JP5467264B2 - Method for producing electrode material for non-aqueous electrolyte secondary battery, electrode material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the electrode material - Google Patents
Method for producing electrode material for non-aqueous electrolyte secondary battery, electrode material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the electrode material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、非水電解液二次電池の電極材料の製造方法、非水電解液二次電池の電極材料およびその電極材料を用いた非水電解液二次電池に関するものである。 The present invention relates to a method for producing an electrode material for a non-aqueous electrolyte secondary battery, an electrode material for the non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery using the electrode material.
電子機器の小型化、軽量化が進み、その電源としてエネルギー密度の高い二次電池が望まれている。二次電池とは、電解質を介した化学反応により正極活物質と負極活物質が持つ化学エネルギーを外部に電気エネルギーとして取り出すものである。このような二次電池において、非水電解液を使用して、リチウムイオンを正極と負極との間で移動させることにより充放電を行う非水電解液二次電池（リチウムイオン二次電池）が知られている。 As electronic devices become smaller and lighter, secondary batteries with high energy density are desired as power sources. A secondary battery is one that extracts chemical energy of a positive electrode active material and a negative electrode active material as electric energy to the outside by a chemical reaction via an electrolyte. In such a secondary battery, there is a non-aqueous electrolyte secondary battery (lithium ion secondary battery) that uses a non-aqueous electrolyte and charges and discharges by moving lithium ions between the positive electrode and the negative electrode. Are known.
リチウムイオン二次電池には、正極の活物質として主にリチウムコバルト複合酸化物等のリチウム含有金属複合酸化物が用いられ、負極の活物質としてはリチウムイオンの層間への挿入（リチウム層間化合物の形成）及び層間からのリチウムイオンの放出が可能な、多層構造を有する炭素材料が主に用いられている。 In lithium ion secondary batteries, lithium-containing metal composite oxides such as lithium cobalt composite oxide are mainly used as the positive electrode active material, and lithium ion insertion (interlayer of lithium intercalation compounds) is used as the negative electrode active material. A carbon material having a multilayer structure that can release lithium ions from the formation layer and between layers is mainly used.
このような炭素材料の中で、植物性高分子を焼成することによって得られる炭素材料が検討されている。植物性高分子は合成高分子に比べて重合度のばらつきが少ないため焼成物のばらつきが小さい。 Among such carbon materials, carbon materials obtained by firing vegetable polymers have been studied. Since the plant polymer has less variation in the degree of polymerization than the synthetic polymer, variation in the fired product is small.
例えば特許文献１には、産業廃棄物として入手できる植物性高分子を焼成し、炭素質化して得られた炭素質化合物を含有する負極材料が記載されている。特許文献１には、焼成時に、植物性高分子を１１００℃または１２００℃で焼成し、炭素質化することが記載されている。 For example, Patent Document 1 describes a negative electrode material containing a carbonaceous compound obtained by firing and carbonizing a plant polymer available as industrial waste. Patent Document 1 describes that, during firing, a plant polymer is fired at 1100 ° C. or 1200 ° C. to be carbonized.
特許文献１に記載のように、産業廃棄物として入手できる植物性高分子（以下植物性廃棄物と記載する）を負極用炭素材料として使用するのには、その放電容量を高容量とするために、ハードカーボンが検討されてきた。しかし特許文献１で得られた炭素質化合物は負極材料として用いられており、負極材料よりも高電位が必要とされる正極材料に用いることは出来ない。 As described in Patent Document 1, a plant polymer (hereinafter referred to as plant waste) available as industrial waste is used as a carbon material for a negative electrode in order to increase the discharge capacity. In addition, hard carbon has been studied. However, the carbonaceous compound obtained in Patent Document 1 is used as a negative electrode material and cannot be used for a positive electrode material that requires a higher potential than the negative electrode material.
また他にも植物性廃棄物を使用して、正極材料としても使用できる程、高電位、高容量でサイクル特性に優れた電極用炭素材料は見あたらない。 In addition, there are no carbon materials for electrodes that have high potential, high capacity, and excellent cycle characteristics to the extent that they can be used as positive electrode materials using plant waste.
本発明は、このような事情に鑑みて為されたものであり、植物性廃棄物を炭素源とし、正極材料でも使用できるほど高電位、高容量であり、優れたサイクル特性を有する電極材料の製造方法およびその電極材料を提供することを目的とする。 The present invention has been made in view of such circumstances, and is an electrode material that uses plant waste as a carbon source, has a high potential and a high capacity so that it can be used as a positive electrode material, and has excellent cycle characteristics. It aims at providing a manufacturing method and its electrode material.
本発明者等が鋭意検討した結果、植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させることによって高電位、高容量であり、優れたサイクル特性を有する電極材料を提供することが出来ることを見いだした。 As a result of intensive studies by the present inventors, an electrode material having a high potential, a high capacity, and excellent cycle characteristics by heating plant waste and sulfur alone in a sealed container at 250 ° C. to 600 ° C. I found that I can provide
すなわち本発明の非水電解液二次電池の電極材料の製造方法は、植物性廃棄物と硫黄単体とを混合して混合物とする混合工程と、混合物を密閉容器に入れ２５０℃〜６００℃で加熱する加熱工程と、を有することを特徴とする。 That is, the manufacturing method of the electrode material of the non-aqueous electrolyte secondary battery of the present invention includes a mixing step of mixing vegetable waste and sulfur alone to form a mixture, and putting the mixture in a sealed container at 250 ° C to 600 ° C. A heating step of heating.
硫黄単体は植物性廃棄物と混合されることによって植物性廃棄物間に分散されている。 The sulfur alone is dispersed among the plant wastes by being mixed with the plant wastes.
植物性廃棄物と硫黄単体とを密閉容器に入れて２５０℃〜６００℃で、加熱することによって植物性廃棄物の低温焼成体と硫黄とを含む複合体が生成する。 Plant waste and sulfur alone are put in a sealed container and heated at 250 ° C. to 600 ° C. to produce a composite containing a low-temperature fired body waste of sulfur and sulfur.
植物性廃棄物は加熱により炭素化され低温焼成体となる。低温焼成体は、完全に炭化していない酸素、窒素などのヘテロ原子が一部残った未炭素化物を含む。 Plant waste is carbonized by heating to form a low-temperature fired body. The low-temperature fired body includes an uncarbonized product in which some hetero atoms such as oxygen and nitrogen that are not completely carbonized remain.
硫黄は、融点が１１３℃あるいは１１９℃であり、３００℃付近で流動性のある液体となり、４４４．６℃で沸騰する。硫黄は高温において水素、炭素、塩素などと反応してＨ２Ｓ、ＣＳ２，Ｓ２Ｃｌ２などを生成する。また硫黄はＡｕを除くほとんど全ての金属と直接化合して硫化物を作る。 Sulfur has a melting point of 113 ° C. or 119 ° C., becomes a fluid liquid around 300 ° C., and boils at 444.6 ° C. Sulfur reacts with hydrogen, carbon, chlorine and the like at high temperatures to produce H 2 S, CS 2 , S 2 Cl 2 and the like. Sulfur combines with almost all metals except Au to form sulfides.
