JP2006032166A - Cathode carbon material for rechargeable lithium-ion battery, and its manufacturing method - Google Patents
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Abstract
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本発明は、リチウムイオン二次電池用負極炭素材料、及びその製造方法に関する。より詳しくは、米澱粉部位を原料に用いて、より原料コスト軽減効果に優れたリチウムイオン二次電池用負極炭素材料、及びその製造方法に関する。 The present invention relates to a negative electrode carbon material for a lithium ion secondary battery and a method for producing the same. More specifically, the present invention relates to a negative electrode carbon material for a lithium ion secondary battery that uses a rice starch portion as a raw material and is more excellent in raw material cost reduction effect, and a method for producing the same.
本明細書において米澱粉部位とは、米由来の澱粉部位であって、中白糠又は上白糠と呼ばれる、澱粉粒子を多く含む胚乳の部分を云う。 In the present specification, the rice starch portion refers to a portion of endosperm containing a large amount of starch particles, which is a starch portion derived from rice and is referred to as middle white rice cake or upper white rice cake.
特許文献１には、リチウムイオン二次電池用負極炭素材料の原料として米糠を用いる技術が開示されている。 Patent Document 1 discloses a technique of using rice bran as a raw material for a negative electrode carbon material for a lithium ion secondary battery.
籾は稲の種子であり、この籾から籾殻を除いたものが玄米である。玄米の組織は、果皮、種皮、胚及び胚乳からなり、胚乳は、外層の糊粉層及び内層の澱粉貯蔵組織からなる。また、果皮及び種皮の部分を赤糠とも云う。玄米の各組織の質量割合は、外側から、赤糠が５〜７％、胚が２〜３％、胚乳が９０〜９３％である。 Rice bran is rice seed, and brown rice is obtained by removing rice husk from this rice bran. The brown rice tissue consists of pericarp, seed coat, embryo and endosperm, and the endosperm consists of an outer paste layer and an inner starch storage tissue. Also, the pericarp and seed coat are also called red coral. From the outside, the mass ratio of each tissue of brown rice is 5-7% for red cocoons, 2-3% for embryos, and 90-93% for endosperm.
なお、精米歩合Ｌが１００〜９１％の玄米の表層部分を赤糠層、精米歩合Ｌが９１〜８１％の胚乳の外側部分をサピオ層、精米歩合Ｌが８１〜６６％の胚乳の内側部分を白糠層、と呼ぶ場合もある。 The surface layer portion of brown rice having a rice polishing ratio L of 100-91% is the red rice layer, the outer part of the endosperm having a rice polishing ratio L of 91-81% is the sapio layer, and the inner part of the endosperm having a rice polishing ratio L of 81-66% Is sometimes called a birch layer.
一般に、玄米の精米過程において、精米度合を精米歩合Ｌで表現することができる。精米歩合Ｌとは玄米質量に対する白米質量の割合を云う（式１）。 Generally, in the process of brown rice polishing, the degree of rice polishing can be expressed by the rice polishing ratio L. The polished rice ratio L refers to the ratio of the white rice mass to the brown rice mass (Formula 1).
（式１） 精米歩合Ｌ（％）＝（白米質量÷玄米質量）×１００ (Formula 1) Rice polishing ratio L (%) = (white rice mass ÷ brown rice mass) × 100
また、精白歩合とは玄米質量に対する研削質量の割合を云う（式２）。 The milling ratio is the ratio of the grinding mass to the brown rice mass (Formula 2).
（式２） 精白歩合（％）＝（研削質量÷玄米質量）×１００ (Formula 2) Polishing rate (%) = (grinding mass ÷ brown rice mass) × 100
玄米質量とは白米質量と研削質量の和である（式３）。 The brown rice mass is the sum of the white rice mass and the grinding mass (Formula 3).
（式３） 白米質量＋研削質量＝玄米質量 (Formula 3) White rice mass + grinding mass = brown rice mass
したがって、玄米の精米度合については、常に次の関係が成立する（式４）。 Therefore, the following relationship is always established for the degree of brown rice polishing (Formula 4).
（式４） 精米歩合Ｌ（％）＋精白歩合（％）＝１００（％） (Formula 4) Milling ratio L (%) + Milling ratio (%) = 100 (%)
ご飯として食べる飯米の精米歩合Ｌは一般に９２〜９０％程である。清酒醸造には精米歩合Ｌが７０〜５０％の白米が通常使用されており、精米歩合Ｌを低くすれば製成酒の品質は一般に向上する。精米歩合Ｌが９０〜７０％（精白歩合１０〜３０％）の部分を中白糠、７０〜５０％（精白歩合３０〜５０％）の部分を上白糠と云う。
The rice polishing ratio L of the rice that is eaten as rice is generally about 92 to 90%. For sake brewing, white rice having a rice polishing ratio L of 70 to 50% is usually used. If the rice polishing ratio L is lowered, the quality of the sake is generally improved. The portion where the rice polishing ratio L is 90 to 70% (
特許文献１では、米糠から油を取り去ったことから分かるように、米糠のうち果皮及び種皮の部分、すなわち、通称赤糠と呼ばれる部分を原料として用いて、熱硬化性樹脂と共に焼成して、負極の炭素材料とした。ここでは、油を取り去った状態の米糠のカスと熱硬化樹脂であるフェノール樹脂を混ぜ、その混ぜたものを焼成している。 In Patent Document 1, as can be seen from the removal of the oil from the rice bran, the part of the pericarp and seed coat of the rice bran, that is, the part commonly referred to as red rice bran, is used as a raw material and is baked with a thermosetting resin. Carbon material. Here, the rice bran residue from which the oil has been removed is mixed with a phenol resin, which is a thermosetting resin, and the mixture is baked.
