JPH10321231A - Negative electrode material, manufacture of negative electrode material, and nonaqueous electrolyte secondary battery - Google Patents
Negative electrode material, manufacture of negative electrode material, and nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH10321231A JPH10321231A JP9125930A JP12593097A JPH10321231A JP H10321231 A JPH10321231 A JP H10321231A JP 9125930 A JP9125930 A JP 9125930A JP 12593097 A JP12593097 A JP 12593097A JP H10321231 A JPH10321231 A JP H10321231A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- electrode material
- chitin
- secondary battery
- electrolyte secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭素質材料よりな
る負極材料及びその製造方法と、炭素質材料を負極材料
とする非水電解液二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode material made of a carbonaceous material, a method for producing the same, and a nonaqueous electrolyte secondary battery using the carbonaceous material as a negative electrode material.
【０００２】[0002]
【従来の技術】近年の電子技術の進歩に伴い、カメラ一
体型ビデオテープレコーダ、携帯電話、ラップトップコ
ンピュータ等の小型のポータブル電子機器が開発されて
いる。それ対応して、これら電子機器に使用するための
ポータブル電源として小型且つ軽量で、高エネルギー密
度を有する二次電池の開発が強く要請されている。2. Description of the Related Art Along with recent advances in electronic technology, small portable electronic devices such as a camera-integrated video tape recorder, a mobile phone, and a laptop computer have been developed. In response, there is a strong demand for the development of a small and lightweight secondary battery having a high energy density as a portable power supply for use in these electronic devices.
【０００３】このような要請に応える二次電池として、
リチウム、ナトリウム、アルミニウム等の軽金属を負極
活物質として用いる非水電解液二次電池が期待されてい
る。[0003] As a secondary battery that meets such demands,
A non-aqueous electrolyte secondary battery using a light metal such as lithium, sodium, and aluminum as a negative electrode active material is expected.
【０００４】この非水電解液二次電池は、理論上高電圧
を発生でき且つ高エネルギー密度を有する。中でも、リ
チウムを負極活物質として用いた非水電解液二次電池
は、高出力及び高エネルギー密度が得られることから活
発に研究開発が行われている。This non-aqueous electrolyte secondary battery can theoretically generate a high voltage and has a high energy density. Among them, a non-aqueous electrolyte secondary battery using lithium as a negative electrode active material has been actively researched and developed because high output and high energy density can be obtained.
【０００５】しかしながら、リチウム金属などの軽金属
をそのまま負極に用いた場合、充電過程において負極か
ら軽金属がデンドライト状に析出し易い。このデンドラ
イト結晶の先端では非常に高い電流密度になるため、非
水電解液が分解してサイクル寿命が低下したり、また負
極から析出したデンドライト結晶が正極にまで到達し、
電池の内部短絡が発生するといった問題がある。[0005] However, when a light metal such as lithium metal is used for the negative electrode as it is, the light metal tends to precipitate in a dendrite form from the negative electrode during the charging process. At the tip of this dendrite crystal, the current density becomes very high, so that the non-aqueous electrolyte is decomposed and the cycle life is reduced, or the dendrite crystal deposited from the negative electrode reaches the positive electrode,
There is a problem that an internal short circuit occurs in the battery.
【０００６】そこで、このようなデンドライト状の金属
析出を防止するために、軽金属をそのまま負極に用いる
のではなく、軽金属のイオンをドープ・脱ドープさせる
ことが可能な炭素質材料に、軽金属のイオンをドープさ
せて負極材料に使用することが行われている。In order to prevent such dendrite-like metal precipitation, light metal is not used for the negative electrode as it is, but light metal ion is added to a carbonaceous material which can be doped and dedoped with light metal ion. For use as a negative electrode material.