そのため、加熱時に植物性廃棄物と硫黄単体は様々な反応をし、植物性廃棄物の低温焼成体と硫黄とはなんらかの複合体となっていると考えられる。 Therefore, it is considered that the plant waste and sulfur alone undergo various reactions during heating, and the low-temperature calcined product of sulfur and sulfur are in some form of complex.
また硫黄単体は１５９℃以上に加熱されるとラジカルを発生する。このラジカルによって植物性廃棄物の炭素化が促進される。 Further, when sulfur alone is heated to 159 ° C. or higher, radicals are generated. This radical promotes the carbonization of plant waste.
植物性廃棄物と硫黄単体とを加熱することにより、ガス類が発生する。発生したガス類は容器が密閉されているので、容器から漏れない。そのためそのガス類により、密閉容器内に圧力がかかることになる。その圧力のために、上記した様々な反応および炭素化が促進される。 Gases are generated by heating plant waste and simple sulfur. The generated gas does not leak from the container because the container is sealed. Therefore, pressure is applied in the sealed container by the gases. The pressure promotes the various reactions and carbonization described above.
このように植物性廃棄物に硫黄単体を混合することによって、混合物の加熱時に植物性廃棄物の炭素化が促進される。 Thus, by mixing sulfur simple substance with vegetable waste, carbonization of vegetable waste is accelerated | stimulated at the time of heating of a mixture.
硫黄単体は植物性廃棄物の炭素化を促進させるだけでなく、硫黄単体そのものが１６００ｍＡｈ／ｇという大きな理論容量を有する。しかし硫黄単体は電子伝導性が乏しい。また硫黄単体は、充放電時に重合、解離を繰り返すと低分子硫黄を生成する。その低分子硫黄は有機溶媒（すなわち電解液）に溶解する。そのため活物質として硫黄単体を用いることは困難である。 Sulfur alone not only promotes carbonization of plant waste, but also sulfur itself has a large theoretical capacity of 1600 mAh / g. However, sulfur alone has poor electronic conductivity. Moreover, a sulfur simple substance will generate | occur | produce low molecular sulfur, when superposition | polymerization and dissociation are repeated at the time of charging / discharging. The low molecular sulfur is dissolved in an organic solvent (that is, an electrolytic solution). Therefore, it is difficult to use simple sulfur as an active material.
本発明の製造方法では植物性廃棄物の低温焼成体と硫黄とを含む複合体が生成する。植物性廃棄物の低温焼成体は炭素を含むため、その複合体は電子伝導性が良好である。またその複合体では硫黄は何らかの形で低温焼成体と複合化しているため、硫黄単体が電解液へ溶出することを抑制できる。 In the production method of the present invention, a complex containing a low-temperature fired body waste and sulfur is produced. Since the low-temperature fired body waste of vegetable waste contains carbon, the composite has good electron conductivity. Moreover, in the composite, since sulfur is complexed with the low-temperature fired body in some form, it is possible to suppress the dissolution of sulfur alone into the electrolyte.
従って硫黄の有する容量を炭素材料の有する容量に付加することが出来る。そのため本発明の電極材料の製造方法は、高容量の電極材料を製造することが出来る。 Therefore, the capacity of sulfur can be added to the capacity of the carbon material. Therefore, the electrode material manufacturing method of the present invention can manufacture a high-capacity electrode material.
上記した製造方法において、加熱温度を１５９℃以上とすることによって、植物性廃棄物の低温焼成体と硫黄とを含む複合体が生成する。 In the manufacturing method described above, by setting the heating temperature to 159 ° C. or higher, a composite containing a low-temperature fired body waste and sulfur is generated.
また加熱温度を２５０℃以上とすることにより植物性廃棄物に含まれる分子量３００以下の低分子化合物からなる不純物が充分に分離される。植物性廃棄物がコーヒー豆の場合、この不純物は例えばカフェインである。 Further, by setting the heating temperature to 250 ° C. or higher, impurities composed of low molecular weight compounds having a molecular weight of 300 or less contained in plant waste are sufficiently separated. If the vegetable waste is coffee beans, this impurity is caffeine, for example.
従って上記した製造方法の加熱温度は２５０℃以上が望ましい。 Therefore, the heating temperature of the above-described manufacturing method is desirably 250 ° C. or higher.
加熱温度を６００℃より高くすると、低温焼成体と硫黄とを含む複合体が分解されてしまう。そのため加熱温度は６００℃以下とすることが必要である。 When heating temperature is made higher than 600 degreeC, the composite_body | complex containing a low-temperature fired body and sulfur will be decomposed | disassembled. Therefore, the heating temperature needs to be 600 ° C. or lower.
原料として植物性廃棄物と硫黄単体の混合割合は、質量比で、５：１〜１：５が好ましい。 The mixing ratio of the plant waste and the simple sulfur as a raw material is preferably 5: 1 to 1: 5 in mass ratio.
また混合工程の前にさらに植物性廃棄物を乾燥させる乾燥工程を有することが好ましい。植物性廃棄物をあらかじめ乾燥させておくことによって水分除去が出来、加熱工程の時間が短縮出来る。 Moreover, it is preferable to have the drying process which dries a vegetable waste further before a mixing process. Moisture can be removed by drying the plant waste in advance, and the heating process time can be shortened.
さらに加熱工程の後に加熱後の混合物を１５０℃〜４００℃で真空加熱して加熱工程で発生した不純物を除く不純物除去工程を有することが好ましい。上記不純物除去工程によって、加熱工程において発生した余分な硫黄反応物等の不純物を簡便に取り除くことが出来る。 Furthermore, it is preferable to have the impurity removal process of removing the impurity which generate | occur | produced in the heating process by vacuum-heating the mixture after a heating at 150 to 400 degreeC after a heating process. By the impurity removal step, impurities such as excess sulfur reactant generated in the heating step can be easily removed.
植物性廃棄物は、コーヒー豆、茶葉、サトウキビ類、トウモロコシ類、果実類、穀物の藁類、糠および籾殻類から選択される少なくとも一種であることが好ましい。 The plant waste is preferably at least one selected from coffee beans, tea leaves, sugar cane, corn, fruits, cereals, straw and rice husks.
本発明の非水電解液二次電池の電極材料は、植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させて得られた生成物を有することを特徴とする。 The electrode material of the non-aqueous electrolyte secondary battery of the present invention is characterized by having a product obtained by heating plant waste and simple sulfur at 250 ° C. to 600 ° C. in a sealed container. .
上記生成物全体を１００質量％としたときに、生成物の硫黄の含有量は３０−８０質量％であることが好ましい。 When the total product is 100% by mass, the sulfur content of the product is preferably 30-80% by mass.
生成物の硫黄の含有量は３０−８０質量％であることによって、高容量の電極材料とすることが出来る。生成物の硫黄の含有量が８０質量％を越えると炭素骨格が硫黄を保持できなくなる。また硫黄の含有量が８０質量％を超えると、導電性が不充分である。 When the sulfur content of the product is 30-80% by mass, a high capacity electrode material can be obtained. If the sulfur content of the product exceeds 80% by mass, the carbon skeleton cannot retain sulfur. On the other hand, if the sulfur content exceeds 80% by mass, the electrical conductivity is insufficient.