しかしながら、上記特許文献１に開示された実施例の場合には、米糠から油を取り去る工程が必要で、そうでないと焼成時に水分以外の大量の揮発物が浮遊して炉内に付着し、悪臭などがあり実用的でない。焼成作業後の電気炉メンテナンスのコスト負担も問題である。更に、フェノール樹脂を用いているが、米糠に比べて価格が高く、植物残渣のひとつである米糠を利用することによるコスト削減化のメリットが享受できない。 However, in the case of the embodiment disclosed in Patent Document 1, a process for removing oil from rice bran is necessary, otherwise a large amount of volatiles other than moisture floats and adheres to the furnace during firing, causing malodor It is not practical. The cost burden of electric furnace maintenance after firing is also a problem. Furthermore, although phenol resin is used, the price is higher than that of rice bran, and the merit of cost reduction by using rice bran which is one of plant residues cannot be enjoyed.
米糠の用途として、中白糠や上白糠は飼料や菓子原料に二次利用もされているが、更なる有効利用の用途開発が望まれている。 As for the use of rice bran, middle white rice cake and upper white rice cake are also used for feed and confectionery raw materials, but further development of effective use is desired.
そこで、本発明は上記従来技術の問題点に鑑みてなされたものであり、本発明が解決しようとする課題は、米の中白糠又は上白糠を有効利用した、従来品と同等以上の性能のリチウムイオン二次電池用負極炭素材料であって、焼成時の悪臭の問題や電気炉メンテナンスの問題を解決するとともに製造コストを改善し、より安価に製造することのできるリチウムイオン二次電池用負極炭素材料を提供することにある。 Accordingly, the present invention has been made in view of the above-mentioned problems of the prior art, and the problem to be solved by the present invention is that lithium having a performance equal to or better than that of a conventional product using rice white birch or white birch effectively. A negative electrode carbon material for lithium ion secondary batteries, which is a negative electrode carbon material for ion secondary batteries, which solves the problem of bad odor during firing and the problem of electric furnace maintenance and can be manufactured at a lower cost by improving the manufacturing cost. To provide materials.
本発明者等は、鋭意検討の結果、玄米から米澱粉部位を取得し、これを焼成することによって、焼成時の悪臭の問題や電気炉メンテナンスの問題を解決するとともに、従来品に比べて同等以上の性能のリチウムイオン二次電池用負極炭素材料を低コストに製造できることを見出し、本発明を完成した。 As a result of intensive studies, the present inventors have acquired a rice starch portion from brown rice and firing it to solve the problem of bad odor during firing and the problem of electric furnace maintenance, and are equivalent to conventional products. The inventors have found that a negative electrode carbon material for lithium ion secondary batteries having the above performance can be produced at low cost, and completed the present invention.
すなわち、本発明のリチウムイオン二次電池用負極炭素材料は、玄米から果皮及び種皮が取り除かれた米澱粉部位を、焼成してなることを特徴とする。 That is, the negative electrode carbon material for a lithium ion secondary battery of the present invention is characterized in that it is obtained by baking a rice starch portion from which pericarp and seed coat are removed from brown rice.
米由来の澱粉部位である胚乳の澱粉貯蔵組織では、ひとつのアミロプラストに、通常、50〜80個くらいの多くの澱粉粒子が密に詰まっている。米の澱粉粒子は、比較的大きな長径40μｍ程のアミロプラストでは径6〜10μｍ、小さなアミロプラストでは径１μｍぐらいの大きさである。すなわち、米の澱粉粒子の大きさは一般に10μm以下であり、他の植物由来の澱粉と比べてかなり小さい。したがって、焼成後の炭素粒子径（一次粒子径）を小さくしてリチウムイオン二次電池用負極炭素材料としての比表面積を大きくすることができる。 In the starch storage tissue of endosperm, which is a starch part derived from rice, normally, about 50 to 80 starch particles are densely packed in one amyloplast. Rice starch particles are about 6 to 10 μm in diameter for amyloplasts with a relatively large major axis of about 40 μm, and about 1 μm in diameter for small amyloplasts. That is, the size of rice starch particles is generally 10 μm or less, which is considerably smaller than starches derived from other plants. Therefore, the specific surface area as the negative electrode carbon material for a lithium ion secondary battery can be increased by reducing the carbon particle diameter (primary particle diameter) after firing.
前記米澱粉部位は玄米を精米した際の中白糠又は上白糠であることが好ましく、該リチウムイオン二次電池用負極炭素材料の粉末Ｘ線（ＣｕＫα）回折図が、２θ＝４０〜５０°に比較的ブロードなピークと、２θ＝４２〜４４°に、よりシャープなピークとを有することが好ましい。２θ＝４２〜４４°に、このシャープなピークを有する場合には、この負極炭素材料を用いてリチウムイオン二次電池を構成したときに、初回の充放電効率が改善し、より良い性能を示した。このシャープなピークをノイズと容易に区別するためには、前記シャープなピークの強度Ａの前記ブロードなピークの強度Ｂに対する比Ａ／Ｂが１．２以上であることが好ましく、１．４以上であることがより好ましい。また、前記ブロードなピークの半価幅が3.5〜5.5°であり、前記シャープなピークの半価幅が0.30〜0.45°であることが好ましい。 It is preferable that the rice starch part is middle white rice cake or upper white rice cake when brown rice is polished, and the powder X-ray (CuKα) diffraction pattern of the negative electrode carbon material for lithium ion secondary battery is compared with 2θ = 40-50 °. It is preferable to have a broad peak and a sharper peak at 2θ = 42 to 44 °. In the case of having this sharp peak at 2θ = 42 to 44 °, when a lithium ion secondary battery is configured using this negative electrode carbon material, the first charge / discharge efficiency is improved and better performance is exhibited. It was. In order to easily distinguish this sharp peak from noise, the ratio A / B of the sharp peak intensity A to the broad peak intensity B is preferably 1.2 or more, and 1.4 or more. It is more preferable that The half-width of the broad peak is preferably 3.5 to 5.5 °, and the half-width of the sharp peak is preferably 0.30 to 0.45 °.