【０００７】この炭素質材料としては、製造コストが低
く抑えられ、また電池に優れたサイクル特性を付与でき
ることから、コークス類（ピッチコークス、ニードルコ
ークス、石油コークス等）、有機高分子化合物焼成体
（フェノール樹脂、フラン樹脂等を適当な温度で焼成し
炭化したもの）等が主に用いられている。As the carbonaceous material, since the production cost can be kept low and excellent cycle characteristics can be imparted to the battery, coke (pitch coke, needle coke, petroleum coke, etc.), organic polymer compound fired body ( Phenol resins, furan resins, and the like are fired at an appropriate temperature and carbonized), and the like.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、これま
での炭素質材料を用いる非水電解液二次電池は、リチウ
ム金属をそのまま負極に用いる電池に比べて、サイクル
特性には優れるものの、エネルギー密度の点で劣ってい
るといった問題がある。However, conventional non-aqueous electrolyte secondary batteries using carbonaceous materials are superior in cycle characteristics to batteries using lithium metal as it is for the negative electrode, but have a lower energy density. There is a problem that it is inferior in point.
【０００９】ここで、このような非水電解液二次電池で
は、エネルギー密度が炭素質材料への軽金属のドープ・
脱ドープ量、すなわち充放電容量に強く依存している、
したがって、エネルギー密度を上げるには、炭素質材料
への軽金属のドープ・脱ドープ量を上げることが必要で
ある。Here, in such a non-aqueous electrolyte secondary battery, the energy density is such that the carbon material is doped with light metal.
Dedoping amount, that is, strongly depends on the charge and discharge capacity,
Therefore, in order to increase the energy density, it is necessary to increase the doping / dedoping amount of the light metal to the carbonaceous material.
【００１０】ところが、これまで負極材料として使用さ
れているコークス類や有機高分子化合物焼成体はこのド
ープ・脱ドープ量が十分に高いとは言えない。しかも炭
素質材料では容量を向上せしめる具体的な理論や方法が
明らかになっておらず、容量を現状以上に上げるのは難
しいのが実情である。However, cokes and organic polymer compound fired bodies which have been used as a negative electrode material do not have sufficiently high doping and undoping amounts. Moreover, the specific theory and method for increasing the capacity of carbonaceous materials have not been clarified, and it is actually difficult to increase the capacity beyond the current level.
【００１１】そこで、本発明はこのような従来の実情に
鑑みて提案されたものであり、電池に大きな充放電容量
を付与できる負極材料及びその製造方法を提供すること
を目的とする。また、そのような負極材料を用いること
で、サイクル特性に優れるとともに高いエネルギー密度
が得られる非水電解液二次電池を提供することを目的と
する。Accordingly, the present invention has been proposed in view of such conventional circumstances, and has as its object to provide a negative electrode material capable of providing a battery with a large charge / discharge capacity, and a method of manufacturing the same. It is another object of the present invention to provide a non-aqueous electrolyte secondary battery having excellent cycle characteristics and high energy density by using such a negative electrode material.
【００１２】[0012]
【課題を解決するための手段】上述の目的を達成するた
めに、本発明者らが鋭意検討を重ねた結果、炭素質材料
を合成する際の原料の選択が、合成される炭素質材料の
充放電容量に大きく影響を及ぼすとの知見を得るに至っ
た。本発明はこのような知見に基づいて完成されたもの
である。Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have conducted intensive studies and as a result, the selection of the raw material when synthesizing the carbonaceous material has been determined. It has been found that the charge-discharge capacity is greatly affected. The present invention has been completed based on such findings.
【００１３】すなわち、本発明の負極材料は、キチンま
たはキトサンの少なくともいずれかを含む材料の焼成体
を含有することを特徴とするものである。That is, the negative electrode material of the present invention is characterized by containing a fired body of a material containing at least one of chitin and chitosan.
【００１４】また、本発明の負極材料の製造方法は、キ
チンまたはキトサンの少なくともいずれかを含む材料
を、非酸化性雰囲気下で焼成することを特徴とするもの
である。Further, the method for producing a negative electrode material of the present invention is characterized in that a material containing at least one of chitin and chitosan is calcined in a non-oxidizing atmosphere.
【００１５】さらに、本発明の非水電解液二次電池は、
負極、正極及び非水電解液を備えてなり、負極は、キチ
ンまたはキトサンの少なくともいずれかを含む材料の焼
成体を含有することを特徴とするものである。Furthermore, the non-aqueous electrolyte secondary battery of the present invention
It comprises a negative electrode, a positive electrode and a non-aqueous electrolyte, wherein the negative electrode contains a fired material of a material containing at least one of chitin and chitosan.