生成物の硫黄の含有量が３０質量％を下回ると、満足できる電池容量が得られない
本発明の非水電解液二次電池は、植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させて得られた生成物を有する正極活物質または負極活物質を備えることを特徴とする。
When the content of sulfur in the product is less than 30% by mass, a satisfactory battery capacity cannot be obtained. The nonaqueous electrolyte secondary battery of the present invention comprises a plant waste and sulfur alone in a sealed container at 250 ° C. A positive electrode active material or a negative electrode active material having a product obtained by heating at ˜600 ° C. is provided.
上記生成物は負極活物質または正極活物質として使用できる。生成物は植物性廃棄物の低温焼成体と硫黄とを含む複合体となっている。この複合体は、電気化学的にリチウムと反応することが可能ななんらかの構造を有していると考える。 The product can be used as a negative electrode active material or a positive electrode active material. The product is a composite containing a low-temperature fired body waste and sulfur. This composite is considered to have some structure capable of electrochemically reacting with lithium.
生成物が正極活物質として用いられるか、負極活物質として用いられるかは、生成物を電極活物質として用いた電極とその対極との関係による。 Whether the product is used as a positive electrode active material or a negative electrode active material depends on the relationship between an electrode using the product as an electrode active material and its counter electrode.
使用される一対の電極のうち、電気化学的に高い電位側が正極といわれ、電気化学的に低い電位側の電極は負極といわれる。従って正極活物質は負極活物質よりも電気化学的に高い電位を有することが必要となる。 Of the pair of electrodes used, the electrochemically high potential side is referred to as the positive electrode, and the electrochemically low potential side electrode is referred to as the negative electrode. Accordingly, the positive electrode active material needs to have a higher electrochemical potential than the negative electrode active material.
対極にリチウム金属もしくはリチウム合金を用いて、生成物がリチウムと反応した際のリチウム電位が０Ｖに近い場合、その生成物は、正極活物質として働く。また対極にＬｉＣｏＯ２等の３Ｖ以上でリチウムの電気化学反応がおこる物質を用いた場合、生成物は負極活物質として働く。 When lithium metal or a lithium alloy is used for the counter electrode and the lithium potential when the product reacts with lithium is close to 0 V, the product acts as a positive electrode active material. In addition, when a material that causes an electrochemical reaction of lithium at 3 V or higher, such as LiCoO 2, is used as the counter electrode, the product functions as a negative electrode active material.
本発明の非水電解液二次電池の場合は、上記生成物を活物質に用いる。生成物は植物性廃棄物の低温焼成体と硫黄とを含む複合体となっている。植物性廃棄物の低温焼成体は炭素を含むため、その複合体は電子伝導性が良好である。またその複合体では硫黄は何らかの形で低温焼成体と複合化しているため、硫黄単体が電解液へ溶出することを抑制できる。 In the case of the non-aqueous electrolyte secondary battery of the present invention, the product is used as an active material. The product is a composite containing a low-temperature fired body waste and sulfur. Since the low-temperature fired body waste of vegetable waste contains carbon, the composite has good electron conductivity. Moreover, in the composite, since sulfur is complexed with the low-temperature fired body in some form, it is possible to suppress the dissolution of sulfur alone into the electrolyte.
従って硫黄の有する容量を炭素材料の有する容量に付加することが出来、硫黄単体が非水溶媒に溶け出すことが抑制される。そのため本発明の非水電解液二次電池は、高容量、高電位でサイクル特性に優れた二次電池とすることが出来る。 Therefore, the capacity | capacitance which sulfur has can be added to the capacity | capacitance which a carbon material has, and it suppresses that a sulfur simple substance melt | dissolves in a non-aqueous solvent. Therefore, the nonaqueous electrolyte secondary battery of the present invention can be a secondary battery having high capacity, high potential and excellent cycle characteristics.
また一般的に硫黄を活物質として使用する場合、一般的な溶媒であるエステル系溶媒は使用できない。これはエステル系溶媒を用いた場合、硫黄とリチウムとの反応が一段階で終了し、それ以降は反応しないためである。硫黄とリチウムとの反応を多段階反応とするために、硫黄を活物質とした場合、エーテル系溶媒が用いられる。しかし、多段階反応の先に出来るリチウムと硫黄との化合物が小分子であるため、エーテル系溶媒を用いても、硫黄が溶媒中に溶け出してしまい電池のサイクル特性が悪くなる。 In general, when sulfur is used as an active material, an ester solvent which is a general solvent cannot be used. This is because when an ester solvent is used, the reaction between sulfur and lithium is completed in one step, and thereafter no reaction occurs. In order to make the reaction between sulfur and lithium a multistage reaction, an ether solvent is used when sulfur is used as an active material. However, since the compound of lithium and sulfur that can be produced prior to the multi-step reaction is a small molecule, even if an ether solvent is used, sulfur dissolves in the solvent and the cycle characteristics of the battery deteriorate.
本発明の非水電解液二次電池は、上記生成物を活物質に用いることによって、理由の詳細は不明であるが、エーテル系溶媒だけでなく、エステル系溶媒を用いても、高容量を示し、サイクル特性の急激な劣化も見られない。 Although the non-aqueous electrolyte secondary battery of the present invention uses the above product as an active material, the details of the reason are unclear. However, not only ether solvents but also ester solvents can be used to achieve high capacity. As shown, there is no rapid deterioration of the cycle characteristics.
従って本発明の非水電解液二次電池は、エーテル系溶媒だけでなく、エステル系溶媒も使用可能である。 Therefore, the nonaqueous electrolyte secondary battery of the present invention can use not only an ether solvent but also an ester solvent.
本発明の非水電解液二次電池の電極材料の製造方法を用いることによって、高電位、高容量の優れたサイクル特性を有する非水電解液二次電池の電極材料を製造することが出来る。また植物性廃棄物を炭素源とし、正極材料でも使用できるほど高電位、高容量であり、優れたサイクル特性を有する電極材料およびその電極材料を用いた非水電解液二次電池を提供できる。 By using the method for producing an electrode material for a non-aqueous electrolyte secondary battery of the present invention, an electrode material for a non-aqueous electrolyte secondary battery having excellent cycle characteristics with a high potential and a high capacity can be produced. In addition, it is possible to provide an electrode material having a high potential and a high capacity that uses plant waste as a carbon source and can be used as a positive electrode material and has excellent cycle characteristics, and a nonaqueous electrolyte secondary battery using the electrode material.
本発明の非水電解液二次電池の電極材料の製造方法は、植物性廃棄物と硫黄単体とを混合して混合物とする混合工程と、上記混合物を密閉容器に入れ２５０℃〜６００℃で加熱する加熱工程と、を有する。 The method for producing an electrode material for a non-aqueous electrolyte secondary battery according to the present invention includes a mixing step of mixing plant waste and simple sulfur to form a mixture, and placing the mixture in a sealed container at 250 ° C to 600 ° C. A heating step of heating.
植物性廃棄物は、産業廃棄物として入手できる植物性高分子であれば特に限定されない。 The plant waste is not particularly limited as long as it is a plant polymer that can be obtained as industrial waste.