本発明のリチウムイオン二次電池用負極炭素材料は、他の植物由来の澱粉に比べてより小さな澱粉粒子からなる澱粉部位を原料として用いており、焼成した後も、リチウムイオン二次電池用負極炭素材料を構成する微細粒子をより小さくすることができ、粒子間の距離を短く、微細構造をより緻密にすることができる。その微細構造が（110）面を形成し、42〜44°にシャープなピークを形成したものと考えられる。焼成後の微細粒子を小さくし、粒子間の距離を狭く緻密な構造とすることができれば、ハードカーボンのような網目構造にした場合により薄い炭素材料でリチウムイオン二次電池用の負極を構成することができる。また、同じ体積の負極について比較すれば、炭素材料の微細構造が緻密な分、網目組織が増え、またリチウムイオンが入り込みやすい空隙の容積も増えることから高容量が期待できる。 The negative electrode carbon material for a lithium ion secondary battery of the present invention uses a starch portion made of starch particles smaller than other plant-derived starch as a raw material, and after firing, a negative electrode for a lithium ion secondary battery The fine particles constituting the carbon material can be made smaller, the distance between the particles can be shortened, and the fine structure can be made denser. It is considered that the fine structure formed a (110) plane and formed a sharp peak at 42 to 44 °. If the fine particles after firing can be made small and the distance between the particles can be made into a dense structure, a negative electrode for a lithium ion secondary battery can be formed with a thinner carbon material when a network structure such as hard carbon is formed. be able to. Further, when comparing negative electrodes having the same volume, a high capacity can be expected because the fine structure of the carbon material increases the network structure and the volume of voids into which lithium ions can easily enter.
本発明のリチウムイオン二次電池用負極炭素材料では、澱粉粒子を多く含有する部位を用いるので、赤糠にフェノール樹脂を加えて炭素材料としたものに比べて焼成後の組織が微細で電池特性も改善される。また、石油系ピッチから製造される炭素材料に比べても製造コスト上有利である。 In the negative electrode carbon material for lithium ion secondary battery of the present invention, since a portion containing a large amount of starch particles is used, the structure after firing is finer than that obtained by adding phenol resin to red rice cake, and battery characteristics. Will be improved. In addition, it is advantageous in terms of production cost as compared with a carbon material produced from petroleum pitch.
また、本発明のリチウムイオン二次電池用負極炭素材料の製造方法は、玄米から果皮及び種皮を取り除いて、米澱粉部位を取得する第一工程と、該米澱粉部位を焼成する第二工程と、を備えたことを特徴とする。第一工程で果皮及び種皮を取り除いているので、第二工程で焼成する米澱粉部位に油分はなく、大量の揮発分が浮遊することはない。例えば清酒製造の精米工程において、米糠のうち果皮及び種皮と他の米澱粉部位とを選別するだけで、副産物として中白糠又は上白糠を取得する第一工程とすることができる。これにより原料コストを格段に削減することができる。第二工程で米澱粉部位を焼成して、リチウムイオン保持に優れた緻密な網目構造を有するリチウムイオン二次電池用負極炭素材料とすることができる。第二工程の焼成は、窒素ガス又はアルゴンガス等の不活性ガス中で行うことができる。 Moreover, the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention includes a first step of removing the pericarp and seed coat from brown rice to obtain a rice starch portion, and a second step of baking the rice starch portion. , Provided. Since the pericarp and seed coat are removed in the first step, there is no oil in the rice starch portion baked in the second step, and a large amount of volatile matter does not float. For example, in the rice milling process for sake production, it is possible to use the first step of obtaining medium white lees or upper white lees as a by-product simply by selecting the pericarp and seed coat and other rice starch parts from the rice bran. Thereby, raw material cost can be reduced significantly. In the second step, the rice starch portion can be fired to obtain a negative electrode carbon material for a lithium ion secondary battery having a dense network structure excellent in lithium ion retention. Firing in the second step can be performed in an inert gas such as nitrogen gas or argon gas.
前記第一工程は、玄米から果皮及び種皮を取り除いた後に、更に糊粉層を取り除く工程を含むことが好ましい。中白糠には一部の糊粉層と胚乳が含まれる。胚乳のみの上白糠の方が、焼成の後に得られる負極炭素材料の組織の均一化・微細化の点で好ましい。ただし、中白糠と上白糠とでは入手コストが上白糠の方が高く、中白糠若しくは上白糠のいずれを原料として用いるか、又は両者を混合して用いるかは、コストとのバランスによる。 The first step preferably includes a step of further removing the paste powder layer after removing the pericarp and seed coat from the brown rice. Medium white cocoons contain some paste layers and endosperm. An upper white rice cake containing only endosperm is preferable in terms of homogenization and refinement of the structure of the negative electrode carbon material obtained after firing. However, the cost of obtaining the white birch is higher for the white birch and the white birch. Whether the white birch or the white birch is used as a raw material or a mixture of both depends on the balance with cost.