【００１６】負極材料として、キチンまたはキトサンの
少なくともいずれかを含む材料の焼成体を用いると、電
池の充放電容量が増大し、エネルギー密度が向上する。When a fired body of a material containing at least one of chitin and chitosan is used as the negative electrode material, the charge / discharge capacity of the battery increases, and the energy density improves.
【００１７】[0017]
【発明の実施の形態】以下、本発明の具体的な実施の形
態について説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described.
【００１８】本発明の負極材料は、キチンまたはキトサ
ンの少なくともいずれかを含む材料の焼成体を含有する
ものである。The negative electrode material of the present invention contains a fired material of a material containing at least one of chitin and chitosan.
【００１９】この焼成体は、リチウムイオンのドープ・
脱ドープ量が大きいため、負極材料として用いると電池
のエネルギー密度が向上する。This fired body is doped with lithium ions.
Since the amount of undoping is large, when used as a negative electrode material, the energy density of the battery is improved.
【００２０】この焼成体は、キチンまたはキトサンの少
なくともいずれかを含有する材料を、非酸化性雰囲気中
で焼成し、炭化することによって得られる。The fired body is obtained by firing and carbonizing a material containing at least one of chitin and chitosan in a non-oxidizing atmosphere.
【００２１】ここで、キチン、キトサンは、含窒素多糖
類であり、節足動物の皮膚、軟体動物の殻、菌類の細胞
膜等の成分をなす。本発明の負極材料の原料としては、
合成物であっても、これら生物から得た物であっても良
い。特に、カニやエビ等の甲殻類の外皮（殻）を焼成す
ると、高容量の負極材料が得られる。なお、カニやエビ
等の外皮から負極材料を合成するには、これらの外皮
を、水洗、アルコール洗浄し、その後、粉砕、脱灰、脱
蛋白質等の処理を施した後、必要に応じて精製し、焼成
すれば良い。Here, chitin and chitosan are nitrogen-containing polysaccharides, and constitute components such as arthropod skin, mollusk shells, fungal cell membranes, and the like. As a raw material of the negative electrode material of the present invention,
It may be a synthetic product or a product obtained from these organisms. In particular, baking the shell (shell) of crustaceans such as crabs and shrimps provides a high capacity negative electrode material. In order to synthesize the negative electrode material from the crust, shrimp, etc., these crusts are washed with water, alcohol, and then crushed, demineralized, deproteinized, etc., and then purified if necessary. Then, it may be fired.
【００２２】キチン、キトサンを含む材料を焼成する際
の非酸化性雰囲気は、例えば窒素、ヘリウム、アルゴン
等の不活性ガスを含有する雰囲気であってもよく、真空
ポンプによって排気した真空雰囲気であっても良い。焼
成温度は、７００〜１５００℃が好ましく、９００〜１
３００℃がより好ましい。昇温速度は１℃／分以上、焼
成時間は５時間以下に設定すれば良い。The non-oxidizing atmosphere for firing the material containing chitin and chitosan may be an atmosphere containing an inert gas such as nitrogen, helium, argon or the like, or a vacuum atmosphere exhausted by a vacuum pump. May be. The firing temperature is preferably from 700 to 1500 ° C.,
300 ° C. is more preferred. The heating rate may be set at 1 ° C./min or more, and the firing time may be set at 5 hours or less.
【００２３】なお、上述の脱灰に先立って、キチン、キ
トサンを含む材料を、非酸化性雰囲気下、温度３００〜
７００℃で予め炭化しておくことが好ましい。Prior to the above-described decalcification, a material containing chitin and chitosan is treated in a non-oxidizing atmosphere at a temperature of 300-300.
It is preferable to carbonize at 700 ° C. in advance.
【００２４】本発明にかかる非水電解液二次電池では、
以上のようなキチンまたはキトサンの少なくともいずれ
かを含有する材料の焼成体が負極材料として用いられ
る。In the non-aqueous electrolyte secondary battery according to the present invention,
A fired body of a material containing at least one of chitin and chitosan as described above is used as a negative electrode material.
