纏めている。   FIG. 4 is a graph showing the results (black circles) of investigating changes in the peak intensity ratio when the processing time is changed at 10, 20, 30, 40, and 50 minutes. In addition, this figure also shows the results (white circles) obtained by processing in 20 minutes, 30 minutes, 35 minutes, 40 minutes, 50 minutes, and 60 minutes by the conventional method. Table 1 also summarizes similar results.

Figure 0004401185
Figure 0004401185

この図4及び表1より理解されるように、従来方法による場合には、処理時間を長くしてもピーク強度比を0.011以上にすることは困難であったが、本実施形態による場合には、処理時間を30分以上とすることによりピーク強度比を0.011以上にすることが可能となった。また、従来よりも短い時間で一定のピーク強度比に到達させることが可能となることにより、製造効率の増大を図ることができる。   As can be seen from FIG. 4 and Table 1, in the case of the conventional method, it was difficult to make the peak intensity ratio 0.011 or more even if the processing time was lengthened. The peak intensity ratio can be made 0.011 or more by setting the treatment time to 30 minutes or more. In addition, since it becomes possible to reach a certain peak intensity ratio in a shorter time than in the past, the production efficiency can be increased.

その理由は、以下の通りである。即ち、ノズル3と5から吹付ける造粒用気体の量を変えることにより、循環容器内の気体及び気体により運ばれる造粒原料の循環時間は左右される。しかし、本実施形態では、ノズル3と5から吹付ける気体の量は、処理時間に関わらずほぼ一定にしているため、造粒原料の循環時間はほぼ一定である。このように造粒原料の循環時間がほぼ一定であっても、本実施形態のように造粒用気体の吹付け位置を増加させることにより、単位時間当たりの造粒原料の衝突箇所が増え、例えば造粒原料が1回循環する間における造粒原料の衝突箇所が増えるため、処理時間を単に増大化する場合には得ることができなかった、球状化黒鉛粒子の丸さ度合いを表すピーク強度比の向上化が可能となったと考えられる。   The reason is as follows. That is, by changing the amount of the granulating gas blown from the nozzles 3 and 5, the circulation time of the granulated raw material carried by the gas and the gas in the circulation container is affected. However, in the present embodiment, the amount of gas blown from the nozzles 3 and 5 is substantially constant regardless of the processing time, and therefore the circulation time of the granulated raw material is substantially constant. Thus, even if the circulation time of the granulated raw material is substantially constant, by increasing the spraying position of the granulating gas as in this embodiment, the number of collisions of the granulated raw material per unit time increases, For example, since the number of collisions of the granulated raw material during one circulation of the granulated raw material increases, the peak intensity representing the degree of roundness of the spheroidized graphite particles that could not be obtained when the processing time was simply increased The ratio can be improved.

なお、ピーク強度比は、配向のランダム性の指標となるX線回折法による002面(黒鉛層と水平な面)と110面(黒鉛層に垂直な面)のピーク強度比[Ih110/Ih002]であり、002面ピーク(26.5゜)、110面ピーク(77.5゜)のピーク面積と、次の式とにより算出される。 The peak intensity ratio is the peak intensity ratio between the 002 plane (plane parallel to the graphite layer) and the 110 plane (plane perpendicular to the graphite layer) [Ih 110 / Ih], which is an index of randomness of orientation. 002 ], which is calculated from the peak area of the 002 plane peak (26.5 °) and the 110 plane peak (77.5 °) and the following equation.

ピーク強度比[Ih110/Ih002
=[net Int(110)面]/[net Int(002)面]
また、ピーク強度比の測定条件は下記の通りである。
・装置:理学株式会社製の「RINT2000」
・セル:内径2.4cm、高さ0.315cm
・セルへの試料の充填:粉体を2.3g計量し、半径1.2cmの金型に入れ、負荷1000kgで厚みが0.315cmになるまでプレスする
・試料密度:2.3g/[(1.2)2cm2×π×0.315cm]=1.6g/cm3
・測定角度:3〜90°
・走査速度:9°/min
・回転数:60rpm
・データ処理:積分強度計算、平滑化点数9点、自動バックグラウンド除去。
Peak intensity ratio [Ih 110 / Ih 002 ]
= [Net Int (110) plane] / [net Int (002) plane]
The measurement conditions for the peak intensity ratio are as follows.
・ Device: “RINT2000” manufactured by Rigaku Corporation
・ Cell: Inner diameter 2.4cm, Height 0.315cm
Filling of the sample to the cell: the powder was 2.3g weighed, placed in a mold having a radius of 1.2 cm, - sample density thickness at load 1000kg is pressed until 0.315cm: 2.3g / [(1.2) 2 cm 2 × π × 0.315 cm] = 1.6 g / cm 3
・ Measurement angle: 3 ~ 90 °
・ Scanning speed: 9 ° / min
・ Rotation speed: 60rpm
-Data processing: integral intensity calculation, 9 smoothing points, automatic background removal.