更に、前記第一工程は、玄米を精米する際の中白糠又は上白糠に相当する米澱粉部位を取得する工程であって、前記第二工程が、前記中白糠又は前記上白糠に相当する米澱粉部位を焼成する工程を含むことが好ましい。このとき、前記米澱粉部位が粉体状であって、第一工程は玄米から果皮及び種皮を取り除いて粉体状の米澱粉部位を取得する工程とすることができ、さらに、この粉体状の米澱粉部位をペレット状に成形して、このペレット状の米澱粉部位を焼成することにより、短時間に均質に焼成することが容易になる。 Further, the first step is a step of obtaining a rice starch portion corresponding to the middle white rice bran or the upper white rice bran when the brown rice is polished, and the second step is a rice starch portion corresponding to the middle white rice bran or the upper white rice bran. It is preferable that the process of baking is included. At this time, the rice starch portion is in the form of powder, and the first step can be a step of removing the pericarp and seed coat from the brown rice to obtain a powdery rice starch portion. By forming the rice starch portion of this into a pellet and firing this pellet-shaped rice starch portion, it becomes easy to fire uniformly in a short time.
本発明のリチウムイオン二次電池用負極炭素材料の製造方法において、第一工程は少なくとも精白歩合7％未満（精米歩合93％を超える）に相当する果皮及び種皮を取り除いて精白歩合7％〜65％の範囲内に相当する米澱粉部位を取得し、第二工程が該米澱粉部位を焼成する工程であることが好ましく、第一工程は少なくとも精白歩合9％未満（精米歩合91％を超える）に相当する果皮及び種皮を取り除いて精白歩合9％〜65％の範囲内に相当する米澱粉部位を取得し、第二工程が該米澱粉部位を焼成する工程であることがより好ましい。 In the method for producing a negative electrode carbon material for a lithium ion secondary battery according to the present invention, the first step is to remove the skin and seed coat corresponding to at least a polishing ratio of less than 7% (exceeding a polishing ratio of 93%) to a polishing ratio of 7% to 65 % Rice starch portion corresponding to within the range, it is preferable that the second step is a step of firing the rice starch portion, the first step is at least less than 9% milling rate (over 91% rice milling rate) More preferably, the pericarp and seed coat corresponding to the above are removed to obtain a rice starch portion corresponding to a whitening ratio of 9% to 65%, and the second step is a step of baking the rice starch portion.
更に、本発明のリチウムイオン二次電池用負極炭素材料の製造方法において、第一工程は少なくとも精白歩合12％未満（精米歩合88％を超える）に相当する果皮、種皮及び糊粉層を取り除いて精白歩合12％〜65％の範囲内に相当する米澱粉部位を取得し、第一工程が該米澱粉部位を焼成する工程であることが特に好ましい。 Furthermore, in the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention, the first step is to remove the skin, seed coat and paste powder layer corresponding to at least a milling ratio of less than 12% (more than a milling ratio of 88%). It is particularly preferable that a rice starch portion corresponding to a whitening ratio of 12% to 65% is obtained, and the first step is a step of firing the rice starch portion.
取得する米澱粉部位の精白歩合の下限は、玄米から果皮及び種皮を取り除くためには少なくとも7％以上である必要があり、より完全に玄米から果皮及び種皮を取り除くために９％以上であることが好ましく、糊粉層を取り除いて、得られる炭化物の組織の均一化・微細化の為には12％以上であることが特に好ましい。取得する米澱粉部位の精白歩合の上限は、精白歩合65％を超えて精米しようとすると米が砕けてしまう為65％以下が好ましく、安価に入手する為に、60％以下がより好ましく、55％以下が特に好ましい。 The lower limit of the refining rate of the rice starch portion to be obtained must be at least 7% in order to remove the peel and seed coat from brown rice, and more than 9% in order to remove the peel and seed coat from brown rice more completely It is particularly preferably 12% or more for removing the paste powder layer and homogenizing and refining the structure of the resulting carbide. The upper limit of the milling rate of the rice starch portion to be obtained is preferably 65% or less because rice breaks when trying to polish the milling rate exceeding 65%, and more preferably 60% or less to obtain it at a low price. % Or less is particularly preferable.
本発明のリチウムイオン二次電池用負極炭素材料の製造方法において、第一工程は清酒製造の精米工程で副産される糠を取得する工程であることが好ましい。精米歩合35％まで精米する場合には、精白歩合65％以下の米澱粉部位を第二工程の焼成原料として用いることができ、精米歩合40％まで精米する場合には、精白歩合60％以下の米澱粉部位を第二工程の焼成原料として用いることができ、精米歩合50％まで精米する場合には、精白歩合50％以下の米澱粉部位を第二工程の焼成原料として用いることができ、精米歩合65％まで精米する場合には、精白歩合35％以下の米澱粉部位を第二工程の焼成原料として用いることができる。 In the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention, the first step is preferably a step of obtaining koji produced as a by-product in the rice milling process of sake production. When milling to a polishing rate of 35%, a rice starch portion with a milling rate of 65% or less can be used as a baking raw material in the second step. When polishing to a polishing rate of 40%, a milling rate of 60% or less The rice starch portion can be used as the baking raw material in the second step. When the rice polishing ratio is polished to 50%, the rice starch portion having a polishing ratio of 50% or less can be used as the baking raw material in the second step. In the case of polishing rice to a proportion of 65%, a rice starch portion having a polishing ratio of 35% or less can be used as a baking raw material in the second step.
本発明のリチウムイオン二次電池用負極炭素材料の製造方法において、第二工程は、前記米澱粉部位を仮焼成して仮焼成物を得る仮焼成工程と、前記仮焼成物を粉砕物に粉砕する粉砕工程と、前記粉砕物を前記仮焼成工程の温度よりも高い温度で本焼成する本焼成工程と、を含むことが好ましい。第二工程をこのようにすることにより、より均一に焼成することができ、粉体特性の良好なリチウムイオン二次電池用負極炭素材料を得ることができる。前記粉砕工程では、例えば、前記仮焼成物を平均粒子径が5〜40μmの粉砕物に粉砕する。 In the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention, the second step is a pre-baking step of pre-baking the rice starch portion to obtain a pre-fired product, and crushing the pre-fired product into a pulverized product It is preferable to include a pulverization step of performing the main calcination of the pulverized product at a temperature higher than the temperature of the preliminary calcination step. By carrying out the second step in this way, it is possible to obtain a negative electrode carbon material for a lithium ion secondary battery that can be fired more uniformly and has good powder characteristics. In the pulverization step, for example, the calcined product is pulverized into a pulverized product having an average particle size of 5 to 40 μm.