【００２５】この負極材料によって負極を形成するに
は、例えばこの負極材料の粉末を、結着剤、分散媒とと
もに混合して負極ミックスを調製し、この負極ミックス
を圧縮成型等によって所望の電極形状に形成しても良
く、上記負極ミックスを帯状集電体の両面に塗布、乾燥
することで電極を形成しても構わない。In order to form a negative electrode from the negative electrode material, for example, a powder of the negative electrode material is mixed with a binder and a dispersion medium to prepare a negative electrode mix, and the negative electrode mix is formed into a desired electrode shape by compression molding or the like. Alternatively, the negative electrode mix may be applied to both sides of the belt-shaped current collector and dried to form an electrode.
【００２６】このようにして形成される負極は、リチウ
ム、ナトリウム、アルミニウム等の軽金属のイオンがド
ープされることによって電池の負極として機能する。特
に電池出力やエネルギー密度の観点からはリチウムイオ
ンをドープすることが好ましい。The negative electrode thus formed functions as a negative electrode of a battery by being doped with ions of a light metal such as lithium, sodium and aluminum. In particular, it is preferable to dope lithium ions from the viewpoint of battery output and energy density.
【００２７】上記非水電解液二次電池の負極以外の材料
は、この種の非水電解液二次電池で通常用いられている
ものがいずれも使用可能である。As the material other than the negative electrode of the non-aqueous electrolyte secondary battery, any of the materials usually used in this type of non-aqueous electrolyte secondary battery can be used.
【００２８】例えば正極材料としては、金属酸化物、金
属硫化物、または特定のポリマーが用いられる。具体的
には、ＴｉＳ2、ＭｏＳ2、ＮｂＳｅ2、Ｖ2Ｏ5等のリチ
ウムを含有しない金属硫化物あるいは酸化物や、Ｌｉx
ＭＯ2（但し、Ｍは１種類以上の遷移金属を表し、また
０．０５≦ｘ≦１．１０である）を主体とするリチウム
複合酸化物が挙げられる。このリチウム複合酸化物にお
いて、遷移金属ＭとしてはＣｏ、Ｎｉ、Ｍｎが好まし
い。Ｃｏ、Ｎｉを含むリチウム複合酸化物としてはＬｉ
ＣｏＯ2、ＬｉＮｉＯ2、ＬｉxＮｉyＣｏ1-yＯ2（ｘ、ｙ
は電池の充放電状態によって異なり、０＜ｘ＜１、０．
７＜ｙ＜１．０２である。但し、１．０≦ｙのときのＣ
ｏのモル比は０である。）、ＬｉＭｎ2Ｏ4等がある。こ
れらのリチウム複合酸化物は、高電圧を発生でき、電池
のエネルギー密度を高める上で優れている。For example, a metal oxide, a metal sulfide, or a specific polymer is used as the positive electrode material. Specifically, metal sulfides or oxides not containing lithium, such as TiS 2 , MoS 2 , NbSe 2 , V 2 O 5 , or Li x
A lithium composite oxide mainly composed of MO 2 (where M represents one or more transition metals and 0.05 ≦ x ≦ 1.10.) Is exemplified. In this lithium composite oxide, the transition metal M is preferably Co, Ni, or Mn. Li as a lithium composite oxide containing Co and Ni is Li
CoO 2 , LiNiO 2 , Li x Ni y Co 1-y O 2 (x, y
Varies depending on the charge / discharge state of the battery, and 0 <x <1, 0.
7 <y <1.02. However, when 1.0 ≦ y, C
The molar ratio of o is 0. ), LiMn 2 O 4 and the like. These lithium composite oxides can generate a high voltage and are excellent in increasing the energy density of a battery.
【００２９】なお、リチウム複合酸化物は、リチウムの
炭酸塩、硝酸塩、酸化物あるいは水酸化物と、遷移金属
の塩を、所望の組成に応じて粉砕混合した後、酸素雰囲
気中、６００〜１０００℃の温度範囲で焼成することに
よって合成される。The lithium composite oxide is prepared by pulverizing and mixing lithium carbonate, nitrate, oxide or hydroxide and a transition metal salt according to a desired composition, and then mixing the mixture in an oxygen atmosphere at 600 to 1000. It is synthesized by firing in a temperature range of ° C.