植物性廃棄物は、コーヒー豆、茶葉、サトウキビ類、トウモロコシ類、果実類、穀物の藁類、糠および籾殻類から選択される少なくとも一種であることが好ましい。これらの植物性廃棄物は純粋な結晶性セルロースと比較すると結晶セルロースの他に他の成分が多量に含まれている。 The plant waste is preferably at least one selected from coffee beans, tea leaves, sugar cane, corn, fruits, cereals, straw and rice husks. These vegetable wastes contain a large amount of other components in addition to crystalline cellulose as compared with pure crystalline cellulose.
例えばコーヒー豆や茶葉の場合、ヘミセルロース、カフェイン、有機酸などが含有されている。またサトウキビ類やトウモロコシ類にはでんぷんや糖類が含有されている。果実類にはヘミセルロース、ビタミン類、ミネラル類が含有されている。穀物の藁類、糠、籾殻類には金属類、リン、硫黄が含有されている。 For example, in the case of coffee beans and tea leaves, hemicellulose, caffeine, organic acids and the like are contained. Sugarcane and corn contain starch and sugars. Fruits contain hemicellulose, vitamins and minerals. Cereals, cocoons and rice husks contain metals, phosphorus and sulfur.
このような植物性廃棄物を上記温度範囲で炭素質化すると、結晶性に低い構造が形成される。 When such plant waste is carbonized in the above temperature range, a structure with low crystallinity is formed.
なお、植物性廃棄物の種類には特に制限がなく、またそれらの形態にも特に制限はない。植物性廃棄物は、生でもよく、あるいは乾燥処理、発酵処理、粉末化処理、焙煎処理、抽出処理などの様々な処理が施されたものでも使用することが出来る。 In addition, there is no restriction | limiting in particular in the kind of vegetable waste, and there is no restriction | limiting in particular also in those forms. The plant waste may be raw or may be used after being subjected to various treatments such as drying treatment, fermentation treatment, powdering treatment, roasting treatment, and extraction treatment.
特に、産業廃棄物の資源化を図るという観点からは、使用済みのコーヒー豆、茶葉、サトウキビの搾りかす、トウモロコシの芯、ミカンやバナナの皮、穀物（米、大麦、小麦、ライ麦、ヒエ、アワなど）の藁、糠、籾殻が使用可能である。これらは産業廃棄物として、食品加工会社や酒類製造会社から大量かつ容易に入手出来る。 In particular, from the viewpoint of recycling industrial waste, spent coffee beans, tea leaves, sugarcane pomace, corn core, mandarin orange and banana peel, grains (rice, barley, wheat, rye, millet, Can be used. These can be easily obtained in large quantities from food processing companies and liquor manufacturers as industrial waste.
硫黄単体としては、市販されている硫黄粉体を用いることが出来る。 As sulfur simple substance, commercially available sulfur powder can be used.
混合は特に限定されず、植物性廃棄物と硫黄単体とが混合できればよい。混合には、プラネタリーミキサー、脱泡ニーダー、ボールミル、ペイントシェーカー、振動ミル、ライカイ機、アジテーターミル等の一般的な混合装置を使用することが出来る。また混合を手で攪拌して行っても良い。 Mixing is not particularly limited, as long as vegetable waste and simple sulfur can be mixed. For mixing, a general mixing device such as a planetary mixer, a defoaming kneader, a ball mill, a paint shaker, a vibration mill, a reiki machine, and an agitator mill can be used. Further, the mixing may be carried out by stirring by hand.
加熱条件も特に限定されない。加熱は、２５０℃〜６００℃に達したらその温度で１時間以上保持すればよい。 The heating conditions are not particularly limited. When heating reaches 250 ° C. to 600 ° C., the temperature may be maintained for 1 hour or more.
混合工程の前にさらに植物性廃棄物を乾燥させる乾燥工程を有してもよい。 You may have the drying process which dries vegetable waste further before a mixing process.
乾燥は市販の乾燥機を用いて行えばよい。 Drying may be performed using a commercially available dryer.
密閉容器は、２５０℃〜６００℃で加熱しても耐えることが出来る耐熱性および耐圧性のある密閉容器であれば特に限定されない。例えば密閉容器としてオートクレーブ、減圧封管した石英管などが使用できる。 The airtight container is not particularly limited as long as it is a heat resistant and pressure resistant airtight container that can withstand heating at 250 ° C to 600 ° C. For example, an autoclave or a quartz tube sealed under reduced pressure can be used as the sealed container.
硫黄の引火点が２４６℃であるため、密閉容器を用いることによって混合物を安全に加熱出来る。 Since the flash point of sulfur is 246 ° C., the mixture can be heated safely by using an airtight container.
また密閉容器とすることによって植物性廃棄物と硫黄単体とを加熱することによって発生するガス類を密閉できる。その発生したガス類によって密閉容器内に圧力がかかり、密閉容器内でおこる加熱による様々な反応が促進される。 Moreover, the gas generated by heating vegetable waste and sulfur simple substance can be sealed by using a sealed container. The generated gas applies pressure in the sealed container and promotes various reactions due to heating in the sealed container.
加熱雰囲気は特に限定されず、空気中または不活性ガス下で加熱することが出来る。 The heating atmosphere is not particularly limited, and heating can be performed in air or under an inert gas.
加熱は、２５０℃〜６００℃に達したらその温度で１時間以上保持する。その後室温まで自然冷却した後、密閉容器を開放する。 When the heating reaches 250 ° C. to 600 ° C., the temperature is maintained for 1 hour or more. Then, after naturally cooling to room temperature, the sealed container is opened.
反応終了後に密閉容器を開放することによって、生成したガス状の副生成物は抜けていき、不純物の除去が簡単にできる。 By opening the sealed container after the completion of the reaction, the generated gaseous by-product is removed, and the impurities can be easily removed.
更に加熱後の混合物を１５０℃〜４００℃で真空加熱して加熱工程で発生した不純物を除く不純物除去工程を有してもよい。不純物除去工程によって複合化されていない硫黄などの不純物を簡便に除去することが出来る。 Furthermore, you may have the impurity removal process of removing the impurity which generate | occur | produced in the heating process by vacuum-heating the mixture after a heating at 150 to 400 degreeC. Impurities such as sulfur that are not combined can be easily removed by the impurity removal step.
植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させると、明確には不明であるが、植物性廃棄物の低温焼成体と硫黄とを含む複合体が生成される。これは加熱によって植物性廃棄物が炭素化されると同時に硫黄が炭素化された植物性廃棄物内に入り込み、炭素化された植物性廃棄物と硫黄とが何らかの複合体を形成していると考えられる。 When plant waste and sulfur alone are heated at 250 ° C. to 600 ° C. in a sealed container, it is unclear clearly, but a complex containing a low-temperature fired body waste of sulfur and sulfur is produced. The This is because when plant waste is carbonized by heating, sulfur enters carbonized plant waste, and the carbonized plant waste and sulfur form a complex. Conceivable.
本発明の非水電解液二次電池の電極材料は、植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させて得られた生成物を有する。 The electrode material of the nonaqueous electrolyte secondary battery of the present invention has a product obtained by heating plant waste and simple sulfur at 250 ° C. to 600 ° C. in a sealed container.