本発明のリチウムイオン二次電池用負極炭素材料の製造方法において、第二工程は、例えば、前記米澱粉部位を500〜2700℃で0.5〜50時間焼成する工程とすることができる。第二工程において仮焼成工程は前記米澱粉部位を500〜1000℃で0.5〜10時間焼成する工程であることが好ましく、本焼成工程は前記粉砕物を700〜1600℃で0.5〜50時間焼成する工程であることが好ましい。また、本焼成工程は前記粉砕物を1100〜1400℃で焼成する工程であることがより好ましく、1200〜1300℃で焼成する工程であることが特に好ましい。 In the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention, the second step can be, for example, a step of baking the rice starch portion at 500 to 2700 ° C. for 0.5 to 50 hours. In the second step, the preliminary baking step is preferably a step of baking the rice starch portion at 500 to 1000 ° C. for 0.5 to 10 hours, and the main baking step is baking the pulverized product at 700 to 1600 ° C. for 0.5 to 50 hours. It is preferable that it is a process. The firing step is more preferably a step of firing the pulverized product at 1100 to 1400 ° C, and particularly preferably a step of firing at 1200 to 1300 ° C.
焼成温度1100〜1400℃で0.5〜50時間焼成することにより、本発明のリチウムイオン二次電池用負極炭素材料を、そのリチウムイオン二次電池用負極炭素材料の粉末Ｘ線（ＣｕＫα）回折図が、２θ＝４０〜５０°に比較的ブロードなピークと、２θ＝４２〜４４°に、よりシャープなピークとを有するものとすることができる。 The negative electrode carbon material for a lithium ion secondary battery of the present invention is calcined at a firing temperature of 1100 to 1400 ° C. for 0.5 to 50 hours, and the powder X-ray (CuKα) diffractogram of the negative electrode carbon material for a lithium ion secondary battery of the present invention It can have a relatively broad peak at 2θ = 40 to 50 ° and a sharper peak at 2θ = 42 to 44 °.
本発明のリチウムイオン二次電池用負極炭素材料の製造方法によれば、玄米から果皮と種皮部が取り除かれているので、焼成作業中に揮発物が浮遊することが少なく作業性に優れ、清酒製造等の副産物として得られる米由来の澱粉部位を利用するので原料コストを低減でき、従来技術である赤糠及びフェノール樹脂の混合物を焼成する場合より作業性、コストの点で改善することができる。果皮部分が取り除かれているので、得られるリチウムイオン二次電池用負極炭素材料の性能を従来品同等以上のものとすることができるうえ、清酒製造等の副産物として得られる米由来の澱粉部位を利用するので原料コストを低減でき、玄米の種皮部分が取り除かれているので、焼成作業中に揮発物が浮遊することが少なく、作業性が優れ、リチウムイオン二次電池用負極炭素材料のトータルの製造コストを大幅に低減することができる。 According to the method for producing a negative electrode carbon material for a lithium ion secondary battery of the present invention, since the pericarp and seed coat are removed from the brown rice, volatiles are less likely to float during the baking operation, and workability is excellent. Since the starch part derived from rice obtained as a by-product such as manufacturing is used, the raw material cost can be reduced, and the workability and cost can be improved compared with the case of baking the mixture of red rice bran and phenol resin, which is a conventional technique. . Since the skin part has been removed, the performance of the obtained negative electrode carbon material for lithium ion secondary batteries can be equal to or higher than that of conventional products, and the starch part derived from rice obtained as a by-product of sake production etc. Since it is used, raw material costs can be reduced, and the seed coat part of brown rice has been removed, so that volatiles are less likely to float during the baking operation, and workability is excellent, and the total of negative electrode carbon materials for lithium ion secondary batteries Manufacturing costs can be greatly reduced.
さらに、本発明のリチウムイオン二次電池用負極炭素材料の製造方法では比較的小さな澱粉粒子を有する米澱粉部位を用いているので、他の植物由来の澱粉部位を焼成してリチウムイオン二次電池用負極炭素材料とする場合に比べて、焼成後のリチウムイオン二次電池用負極炭素材料の微細構造をより小さく緻密にすることができ、二次電池において薄く小さな負極の構成が可能となり、その結果、単位体積当たりの充放電容量を大きくすることができる。 Further, in the method for producing a negative electrode carbon material for a lithium ion secondary battery according to the present invention, a rice starch portion having relatively small starch particles is used. Therefore, a starch portion derived from another plant is baked to obtain a lithium ion secondary battery. Compared with the case of the negative electrode carbon material for use, the fine structure of the negative electrode carbon material for the lithium ion secondary battery after firing can be made smaller and denser, and the secondary battery can be configured as a thin and small negative electrode. As a result, the charge / discharge capacity per unit volume can be increased.