なお、上述した実施形態では環状容器の側面に吹付け用ノズルを1組3個で2組設けるようにしているが、本発明はこれに限らない。例えば、1組の吹付け用ノズルを2個又は4個以上としてもよく、要はノズルから吐出される気体が衝突して衝突域が形成され得れば、ノズルの本数と角度は限定されない。また、2組を上下方向に隔てた状態に配置しているが、3組以上を上下方向に隔てた状態(高さ位置を各組で異ならせた状態)に配置してもよい。   In the above-described embodiment, two sets of three nozzles for spraying are provided on the side surface of the annular container, but the present invention is not limited to this. For example, the number of nozzles for spraying may be two or four or more. In short, the number and angle of the nozzles are not limited as long as the gas discharged from the nozzles collides to form a collision zone. Moreover, although 2 sets are arrange | positioned in the state separated in the up-down direction, you may arrange | position in the state (state in which the height position was varied in each set) which separated 3 sets or more in the up-down direction.

また、上述した実施形態では、吹付け用ノズルに加えて環状容器の底部に設けた吹き上げ用ノズルからも気体を吹出すことで、造粒原料を環状に移動させる環状気流を形成するようにしているが、本発明はこれに限らない。例えば、吹付け用ノズルからの気体のみにより環状気流を形成するようにしてもよい。この場合には、吹き上げ用ノズルは、処理後の造粒原料の取出しにのみ用いることとなる。   Moreover, in embodiment mentioned above, it was made to form the cyclic | annular airflow which moves a granulation raw material circularly by blowing gas also from the nozzle for blowing provided in the bottom part of the cyclic | annular container in addition to the nozzle for blowing. However, the present invention is not limited to this. For example, you may make it form annular airflow only with the gas from the nozzle for spraying. In this case, the blowing nozzle is used only for taking out the granulated raw material after processing.

また、上述した実施形態では、天井と底が塞がれた筒状のものを環状容器として使用しているが、本発明はこれに限らない。例えば、長い筒をリング状に湾曲させるとともに両端同士を接合したリング状の環状容器を用いてもよい。この場合には、造粒原料が環状容器の形に添って流動していくため、2組以上の吹付け用ノズルは任意の箇所に配置してもよい。   Further, in the above-described embodiment, a cylindrical container whose ceiling and bottom are closed is used as the annular container, but the present invention is not limited to this. For example, you may use the ring-shaped annular container which curved the long cylinder in the ring shape and joined both ends. In this case, since the granulated raw material flows along the shape of the annular container, two or more sets of spray nozzles may be arranged at arbitrary locations.

本発明の一実施形態に係る二次電池用電極材料の製造装置を示す正面断面図である。It is front sectional drawing which shows the manufacturing apparatus of the electrode material for secondary batteries which concerns on one Embodiment of this invention. 図1の製造装置に備わった吹付け用ノズルの配置を示す平面図である。It is a top view which shows arrangement | positioning of the nozzle for spraying with which the manufacturing apparatus of FIG. 1 was equipped. 図2の吹付け用ノズルの取付け状態を示す断面図である。It is sectional drawing which shows the attachment state of the nozzle for spraying of FIG. 本発明方法により処理した場合のピーク強度比の変化を調査した結果(黒丸印)と、従来の方法により処理した結果(白丸印)とを示すグラフである。It is a graph which shows the result (black circle mark) which investigated the change of the peak intensity ratio at the time of processing by the method of this invention (black circle mark), and the result (white circle mark) processed by the conventional method.

符号の説明Explanation of symbols

1 環状容器
2 フィーダー
3 吹付け用ノズル
4 分級機
5 吹き上げ用ノズル
1 annular container 2 feeder 3 nozzle for spraying 4 classifier 5 nozzle for blowing up

Claims (2)

少なくとも鱗片状黒鉛を含む造粒原料を、該造粒原料が循環するように構成された循環容器内に供給し、かつ該造粒原料の循環域の途中に向けてその周囲の複数箇所からその途中部分に造粒用気体を吹付け、該鱗片状黒鉛を凝集させて二次電池用電極材料を製造する際に、上記造粒用気体の吹付けを、上記造粒原料の循環域に対し、該造粒原料の移動方向に沿った2以上の位置で行うことを特徴とする二次電池用電極材料の製造方法。   A granulated raw material containing at least scaly graphite is supplied into a circulation container configured so that the granulated raw material circulates, and the granulated raw material is fed from a plurality of surrounding locations toward the middle of the circulation region of the granulated raw material. When producing a secondary battery electrode material by spraying a gas for granulation on the middle part and agglomerating the flake graphite, the gas for granulation is sprayed on the circulation region of the granulation raw material. The method for producing an electrode material for a secondary battery, which is performed at two or more positions along the moving direction of the granulated raw material. 少なくとも鱗片状黒鉛を含む造粒原料が循環するように構成された循環容器と、
該循環容器の内部に上記造粒原料を供給する供給手段と、
該造粒原料の循環域であって造粒原料の移動方向に沿った2以上の位置に対して、各位置の周囲の複数箇所から造粒用気体を吹付ける気体吹付手段とを具備することを特徴とする二次電池用電極材料の製造装置。
A circulation container configured to circulate a granulated raw material containing at least scaly graphite;
Supply means for supplying the granulated raw material into the circulation container;
Gas spraying means for spraying a granulating gas from a plurality of locations around each position with respect to two or more positions along the moving direction of the granulated raw material in the circulation region of the granulated raw material An apparatus for producing an electrode material for a secondary battery.
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