上記生成物全体を１００質量％としたときに、生成物の硫黄の含有量は３０−８０質量％であることが好ましい。 When the total product is 100% by mass, the sulfur content of the product is preferably 30-80% by mass.
硫黄の含有量が多いほど、電極の電池容量が大きくなる。生成物の硫黄の含有量は、目的とする電池容量によって、適宜選択すればよい。硫黄は植物性廃棄物の炭化の際に、植物性廃棄物の表面もしくは内部に取り込まれている。 The higher the sulfur content, the greater the battery capacity of the electrode. What is necessary is just to select suitably sulfur content of a product according to the target battery capacity. Sulfur is incorporated into the surface or inside of the plant waste during carbonization of the plant waste.
本発明の非水電解液二次電池は、植物性廃棄物と硫黄単体とを密閉容器にて２５０℃〜６００℃で、加熱させて得られた生成物を有する正極活物質または負極活物質を備えている。 The non-aqueous electrolyte secondary battery of the present invention includes a positive electrode active material or a negative electrode active material having a product obtained by heating vegetable waste and sulfur alone in a sealed container at 250 ° C. to 600 ° C. I have.
本発明の非水電解液二次電池は、上記正極活物質または負極活物質を用いる以外は一般的な非水電解液二次電池の構成を有すればよい。 The nonaqueous electrolyte secondary battery of the present invention may have a general configuration of a nonaqueous electrolyte secondary battery except that the positive electrode active material or the negative electrode active material is used.
例えば非水電解液リチウム二次電池の場合は、正極と、負極と、電解液と、セパレータとを含むことが出来る。 For example, in the case of a non-aqueous electrolyte lithium secondary battery, a positive electrode, a negative electrode, an electrolytic solution, and a separator can be included.
上記生成物を正極活物質として用いた場合、上記正極は、集電体に、上記正極活物質をバインダーで結着させたものである。 When the product is used as a positive electrode active material, the positive electrode is obtained by binding the positive electrode active material to a current collector with a binder.
バインダーは集電体に正極活物質を結着させられるものであれば特に限定されない。例えばポリフッ化ビニリデン（ＰＶＤＦ），ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素系樹脂、スチレンブタジエンゴム（ＳＢＲ）等のゴムなどを用いることが出来る。 The binder is not particularly limited as long as it can bind the positive electrode active material to the current collector. For example, fluorine resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), rubber such as styrene butadiene rubber (SBR), and the like can be used.
また正極活物質と共に導電助剤を集電体に結着することが出来る。導電助剤として、炭素質微粒子であるカーボンブラック、黒鉛、アセチレンブラック、ケッチェンブラック、カーボンファイバ等を単独で又は二種以上組み合わせて用いることが出来る。 In addition, the conductive additive can be bound to the current collector together with the positive electrode active material. As the conductive auxiliary agent, carbon black, graphite, acetylene black, ketjen black, carbon fiber, etc., which are carbon fine particles, can be used alone or in combination of two or more.
集電体としてはリチウムイオン二次電池で一般に使用されているアルミ箔のほか、アルミメッシュなどの多孔基材が使用できる。また上記生成物はリチウムと反応する電位が3V付近までと一般のリチウムイオン二次電池に比べて低い為、基材にはアルミのほかニッケルやステンレスなどの箔や多孔体も使用可能である。 As the current collector, a porous substrate such as an aluminum mesh can be used in addition to an aluminum foil generally used in lithium ion secondary batteries. In addition, since the potential of the product to react with lithium is lower than that of a general lithium ion secondary battery up to about 3 V, a foil or a porous material such as nickel or stainless steel can be used as the base material.
上記生成物を正極活物質として用いた場合、負極の活物質はリチウム、リチウムを含む合金、カーボン等が用いられる。リチウムを含まない負極を用いる場合は、プレドープなどの手法を用いて電気化学反応に寄与するリチウムを系内に入れる。リチウムを系内にいれてやることで、電池として働くことが出来る。これらの活物質は単独で又は２種以上組み合わせて用いられることが出来る。 When the product is used as the positive electrode active material, lithium, an alloy containing lithium, carbon, or the like is used as the negative electrode active material. When using a negative electrode that does not contain lithium, lithium that contributes to the electrochemical reaction is introduced into the system using a technique such as pre-doping. By putting lithium into the system, it can work as a battery. These active materials can be used alone or in combination of two or more.
また上記生成物を負極活物質として用いた場合、３Ｖ以上の電位を示す正極活物質を使用する。この場合、正極活物質としてリチウム複合酸化物等が用いることが出来る。リチウム複合酸化物として、例えばＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４等が使用できる。 When the product is used as a negative electrode active material, a positive electrode active material exhibiting a potential of 3 V or higher is used. In this case, a lithium composite oxide or the like can be used as the positive electrode active material. As the lithium composite oxide, for example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 and the like can be used.
セパレータは、非水電解質二次電池に使用されることが出来るものであれば特に限定されない。 A separator will not be specifically limited if it can be used for a nonaqueous electrolyte secondary battery.
電解液は非水溶媒系の電解液であれば、特に限定されない。例えば電解液として環状エステル類、鎖状エステル類、エーテル類が使用できる。 The electrolytic solution is not particularly limited as long as it is a non-aqueous solvent based electrolytic solution. For example, cyclic esters, chain esters, and ethers can be used as the electrolytic solution.
環状エステル類として、例えばエチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ガンマブチロラクトン、ビニレンカーボネート、２−メチル−ガンマブチロラクトン、アセチル−ガンマブチロラクトン、ガンマバレロラクトン等が使用できる。 Examples of cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
鎖状エステル類として、例えばジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジプロピルカーボネート、メチルエチルカーボネート、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステル等が使用できる。 Examples of chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
エーテル類として、例えばテトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、１，２−ジブトキシエタン等が使用できる。 Examples of ethers that can be used include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and the like.
また上記電解液に溶解させる電解質として、目的とする電池の種類に応じて、リチウム、ナトリウム、アルミニウム等の軽金属の塩を使用できる。 In addition, as an electrolyte to be dissolved in the electrolytic solution, a salt of a light metal such as lithium, sodium, or aluminum can be used depending on the intended battery type.
例えば非水電解液リチウム二次電池を構成する場合は、電解質としてＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２等のリチウム塩を使用することが出来る。 For example, when a non-aqueous electrolyte lithium secondary battery is configured, a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 is used as an electrolyte. I can do it.
また非水電解液二次電池の形状についても特に限定されることはなく、円筒形、角形、コイン形、ボタン形などの種々の形状にすることが出来る。 Further, the shape of the non-aqueous electrolyte secondary battery is not particularly limited, and can be various shapes such as a cylindrical shape, a square shape, a coin shape, and a button shape.
以下、一実施例を挙げて本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to an example.
非水電解液リチウム二次電池用正極を以下のように作製し、評価用モデル電池を用いて充放電サイクル試験を行った。試験には正極を評価極とした、CR2032型コインセル（宝泉株式会社製）を用いた。 A positive electrode for a non-aqueous electrolyte lithium secondary battery was prepared as follows, and a charge / discharge cycle test was performed using a model battery for evaluation. In the test, a CR2032 type coin cell (manufactured by Hosen Co., Ltd.) using a positive electrode as an evaluation electrode was used.