また、米糠のうち赤糠の部分は、利用した玄米の産地、気候変動、収穫時期等により成分変動が起きやすく、得られるリチウムイオン二次電池用負極炭素材料の品質管理が難しいのに対して、本発明のリチウムイオン二次電池用負極炭素材料の製造方法では、米糠のうち赤糠の部分が除かれているので、原料由来の成分変動が小さく、品質管理が容易となる。 In addition, the red rice bran portion of the rice bran tends to undergo component fluctuations depending on the production area of the brown rice used, climate change, harvest time, etc., whereas the quality control of the obtained negative electrode carbon material for lithium ion secondary batteries is difficult. In the method for producing a negative electrode carbon material for a lithium ion secondary battery according to the present invention, since the red rice bran portion is removed from the rice bran, the component variation derived from the raw material is small, and quality control becomes easy.
以下に、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
（実施例１〜１３）
（米澱粉部位取得工程）
600kgの玄米を、チヨダ式醸造用精米機（ＨＳ−１５型ＣＮＣ）で、28時間かけて、精米歩合Ｌ＝50％の精白酒米にまで精米した。この時に、赤糠層（Ｌ＝100〜91％）及びサピオ層（Ｌ＝91〜85％）を取り除いて、中白糠（Ｌ＝85〜75％、精白歩合15〜25％）に相当する粉体状の米澱粉部位約60kgを取得した（実施例１、２）。同様にして、赤糠層及びサピオ層（Ｌ＝100〜80％）を取り除いて、中白糠（Ｌ＝80〜70％、精白歩合20〜30％）に相当する粉体状の米澱粉部位を取得した（実施例３）。赤糠層及びサピオ層（Ｌ＝100〜90％）を取り除いて、中白糠（Ｌ＝90〜70％、精白歩合10〜30％）に相当する粉体状の米澱粉部位を取得した（実施例４〜９）。同様にして、上白糠（Ｌ＝65〜50％、精白歩合35〜50％）に相当する粉体状の米澱粉部位を取得した（実施例１０、１１）。中白糠及び上白糠（Ｌ＝85〜50％、精白歩合15〜50％）に相当する粉体状の米澱粉部位を取得した（実施例１２、１３）。これらの米澱粉部位に対してそれぞれ質量比約５％の水を散布して混合攪拌し、造粒機（デスクペレッター、F20/330型）にて3mmφ×3mmのペレット状に成形し、70〜80℃、５分間乾燥した。
(Examples 1 to 13)
(Rice starch part acquisition process)
600 kg of brown rice was polished with a Chiyoda type brewing machine (HS-15 CNC) over 28 hours to a polished rice with a polishing ratio L = 50%. At this time, the red coral layer (L = 100-91%) and the sapio layer (L = 91-85%) are removed, and the powder corresponding to the medium white coral (L = 85-75%, whitening ratio 15-25%) About 60 kg of body-shaped rice starch portion was obtained (Examples 1 and 2). Similarly, the red rice bran layer and the sapio layer (L = 100-80%) are removed, and the powdery rice starch portion corresponding to the medium white rice cake (L = 80-70%, whitening rate 20-30%) is obtained. Obtained (Example 3). The red rice bran layer and the sapio layer (L = 100-90%) were removed, and a powdery rice starch portion corresponding to the medium white rice cake (L = 90-70%, whitening ratio 10-30%) was obtained (implementation) Examples 4-9). In the same manner, powdery rice starch portions corresponding to upper white rice bran (L = 65-50%, whitening ratio 35-50%) were obtained (Examples 10 and 11). Powdered rice starch portions corresponding to medium white rice cake and upper white rice cake (L = 85-50%, whitening rate 15-50%) were obtained (Examples 12 and 13). Each of these rice starch parts was sprayed with water at a mass ratio of about 5%, mixed and stirred, and formed into pellets of 3mmφ × 3mm with a granulator (desk pelleter, F20 / 330 type). Dry at -80 ° C for 5 minutes.
（焼成工程）
得られたペレット状の各米澱粉部位を、ロータリーキルンにて、窒素ガス中、450〜900℃、０．４〜９時間で仮焼成した。次に、この仮焼成物を、平均粒子径が20〜30μｍの粉砕物に粉砕し、この粉砕物をるつぼに入れて、650〜2700℃、0.45〜48時間本焼成して、リチウムイオン二次電池用負極炭素材料を得た。これらの条件を、表１にまとめて示す。
(Baking process)
Each pellet-shaped rice starch site | part obtained was provisionally baked in a rotary kiln in nitrogen gas at 450 to 900 ° C. for 0.4 to 9 hours. Next, the calcined product is pulverized into a pulverized product having an average particle size of 20 to 30 μm, and the pulverized product is put into a crucible and subjected to main calcination at 650 to 2700 ° C. for 0.45 to 48 hours. A negative electrode carbon material for a battery was obtained. These conditions are summarized in Table 1.
このうち、1200℃、5ｈにて本焼成して得られたリチウムイオン二次電池用負極炭素材料（実施例１）について、Ｘ線回折図の結果を図１に示す。Ｘ線源はＣｕＫα（40kV、30mA）、発散スリット幅は1/2deg、散乱スリット幅は1/2deg、受光スリットは0.15mm、Ｋβフィルタを用い、10〜90°の走査範囲で測定した。得られたＸ線回折図の横軸は２θ（°）、縦軸は検出強度（ｃｐｓ）である。２θ＝４０〜５０°に比較的ブロードなピークと、２θ＝４２〜４４°に、よりシャープなピークとを有していることが分かる。より詳細には、２θ＝４０〜５０°（ピークトップが２θ＝44°）の比較的ブロードなピークの半価幅は4.6°であり、ピーク高さは24cpsであった。２θ＝４２〜４４°（ピークトップが２θ＝42.9°）の、よりシャープなピークの半価幅は0.36°であり、ピーク高さは46cpsであった。また、このシャープなピークの強度の、このブロードなピークの強度に対する比は1.92であった。 Among these, about the negative electrode carbon material (Example 1) for lithium ion secondary batteries obtained by carrying out this baking at 1200 degreeC and 5 hours, the result of an X-ray-diffraction figure is shown in FIG. The X-ray source was CuKα (40 kV, 30 mA), the divergence slit width was 1/2 deg, the scattering slit width was 1/2 deg, the light receiving slit was 0.15 mm, and a Kβ filter was used to measure in a scanning range of 10 to 90 °. The horizontal axis of the obtained X-ray diffraction diagram is 2θ (°), and the vertical axis is the detection intensity (cps). It can be seen that there is a relatively broad peak at 2θ = 40 to 50 ° and a sharper peak at 2θ = 42 to 44 °. More specifically, the half width of a relatively broad peak at 2θ = 40 to 50 ° (peak top is 2θ = 44 °) was 4.6 °, and the peak height was 24 cps. The half width of the sharper peak at 2θ = 42 to 44 ° (peak top is 2θ = 42.9 °) was 0.36 °, and the peak height was 46 cps. The ratio of the sharp peak intensity to the broad peak intensity was 1.92.