【００３０】この正極材料によって正極を形成するに
は、例えばこの正極材料の粉末を、結着剤、導電剤、分
散媒とともに混合して正極ミックスを調製し、この正極
ミックスを圧縮成型等によって所望の電極形状に形成し
ても良く、上記正極ミックスを帯状集電体の両面に塗
布、乾燥することで電極を形成しても構わない。In order to form a positive electrode from this positive electrode material, for example, a powder of this positive electrode material is mixed with a binder, a conductive agent and a dispersion medium to prepare a positive electrode mix, and this positive electrode mix is subjected to compression molding or the like. The positive electrode mix may be applied to both sides of the belt-shaped current collector and dried to form an electrode.
【００３１】非水電解液としては、電解質である軽金属
の塩を、有機溶媒に溶解したものが用いられる。As the non-aqueous electrolyte, a solution in which a salt of a light metal as an electrolyte is dissolved in an organic solvent is used.
【００３２】有機溶媒としては、例えばプロピレンカー
ボネート、エチレンカーボネート、ジエチルカーボネー
ト、メチルエチルカーボネート、１，２−ジメトキシエ
タン、１，２−ジエトキシエタン、γ−ブチルラクト
ン、テトラヒドロフラン、２−メチルテトラヒドロフラ
ン、１，３−ジオキソラン、４−メチル−１，３−ジオ
キソラン、ジプロピルカーボネート、ジエチルエーテ
ル、スルホラン、メチルスルホラン、アセトニトリル、
プロピルニトリル、アニソール、酢酸エステル、酪酸エ
ステル、プロピオン酸エステル等が挙げられる。これら
有機溶媒は、１種類を単独で用いても良く、２種類以上
を組み合わせて使用しても構わない。Examples of the organic solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyl lactone, tetrahydrofuran, 2-methyltetrahydrofuran, , 3-dioxolane, 4-methyl-1,3-dioxolane, dipropyl carbonate, diethyl ether, sulfolane, methylsulfolane, acetonitrile,
Examples thereof include propyl nitrile, anisole, acetate, butyrate, and propionate. One of these organic solvents may be used alone, or two or more thereof may be used in combination.
【００３３】電解質としては、リチウム、ナトリウム、
アルミニウム等の軽金属の塩が使用される。例えばリチ
ウム塩としては、ＬｉＣｌＯ4、ＬｉＡｓＦ6、ＬｉＰＦ
6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）
2等が挙げられる。As the electrolyte, lithium, sodium,
A salt of a light metal such as aluminum is used. For example, lithium salts include LiClO 4 , LiAsF 6 , LiPF
6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 )
And the like.
【００３４】電池の形状は特に限定されず、円筒形、角
形、コイン型、ボタン型等の種々の形状が採用できる。
但し、電池を密閉型とする場合には、より高い安全性を
確保するために、過充電等の異常状態が発生したときに
電池内圧の上昇に応じて電流を遮断する保護装置を設け
ることが好ましい。The shape of the battery is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a button shape can be adopted.
However, if the battery is sealed, a protection device that shuts off the current in response to an increase in the battery internal pressure when an abnormal condition such as overcharge occurs should be provided to ensure higher safety. preferable.
【００３５】[0035]
【実施例】本発明の具体的な実施例を実験結果に基づい
て説明する。EXAMPLES Specific examples of the present invention will be described based on experimental results.
【００３６】実施例１ キチン（和光純薬工業社製）４０ｇを、窒素気流中、温
度５００℃で５時間加熱することにより炭化させた。こ
の炭化物試料のうち１０ｇをアルミナ製のルツボに仕込
み、１０リットル／分の窒素気流中、５℃／分の昇温速
度で１２００℃（到達温度）まで加熱した。そして、こ
の温度を１時間保持することによって試料を焼成して十
分に炭化させ、負極用炭素質材料を得た。 Example 1 40 g of chitin (manufactured by Wako Pure Chemical Industries, Ltd.) was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream. 10 g of this carbide sample was charged into an alumina crucible and heated to 1200 ° C. (attained temperature) at a rate of 5 ° C./min in a nitrogen flow of 10 L / min. Then, the sample was fired by maintaining this temperature for 1 hour, and sufficiently carbonized to obtain a carbonaceous material for a negative electrode.