＜正極活物質の作製＞
（生成物１）
コーヒーの出し殻を真空乾燥機にて乾燥した。乾燥後のコーヒー出し殻と硫黄粉末（アルドリッチ社製、平均粒径３μｍ）をコーヒーの出し殻：硫黄粉末＝１：４（質量比）で手攪拌して混合した。
<Preparation of positive electrode active material>
(Product 1)
The coffee grounds were dried in a vacuum dryer. The dried coffee grounds and sulfur powder (manufactured by Aldrich,
コーヒー出し殻と硫黄粉末の混合物（0.17875ｇ）をペレット状にし、オートクレーブ（オーエムラボテック社製）に入れ、温度制御ユニット（チノー製）を接続した坩堝炉（タナカテック製）で室温から１５０℃まで１時間で昇温し、その温度を1時間保持した。 Mix the coffee grounds and sulfur powder (0.17875g) into pellets, put them in an autoclave (Om Lab Tech), and from room temperature to 150 ° C in a crucible furnace (Tanaka Tech) connected with a temperature control unit (Chino) The temperature was raised in 1 hour, and the temperature was maintained for 1 hour.
さらに４００℃まで1時間で昇温し、その温度を２時間保持した。その後、室温になるまで放冷した。 Further, the temperature was raised to 400 ° C. over 1 hour, and the temperature was maintained for 2 hours. Then, it stood to cool to room temperature.
得られた黒色粉末を耐熱ガラス容器に入れ、真空引きし３００℃で５時間保持した。 その後室温になるまで放冷し、生成物１（0.02065g）を得た。 The obtained black powder was put into a heat-resistant glass container, vacuumed and held at 300 ° C. for 5 hours. Thereafter, the mixture was allowed to cool to room temperature to obtain Product 1 (0.02065 g).
原料全体の質量と生成物の質量とを比較すると、生成物は原料の１１．６質量％であり、原料の８８．４質量％が不純物として除去されたことになる。 Comparing the mass of the entire raw material with the mass of the product, the product was 11.6% by mass of the raw material, and 88.4% by mass of the raw material was removed as impurities.
出来上がった生成物１は黒色の粉末であった。 The finished product 1 was a black powder.
この生成物１の有機元素分析を行い、硫黄、炭素、水素、窒素の含有量を測定した。生成物１全体の質量を１００質量％として、硫黄の含有量は７３．６質量％、炭素の含有量は２２．７質量％、水素０．６質量％、窒素０．６質量％であった。 The organic elemental analysis of this product 1 was performed and the content of sulfur, carbon, hydrogen, and nitrogen was measured. The total mass of the product 1 was 100% by mass, the sulfur content was 73.6% by mass, the carbon content was 22.7% by mass, hydrogen 0.6% by mass, and nitrogen 0.6% by mass. .
（生成物２）
生成物１の製造において「４００℃まで１時間で昇温し、２時間保持した」ところを「３００℃」とした以外は生成物１と同様にして生成物２を得た。生成物２の質量は原料質量の１８．７質量％であった。
(Product 2)
Product 2 was obtained in the same manner as Product 1, except that in the production of Product 1, the temperature was raised to 400 ° C. over 1 hour and held for 2 hours was changed to “300 ° C.”. The mass of the product 2 was 18.7% by mass of the raw material mass.
（生成物３）
生成物１の製造において「得られた黒色粉末を耐熱ガラス容器に入れ、真空引きし３００℃で５時間保持した」ところを「真空引きし、室温で５時間保持した」以外は生成物１と同様にして生成物３を得た。生成物３の質量は原料質量の３４．４質量％であった。
(Product 3)
In the production of the product 1, except that “the obtained black powder was put in a heat-resistant glass container, vacuumed and kept at 300 ° C. for 5 hours”, except that “evacuated and kept at room temperature for 5 hours” Similarly,
（生成物４）
生成物１の製造においてコーヒー出し殻を緑茶出し殻とした以外は生成物１と同様にして生成物４を得た。生成物４の質量は原料質量の１３．０質量％であった。
(Product 4)
Product 4 was obtained in the same manner as Product 1 except that the coffee grounds were changed to green tea grounds in the production of Product 1. The mass of the product 4 was 13.0% by mass of the raw material mass.
（生成物５）
生成物１の製造においてコーヒー出し殻を糠とした以外は生成物１と同様にして生成物５を得た。生成物５の質量は原料質量の１４．５質量％であった。
(Product 5)
The
（比較物１）
コーヒー出し殻のみを生成物１の作製方法と同様に処理して比較物１を得た。
(Comparative product 1)
Only the coffee grounds was processed in the same manner as the production method of the product 1 to obtain a comparative product 1.
（比較物２）
比較物１に生成物１と同量の硫黄粉末を混合して比較物２を得た。比較物２の質量は硫黄粉末とコーヒー出し殻の質量の和の７．０質量％であった。
(Comparative product 2)
The comparative product 1 was mixed with the same amount of sulfur powder as the product 1 to obtain a comparative product 2. The mass of the comparative product 2 was 7.0% by mass of the sum of the masses of the sulfur powder and the coffee grounds.
（比較物３）
コーヒー出し殻をアセチレンブラックにした以外は生成物１の作製方法と同様に処理して比較物３を得た。比較物３の質量は原料質量の２０．６質量％であった。
(Comparative product 3)
A
＜正極活物質の評価１＞
乾燥後のコーヒーの出し殻と上記生成物１とをＦＴ−ＩＲ（ＢＲＵＫＥＲ社製）で測定した。
<Evaluation 1 of positive electrode active material>
The coffee grounds after drying and the product 1 were measured by FT-IR (manufactured by BRUKER).
赤外線スペクトルの測定結果を図３に示す。図３で点線で示されたコーヒーの出し殻に示される様々なピークが、図３で実線で示される生成物１には見られないことがわかった。 The measurement result of the infrared spectrum is shown in FIG. It was found that the various peaks shown in the coffee grounds indicated by the dotted line in FIG. 3 are not observed in the product 1 indicated by the solid line in FIG.
この結果から生成物１には出し殻が有する各種官能基がないことがわかった。また生成物１には不純物が含まれていないこともわかった。 From this result, it was found that the product 1 does not have various functional groups of the husk. It was also found that the product 1 did not contain impurities.
また生成物２、生成物３、生成物４および生成物５についても、生成物１と同様にしてＦＴ−ＩＲで測定し、各種官能基が消失していることを確認した。
Further, the product 2, the
＜正極活物質の評価２＞
上記生成物１をラマン分光光度計（日本分光社製）で測定した。得られたラマンスペクトルを図４に示す。生成物１は図４に示すラマンスペクトルを有することがわかった。
<Evaluation 2 of positive electrode active material>
The product 1 was measured with a Raman spectrophotometer (manufactured by JASCO Corporation). The obtained Raman spectrum is shown in FIG. Product 1 was found to have the Raman spectrum shown in FIG.