なお、実施例２、３、１０、１２のリチウムイオン二次電池用負極炭素材料についても、実施例１と同様、２θ＝４０〜５０°に比較的ブロードなピークと、２θ＝４２〜４４°に、よりシャープなピークとを有していた。しかし、実施例４〜９、１１、１３のリチウムイオン二次電池用負極炭素材料については、２θ＝４０〜５０°に比較的ブロードなピークを有していたが、２θ＝４２〜４４°にあるピークの半価幅が0.30°未満、又はこのピークの強度Ａの、ブロードなピークの強度Ｂに対する比Ａ／Ｂが１．２未満であり、ノイズと区別することはできなかった（表２）。実施例８の負極炭素材料のＸ線回折図を図２に示す。 In addition, the negative electrode carbon materials for lithium ion secondary batteries of Examples 2, 3, 10, and 12 also have a relatively broad peak at 2θ = 40 to 50 ° and 2θ = 42 to 44 ° as in Example 1. And a sharper peak. However, the negative electrode carbon materials for lithium ion secondary batteries of Examples 4 to 9, 11, and 13 had a relatively broad peak at 2θ = 40 to 50 °, but at 2θ = 42 to 44 °. The half width of a peak is less than 0.30 °, or the ratio A / B of the intensity A of this peak to the intensity B of a broad peak is less than 1.2, and cannot be distinguished from noise (Table 2). ). The X-ray diffraction pattern of the negative electrode carbon material of Example 8 is shown in FIG.
なお、表１において、2700℃にて本焼成した実施例７のリチウムイオン二次電池用負極炭素材料は黒鉛組織を有する。それ以外のリチウムイオン二次電池用負極炭素材料はアモルファス系ハードカーボン組織を有する。 In Table 1, the negative electrode carbon material for a lithium ion secondary battery of Example 7 that was calcined at 2700 ° C. has a graphite structure. Other negative electrode carbon materials for lithium ion secondary batteries have an amorphous hard carbon structure.
次に、これらのリチウムイオン二次電池用負極炭素材料を用いて、次に示す要領で、マンガン酸リチウムLiMn2O4を正極活物質とする二次電池を作成した。 Next, using these negative electrode carbon materials for lithium ion secondary batteries, secondary batteries using lithium manganate LiMn 2 O 4 as a positive electrode active material were prepared in the following manner.
（負極の作製）
上記のリチウムイオン二次電池用負極炭素材料と、ポリビニリデンフルオライド（結着剤）とを91:9の質量比でN-メチルピロリジノン溶媒中で均一に混合した。厚さ14μmの銅箔（負極集電体）の両面に、厚さが約80μmになるようにこの混合物を塗布した後、乾燥させてシート状負極を作製した。この負極を14.8cm×13.0cmに切り出した。
(Preparation of negative electrode)
The negative electrode carbon material for a lithium ion secondary battery and polyvinylidene fluoride (binder) were uniformly mixed in a N: methylpyrrolidinone solvent at a mass ratio of 91: 9. This mixture was applied on both sides of a 14 μm thick copper foil (negative electrode current collector) to a thickness of about 80 μm, and then dried to prepare a sheet-like negative electrode. This negative electrode was cut out to 14.8 cm × 13.0 cm.
（正極の作製）
市販のマンガン酸リチウムLiMn2O4（正極活物質、平均粒径10μm）と、アセチレンブラック（導電剤）と、ポリビニリデンフルオライド（結着剤）とを89:6:5の質量比でN-メチルピロリドンを用いて混合した。厚さ15μmのアルミニウムシート（正極集電体）の両面に、厚さが約130μmになるようにこの混合物を塗布した後、乾燥させてシート状正極を作製した。この正極を14.3cm×12.9 cmに切り出した。
(Preparation of positive electrode)
Commercially available lithium manganate LiMn 2 O 4 (positive electrode active material,
（非水系電解液の調製）
EC（Ethylene carbonate）とDMC（Dimethyl carbonate）とを50:50の質量比で混合した溶媒に、LiPF6を１mol/Lの濃度で溶解して、非水系電解液を調製した。
(Preparation of non-aqueous electrolyte)
LiPF 6 was dissolved at a concentration of 1 mol / L in a solvent in which EC (Ethylene carbonate) and DMC (Dimethyl carbonate) were mixed at a mass ratio of 50:50 to prepare a non-aqueous electrolyte.
（セパレータ）
市販の多孔性延伸ポリプロピレンシート（宇部興産株式会社製、ＵＰ３０２５）をセパレータとして用いた。このセパレータを14.8cm×12.8cmに切り出した。
(Separator)
A commercially available porous stretched polypropylene sheet (manufactured by Ube Industries, Ltd., UP3025) was used as a separator. This separator was cut into 14.8 cm × 12.8 cm.