【００３７】実施例２ 原料としてキチンの代わりにキトサン（和光純薬工業社
製）を用いたこと以外は実施例１と同様にして、負極用
炭素質材料を得た。 Example 2 A carbonaceous material for a negative electrode was obtained in the same manner as in Example 1 except that chitosan (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of chitin as a raw material.
【００３８】実施例３ 中尾類のカニ（福井産・タラバ蟹）の外皮４０ｇを、水
洗、アルコール洗浄した後、窒素気流中、温度５００℃
で５時間加熱することにより炭化させた。次に、この炭
化物試料を塩酸で処理（脱灰）した後、中性になるまで
水洗した。そして、試料のうち１０ｇをアルミナ製のル
ツボに仕込み、１０リットル／分の窒素気流中、５℃／
分の昇温速度で１２００℃（到達温度）にまで加熱し、
この温度を１時間保持することによって試料を焼成して
十分に炭化させ、負極用炭素質材料を得た。 Example 3 40 g of the crust of a crab of the middle order (Fukui-produced king crab) was washed with water and alcohol, and then at a temperature of 500 ° C. in a nitrogen stream.
For 5 hours. Next, this carbide sample was treated (decalcified) with hydrochloric acid, and then washed with water until neutral. Then, 10 g of the sample was charged into an alumina crucible and placed in a nitrogen stream at 10 L / min.
Heated to 1200 ° C (attained temperature) at a heating rate of
By maintaining this temperature for 1 hour, the sample was fired and sufficiently carbonized to obtain a carbonaceous material for a negative electrode.
【００３９】比較例１ 原料としてキチンの代わりに石油ピッチを用い、実施例
１と同様の炭化、焼成処理を行うことによって負極用炭
素質材料を得た。 Comparative Example 1 A carbonaceous material for a negative electrode was obtained by performing the same carbonization and firing treatment as in Example 1 using petroleum pitch instead of chitin as a raw material.
【００４０】そして、得られた炭素質材料を用いてテス
トセルを作製し、負極材料としての特性を評価した。テ
ストセルの作製方法、負極容量の試験方法を以下に示
す。Then, a test cell was prepared using the obtained carbonaceous material, and the characteristics as a negative electrode material were evaluated. A method for manufacturing a test cell and a method for testing a negative electrode capacity are described below.
【００４１】＜テストセルの作製＞各負極用炭素質材料
を乳鉢で粉砕し、篩いにより分級することで径が３８μ
ｍ以下の炭素質粉末を収集した。<Preparation of Test Cell> Each negative electrode carbonaceous material was pulverized in a mortar and classified by a sieve to obtain a 38 μm diameter.
m or less of carbonaceous powder was collected.
【００４２】次いで、この炭素質粉末表面に吸着した水
分等を揮発除去するために、当該炭素質粉末を、アルゴ
ン雰囲気中、３０℃／分の昇温速度で６００℃（到達温
度）にまで加熱し、この温度を１時間保持し、その後室
温まで冷却した。Next, in order to volatilize and remove the moisture and the like adsorbed on the surface of the carbonaceous powder, the carbonaceous powder is heated to 600 ° C. (attained temperature) at a rate of 30 ° C./min in an argon atmosphere. Then, this temperature was maintained for 1 hour, and then cooled to room temperature.
【００４３】冷却後、直ちにこの炭素質粉末９０重量％
と、結着剤となるポリフッ化ビニリデン（ＰＶＤＦ）１
０重量％、溶剤となるジメチルホルムアミドとを均一に
混合し、乾燥させることで負極ミックスを調製した。Immediately after cooling, 90% by weight of this carbonaceous powder
And polyvinylidene fluoride (PVDF) 1 as a binder
A negative electrode mix was prepared by uniformly mixing 0% by weight of dimethylformamide as a solvent and drying.