＜評価用電極作製＞
下記のように評価用の正極を作製した。
（実施例１）。
生成物１（2.5mg）、アセチレンブラック (1.8mg)、ＴＡＢ (アセチレンブラックとＰＴＦＥが２：１で混合している物質,0.75 mg)を混合してシート化し、アルミメッシュ（１４φ）に圧着した。それを１２０℃で６時間乾燥し、上記生成物１を含む実施例１の正極を得た。
<Production of electrode for evaluation>
A positive electrode for evaluation was produced as follows.
(Example 1).
Product 1 (2.5 mg), acetylene black (1.8 mg), and TAB (substance in which acetylene black and PTFE are mixed at a ratio of 2: 1, 0.75 mg) are mixed to form a sheet, which is pressure-bonded to an aluminum mesh (14φ). . It was dried at 120 ° C. for 6 hours to obtain a positive electrode of Example 1 containing the product 1 described above.
（比較例１）
活物質として、比較物１を用いたこと以外は実施例１と同様にして比較例１の正極を得た。
(Comparative Example 1)
A positive electrode of Comparative Example 1 was obtained in the same manner as Example 1 except that Comparative Example 1 was used as the active material.
（実施例２）
生成物１の代わりに生成物２を用いたこと以外は実施例１と同様にして実施例２の正極を得た。
(Example 2)
A positive electrode of Example 2 was obtained in the same manner as in Example 1 except that the product 2 was used instead of the product 1.
（実施例３）
生成物１の代わりに生成物３を用いたこと以外は実施例１と同様にして実施例３の正極を得た。
(Example 3)
A positive electrode of Example 3 was obtained in the same manner as in Example 1 except that the
（実施例４）
生成物１の代わりに生成物４を用いたこと以外は実施例１と同様にして実施例４の正極を得た。
Example 4
A positive electrode of Example 4 was obtained in the same manner as in Example 1 except that the product 4 was used instead of the product 1.
（実施例５）
生成物１の代わりに生成物５を用いたこと以外は実施例１と同様にして実施例５の正極を得た。
(Example 5)
A positive electrode of Example 5 was obtained in the same manner as in Example 1 except that the
（比較例２）
活物質として、比較物２を用いたこと以外は実施例１と同様にして比較例２の正極を得た。
(Comparative Example 2)
A positive electrode of Comparative Example 2 was obtained in the same manner as Example 1 except that Comparative Example 2 was used as the active material.
（比較例３）
活物質として、比較物３を用いたこと以外は実施例１と同様にして比較例３の正極を得た。
(Comparative Example 3)
A positive electrode of Comparative Example 3 was obtained in the same manner as in Example 1 except that Comparative Example 3 was used as the active material.
＜ＣＲ２０３２型コインセル電池作製＞
上記した電極を正極とし、５００μmの金属リチウム（本城金属製）を負極とし、１mol/lのＬｉＰＦ6／エチレンカ−ボネ−ト（ＥＣ）＋ジエチルカ−ボネ−ト（ＤＥＣ）（ＥＣ：ＤＥＣ＝１：１（体積比））（キシダ化学製）を電解液として、セパレータ（セルガード製）及びガラスフィルター（アドバンテック製）に保持させ、これをCR２０３２型コインセル（宝泉製）に入れて電池とした。
<CR2032-type coin cell battery production>
The above electrode is used as a positive electrode, 500 μm of metallic lithium (made by Honjo Metal) is used as a negative electrode, and 1 mol / l LiPF 6 / ethylene carbonate (EC) + diethyl carbonate (DEC) (EC: DEC = 1: 1 (volume ratio)) (manufactured by Kishida Chemical Co., Ltd.) was used as an electrolyte solution, held in a separator (manufactured by Celgard) and a glass filter (manufactured by Advantech), and placed in a CR2032-type coin cell (manufactured by Hosen) to obtain a battery. .
＜CR２０３２型コインセル電池評価＞
このモデル電池における評価極の評価を次の方法で行った。
<CR2032-type coin cell battery evaluation>
Evaluation of the evaluation electrode in this model battery was performed by the following method.
（サイクル試験）
試験は充放電電流値を０．０５ｍＡで、放電電位を０．５Ｖｖｓ Ｌｉ／Ｌｉ＋、充電電位を３Ｖ ｖｓ Ｌｉ／Ｌｉ＋としこれを１サイクルとした。室温（２５℃）で繰り返し充放電を行い、活物質あたりの放電容量（ｍＡｈ／ｇ）を調べた。
(Cycle test)
Tested in 0.05mA a charge-discharge current value, the discharge potential 0.5Vvs Li / Li +, the charge potential was 3V vs Li / Li + and then 1 cycle it. Charging / discharging was repeated at room temperature (25 ° C.), and the discharge capacity (mAh / g) per active material was examined.
実施例１の正極を有するモデル電池について、サイクル数と活物質あたりの放電容量（ｍＡｈ／ｇ）の関係を示すグラフを図２に示す。また実施例１の正極を有するモデル電池および比較例１の正極を有するモデル電池の１サイクル目と２サイクル目の活物質あたりの放電容量（ｍＡｈ／ｇ）と電圧（Ｖ）(VS. Li/Li+)の関係を示すグラフを図１に示す。 FIG. 2 shows a graph showing the relationship between the number of cycles and the discharge capacity per unit active material (mAh / g) for the model battery having the positive electrode of Example 1. Further, the discharge capacity (mAh / g) and voltage (V) (VS. Li /) per active material in the first and second cycles of the model battery having the positive electrode of Example 1 and the model battery having the positive electrode of Comparative Example 1 were compared. A graph showing the relationship of Li + ) is shown in FIG.
図１より、１サイクル目の実施例１の放電容量は１３９４．６ｍＡｈ／ｇもあり、比較例１の放電容量（５１１．９ｍＡｈ／ｇ）と比べて大幅に向上していることがわかった。 From FIG. 1, it was found that the discharge capacity of Example 1 in the first cycle was 1394.6 mAh / g, which was significantly improved as compared with the discharge capacity of Comparative Example 1 (511.9 mAh / g).
また２サイクル目の実施例１の放電容量は８２２．８ｍＡｈ／ｇもあり、比較例１の放電容量（１３５．６ｍＡｈ／ｇ）と比べて２サイクル目の放電容量も大きいことがわかった。 Further, the discharge capacity of Example 1 in the second cycle was 822.8 mAh / g, and it was found that the discharge capacity in the second cycle was larger than the discharge capacity of Comparative Example 1 (135.6 mAh / g).
またこの１サイクル目と２サイクル目の平均電圧を測定すると、実施例１の１サイクル目の平均電圧は０．９０５Ｖであり、２サイクル目の平均電圧は１．１７Ｖであった。 Further, when the average voltage of the first cycle and the second cycle was measured, the average voltage of the first cycle of Example 1 was 0.905V, and the average voltage of the second cycle was 1.17V.
比較例１の１サイクル目の平均電圧は０．８６９Ｖであり、２サイクル目の平均電圧は０．８３０Ｖであった。 The average voltage in the first cycle of Comparative Example 1 was 0.869V, and the average voltage in the second cycle was 0.830V.
これより、硫黄と植物性廃棄物を処理することで硫黄も活物質として働いていることがわかった。 As a result, it was found that sulfur also works as an active material by treating sulfur and plant waste.