（電池の組み立て）
正極及び負極に上記セパレータを挾んだ積層体を試験電池の基本構成とした。これを上記で調製した非水系電解液に10分間浸漬して多孔性延伸ポリプロピレンシートに非水系電解液を含浸させ、リチウムイオン二次電池を組み立てた。正極及び負極の集電体にリード線を取り付け、30℃において定電流で充放電サイクル試験を行なった。充放電試験は、充電終止電圧4.2V、放電終止電圧2.9V、充放電電流密度１mA/cm2として、初回充放電容量を測定した。これらの結果を、初回充放電効率（初回効率＝初回放電容量／初回充電容量×１００（％））の結果と共に表２に示す。本発明のリチウムイオン二次電池用負極炭素材料の初回充放電効率は、従来品のものと同等（△）か、又は、優れており（◎、○）、２θ＝４０〜５０°に比較的ブロードなピークと、２θ＝４２〜４４°に、よりシャープなピークとを有するリチウムイオン二次電池用負極炭素材料の充放電性能は特に優れていた（◎）。
(Battery assembly)
A laminate in which the separator was sandwiched between the positive electrode and the negative electrode was used as the basic configuration of the test battery. This was immersed in the non-aqueous electrolyte prepared above for 10 minutes to impregnate the porous stretched polypropylene sheet with the non-aqueous electrolyte, and a lithium ion secondary battery was assembled. Lead wires were attached to the positive and negative electrode current collectors, and a charge / discharge cycle test was conducted at a constant current at 30 ° C. In the charge / discharge test, the initial charge / discharge capacity was measured at a charge end voltage of 4.2 V, a discharge end voltage of 2.9 V, and a charge / discharge current density of 1 mA / cm 2 . These results are shown in Table 2 together with the results of initial charge / discharge efficiency (initial efficiency = initial discharge capacity / initial charge capacity × 100 (%)). The initial charge / discharge efficiency of the negative electrode carbon material for a lithium ion secondary battery of the present invention is equivalent to (△) or superior to that of a conventional product (◎, ○), and relatively relatively 2θ = 40 to 50 °. The charge / discharge performance of the negative electrode carbon material for a lithium ion secondary battery having a broad peak and a sharper peak at 2θ = 42 to 44 ° was particularly excellent (◎).
（比較例１〜３）
赤糠層の部分（Ｌ＝99.5〜94％、精白歩合0.5〜6％）を取得して、フェノール樹脂を加えて、特開2001-266850号公報を参考にして、赤糠層75質量％にフェノール樹脂25質量％を混合した。実施例１と同様に、ペレット状にした原料を、ロータリーキルンにて、窒素ガス中800〜900℃、６時間で仮焼成した。次に、この仮焼成物を、平均粒子径が20〜30μｍの粉砕物に粉砕し、この粉砕物をるつぼに入れて、900〜1550℃、5〜10時間本焼成して、リチウムイオン二次電池用負極炭素材料を得た（表１）。実施例１と同様にしてリチウムイオン二次電池を組み立てて、充放電性能を評価した。その評価結果を表２に示す。
(Comparative Examples 1-3)
Acquire the red cocoon layer part (L = 99.5-94%, whitening ratio 0.5-6%), add phenol resin, and refer to JP-A-2001-266850 to make 75% by mass of red cocoon layer. 25% by mass of phenol resin was mixed. In the same manner as in Example 1, the pelletized raw material was calcined in a rotary kiln in nitrogen gas at 800 to 900 ° C. for 6 hours. Next, the calcined product is pulverized into a pulverized product having an average particle size of 20 to 30 μm, and the pulverized product is put into a crucible and subjected to main firing at 900 to 1550 ° C. for 5 to 10 hours. Battery negative electrode carbon materials were obtained (Table 1). A lithium ion secondary battery was assembled in the same manner as in Example 1, and the charge / discharge performance was evaluated. The evaluation results are shown in Table 2.
（比較例４〜６）
玄米の精米工程のうち、果皮及び種皮に相当する赤糠（比較例４）、中白糠（比較例５）、及び上白糠（比較例６）の各部分をサンプルとして、電気炉にて焼成を試みた。それぞれ約50ｇのサンプルについて、Ａｒガス雰囲気下、1600℃、２ｈの条件で試験したところ、赤糠（比較例４）では、電気炉内部の天板に、サンプルの10質量％を超える大量の揮発性物が付着し、焼成中の異臭が強かった。中白糠（比較例５）、及び上白糠（比較例６）では、電気炉内部の天板での揮発性物の付着は、いずれも２質量％未満であった。比較例４では、回収率の低さと電気炉のメンテナンスの時間も含めると、中白糠（比較例５）と同量の焼成材を得るには５倍以上の時間と労力を要した。
(Comparative Examples 4-6)
In the milling process of brown rice, the red rice bran (Comparative Example 4), the medium white rice bran (Comparative Example 5), and the upper white rice bran (Comparative Example 6) corresponding to the pericarp and seed coat were used as samples to try firing in an electric furnace. It was. About 50 g of each sample was tested under conditions of 1600 ° C. and 2 h in an Ar gas atmosphere. In Akamine (Comparative Example 4), a large amount of volatilization exceeding 10% by mass of the sample was placed on the top plate inside the electric furnace. Adherent material was attached, and a bad odor during baking was strong. In the middle birch (Comparative Example 5) and the upper white birch (Comparative Example 6), the adhesion of volatile substances on the top plate inside the electric furnace was less than 2 mass%. In Comparative Example 4, including the low recovery rate and the time for maintenance of the electric furnace, it took five times or more time and labor to obtain the same amount of fired material as that of Nakashiragi (Comparative Example 5).
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