【００４４】そして、この負極ミックス３５ｍｇと、集
電体であるニッケルメッシュ（ニッケル繊維径２０μ
ｍ）とを合わせてカーボン電極を作製し、このカーボン
電極を次に示すセル構成のコイン型テストセル（直径２
０ｍｍ、厚さ２．５ｍｍ）に組み込んだ。Then, 35 mg of the negative electrode mix and a nickel mesh (nickel fiber diameter: 20 μm) as a current collector were used.
m) to form a carbon electrode, and this carbon electrode is used as a coin-type test cell (diameter 2
0 mm, thickness 2.5 mm).
【００４５】セル構成： 対極 ；Ｌｉ金属 セパレータ；ポリプロピレン製多孔質膜 電解液 ；プロピレンカーボネートとジメトキシエタ
ンとの混合溶媒（容積比１：１）に電解質としてＬｉＣ
ｌＯ4を１モル／リットルの割合で溶解させた溶液 集電体 ；銅箔Cell configuration: Counter electrode; Li metal separator; Polypropylene porous membrane Electrolyte; LiC as solvent in mixed solvent of propylene carbonate and dimethoxyethane (volume ratio 1: 1)
Solution in which 10 4 is dissolved at a rate of 1 mol / liter Current collector; copper foil
【００４６】＜負極容量試験＞テストセルに対して、１
ｍＡ（電流密度０．５３ｍＡ／ｃｍ2）の定電流で以下
の充放電を行った。なお、この方法で見積もられた充放
電（負極）容量は、平衡電位を基準としているので、材
料固有の特性を反映したものとなる。<Negative electrode capacity test>
The following charge / discharge was performed at a constant current of mA (current density 0.53 mA / cm 2 ). It should be noted that the charge / discharge (negative electrode) capacity estimated by this method is based on the equilibrium potential, and therefore reflects characteristics inherent to the material.
【００４７】充電：１時間の通電（充電）と２時間の休
止とを繰り返し行った。ここで、各休止時において休止
時間のマイナス０．５乗を横軸にして電圧をプロット
し、このプロットを無限時間に外挿し、充放電容量によ
って平衡電位を見積もった（断続充放電法）。なお、充
電は、平衡電位がリチウムに対し３ｍＶとなった時点で
終了にした。Charging: The energization (charging) for one hour and the rest for two hours were repeated. Here, the voltage was plotted with the pause time minus 0.5 raised to the abscissa at each pause, the plot was extrapolated to infinite time, and the equilibrium potential was estimated from the charge / discharge capacity (intermittent charge / discharge method). The charging was terminated when the equilibrium potential became 3 mV with respect to lithium.
【００４８】放電：１時間の通電（放電）と２時間の休
止とを繰り返し、通電状態で電圧が１．５Ｖを下回った
時点で放電を終了にした。ここでは、このとき測定され
る放電容量を、カーボン電極の炭素重量で除した値を、
カーボン電極の充放電容量とした。Discharge: One hour of energization (discharge) and two hours of rest were repeated, and the discharge was terminated when the voltage fell below 1.5 V in the energized state. Here, the value obtained by dividing the discharge capacity measured at this time by the carbon weight of the carbon electrode,
The charge / discharge capacity of the carbon electrode was used.
【００４９】この負極容量試験の結果を表１に示す。な
お、表１中、実施例１〜実施例３については、比較例１
の放電容量に対する放電容量の増加分及び増加率も併せ
て示した。Table 1 shows the results of the negative electrode capacity test. In Table 1, for Examples 1 to 3, Comparative Example 1
The increase and the rate of increase of the discharge capacity with respect to the discharge capacity of Table 2 are also shown.
【００５０】[0050]
【表１】 [Table 1]
【００５１】表１に示すように、キチン、キトサンまた
はカニの上皮を原料にして合成された炭素質材料は、石
油ピッチを原料にして合成された炭素質材料に比べて大
きな充放電容量が得られる。As shown in Table 1, the carbonaceous material synthesized using chitin, chitosan or crab epithelium as a raw material has a larger charge / discharge capacity than the carbonaceous material synthesized using petroleum pitch as a raw material. Can be
【００５２】このことから、キチン、キトサンあるいは
カニの上皮を原料にすると、負極としての特性に優れた
炭素質材料が合成できることがわかった。From this, it was found that a carbonaceous material having excellent characteristics as a negative electrode can be synthesized by using the epithelium of chitin, chitosan or crab as a raw material.