図１より実施例１は比較例１に比べて高容量であることが確認できた。この結果から実施例１の正極は、植物性廃棄物を炭化させた比較例１の正極とは異なり、硫黄が系内に含まれこれが活物質として働いている硫黄変性材料であることがわかった。 From FIG. 1, it was confirmed that Example 1 had a higher capacity than Comparative Example 1. From this result, it was found that the positive electrode of Example 1 was a sulfur-modified material containing sulfur in the system and acting as an active material, unlike the positive electrode of Comparative Example 1 in which plant waste was carbonized. .
また図２より、放電容量および充電容量は２サイクル目から１０サイクル目まで変化があまりないことが確認できた。なおサイクル試験は１００回まで行ったが放電容量および充電容量は急激な低下を示さなかった。 Further, from FIG. 2, it was confirmed that the discharge capacity and the charge capacity did not change much from the second cycle to the tenth cycle. Although the cycle test was conducted up to 100 times, the discharge capacity and the charge capacity did not show a sharp drop.
実施例１と同様にして実施例２〜実施例５および比較例２、比較例３のサイクル試験を行った。１サイクル目の放電容量および平均電圧と２サイクル目の放電容量および平均電圧の結果を下記に示す。 In the same manner as in Example 1, the cycle tests of Examples 2 to 5, Comparative Example 2, and Comparative Example 3 were performed. The results of the discharge capacity and average voltage of the first cycle and the discharge capacity and average voltage of the second cycle are shown below.
実施例２
放電容量 １サイクル目 1398.4 mAh/g 2サイクル目 928.0 mAh/g
平均電圧 １サイクル目 1.081V 2サイクル目 1.339V
実施例３
放電容量 １サイクル目 859.3 mAh/g 2サイクル目 488.2 mAh/g
平均電圧 １サイクル目 1.139V 2サイクル目 1.374V
実施例４
放電容量 １サイクル目 702.8 mAh/g 2サイクル目 347.1 mAh/g
平均電圧 １サイクル目 0.852V 2サイクル目 1.028V
実施例５
放電容量 １サイクル目 902.9 mAh/g 2サイクル目 609.6 mAh/g
平均電圧 １サイクル目 0.941V 2サイクル目 1.109V
比較例２
放電容量 １サイクル目 739.3 mAh/g 2サイクル目 380.3 mAh/g
平均電圧 １サイクル目 0.897V 2サイクル目 1.078V
比較例３
放電容量 １サイクル目 408.1 mAh/g 2サイクル目 94.1 mAh/g
平均電圧 １サイクル目 0.832V 2サイクル目 0.871V
Example 2
Discharge capacity 1st cycle 1398.4 mAh / g 2nd cycle 928.0 mAh / g
Average voltage 1st cycle 1.081V 2nd cycle 1.339V
Example 3
Discharge capacity 1st cycle 859.3 mAh / g 2nd cycle 488.2 mAh / g
Average voltage 1st cycle 1.139V 2nd cycle 1.374V
Example 4
Discharge capacity 1st cycle 702.8 mAh / g 2nd cycle 347.1 mAh / g
Average voltage 1st cycle 0.852V 2nd cycle 1.028V
Example 5
Discharge capacity 1st cycle 902.9 mAh / g 2nd cycle 609.6 mAh / g
Average voltage 1st cycle 0.941V 2nd cycle 1.109V
Comparative Example 2
Discharge capacity 1st cycle 739.3 mAh / g 2nd cycle 380.3 mAh / g
Average voltage 1st cycle 0.897V 2nd cycle 1.078V
Comparative Example 3
Discharge capacity 1st cycle 408.1 mAh / g 2nd cycle 94.1 mAh / g
Average voltage 1st cycle 0.832V 2nd cycle 0.871V
実施例１と実施例２の放電容量、平均電圧を比較すると、ほぼ同様の高容量、高電圧の結果となった。従って生成物の加熱温度が３００℃においても同様の結果となることがわかった。 When the discharge capacities and average voltages of Example 1 and Example 2 were compared, the results were almost the same high capacity and high voltage. Therefore, it was found that the same result was obtained when the heating temperature of the product was 300 ° C.
実施例１、実施例３および比較例１とを比較すると、実施例３も実施例１と同様に比較例１より高容量、高電位であることがわかった。また実施例３では放電容量が実施例１よりも若干低下することがわかった。生成物１と生成物３の原料における質量の割合を比較すると、生成物３は生成物１に比べて質量割合が大きい。
When Example 1, Example 3, and Comparative Example 1 were compared, it was found that Example 3 also had higher capacity and higher potential than Comparative Example 1, as in Example 1. In Example 3, it was found that the discharge capacity was slightly lower than that in Example 1. When the ratio of the mass in the raw material of the product 1 and the
このことより実施例３では生成物に不純物が残っており、不純物が残っていると容量が低下すると考えられる。 From this, in Example 3, impurities remain in the product, and it is considered that the capacity decreases when impurities remain.
実施例１、実施例４、実施例５および比較例１とを比べると、実施例４および実施例５も実施例１と同様に比較例１より高容量、高電位であることがわかった。 Comparing Example 1, Example 4, Example 5, and Comparative Example 1, it was found that Example 4 and Example 5 also had higher capacity and higher potential than Comparative Example 1 as in Example 1.
比較例２、比較例３および実施例１とを比べると、比較例２および比較例３は実施例１よりも低容量、低電位であることがわかった。比較例２ではコーヒー出し殻を先に炭化させ、炭化したコーヒー出し殻と硫黄粉末とを混合している。この結果からコーヒー出し殻と硫黄粉末とは原料の段階で混合してから炭化することが重要であることがわかった。 Comparing Comparative Example 2, Comparative Example 3 and Example 1, it was found that Comparative Example 2 and Comparative Example 3 had lower capacity and lower potential than Example 1. In Comparative Example 2, the coffee grounds are first carbonized, and the carbonized coffee grounds and sulfur powder are mixed. From this result, it was found that coffee grounds and sulfur powder are important to be carbonized after mixing at the raw material stage.
またコーヒーだし殻をアセチレンブラックに代えた比較例３では最も低容量、低電位となった。このことより、植物成廃棄物のようなある程度官能基が存在する原料と硫黄粉末は処理される必要があることがわかった。 Further, Comparative Example 3 in which the coffee grounds was replaced with acetylene black had the lowest capacity and the lowest potential. From this, it was found that raw materials and sulfur powders having functional groups to some extent, such as plant waste, need to be treated.
Claims (12)
前記混合物を密閉容器に入れ２５０℃〜６００℃で１時間以上加熱する加熱工程と、
を有し、
前記植物性廃棄物は、コーヒー豆、茶葉、サトウキビ類、トウモロコシ類、果実類、穀物の藁類、糠および籾殻類から選択される少なくとも一種である非水電解液二次電池の正極活物質の製造方法。 A mixing step of mixing vegetable waste and sulfur alone to form a mixture;
A heating step of placing the mixture in a sealed container and heating at 250 ° C. to 600 ° C. for 1 hour or more ;
I have a,
The plant waste is a positive electrode active material of a non-aqueous electrolyte secondary battery that is at least one selected from coffee beans, tea leaves, sugar cane, corn, fruits, cereals, straw and rice husks . Production method.
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