【００５３】[0053]
【発明の効果】以上の説明からも明らかなように、本発
明では、キチンまたはキトサンの少なくともいずれかを
含有する材料の焼成体を含有する負極材料を使用する。
この焼成体は充放電容量が非常に大きいので、負極材料
として用いることによってエネルギー密度の高い非水電
解液二次電池が得られる。また、キチン、キトサンは、
カニやエビの外皮等から豊富に抽出できるので、廃棄物
となったカニやエビの外皮を負極材料の原料として有効
利用することが可能になる。As is apparent from the above description, the present invention uses a negative electrode material containing a fired body of a material containing at least one of chitin and chitosan.
Since this fired body has a very large charge / discharge capacity, a non-aqueous electrolyte secondary battery having a high energy density can be obtained by using it as a negative electrode material. Also, chitin and chitosan are
Since the crab and shrimp can be abundantly extracted from the crust and the shrimp, the crust and the shrimp can be effectively used as a raw material of the negative electrode material.
Claims (5)
れかを含む材料の焼成体を含有することを特徴とする負
極材料。1. A negative electrode material comprising a fired body of a material containing at least one of chitin and chitosan.
れかを含む材料は、カニの外皮であることを特徴とする
請求項１記載の負極材料。2. The negative electrode material according to claim 1, wherein the material containing at least one of chitin and chitosan is a crab skin.
れかを含む材料を、非酸化性雰囲気下で焼成することを
特徴とする負極材料の製造方法。3. A method for producing a negative electrode material, comprising firing a material containing at least one of chitin and chitosan in a non-oxidizing atmosphere.
り、 負極は、キチンまたはキトサンの少なくともいずれかを
含む材料の焼成体を含有することを特徴とする非水電解
液二次電池。4. A non-aqueous electrolyte secondary battery comprising a negative electrode, a positive electrode and a non-aqueous electrolyte, wherein the negative electrode contains a fired body of a material containing at least one of chitin and chitosan.
ことを特徴とする請求項４記載の非水電解液二次電池。5. The non-aqueous electrolyte secondary battery according to claim 4, wherein the positive electrode contains a lithium-containing compound.
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| JP12593097A JP3713892B2 (en) | 1997-05-15 | 1997-05-15 | Negative electrode material, negative electrode material manufacturing method, and non-aqueous electrolyte secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12593097A JP3713892B2 (en) | 1997-05-15 | 1997-05-15 | Negative electrode material, negative electrode material manufacturing method, and non-aqueous electrolyte secondary battery |
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| Publication Number | Publication Date |
|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008015828A1 (en) * | 2006-08-04 | 2008-02-07 | Kyoritsu Chemical & Co., Ltd. | Coating liquid for manufacturing electrode plate, undercoating agent, and use thereof |
| JP2009272311A (en) * | 2009-07-21 | 2009-11-19 | Kyoritsu Kagaku Sangyo Kk | Adhesive for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same |
| JP2015220037A (en) * | 2014-05-15 | 2015-12-07 | 国立大学法人 名古屋工業大学 | Method for manufacturing air electrode using nitrogen-containing natural organic matter |
-
1997
- 1997-05-15 JP JP12593097A patent/JP3713892B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008015828A1 (en) * | 2006-08-04 | 2008-02-07 | Kyoritsu Chemical & Co., Ltd. | Coating liquid for manufacturing electrode plate, undercoating agent, and use thereof |
| JP2008060060A (en) * | 2006-08-04 | 2008-03-13 | Kyoritsu Kagaku Sangyo Kk | Coating liquid for manufacturing electrode plate, undercoating agent, and use thereof |
| US8537525B2 (en) | 2006-08-04 | 2013-09-17 | Kyoritsu Chemical & Co., Ltd. | Coating liquid for manufacturing electrode plate, undercoating agent, and use therof |
| US9269501B2 (en) | 2006-08-04 | 2016-02-23 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Coating formulation for manufacturing electrode plate and use thereof |
| JP2009272311A (en) * | 2009-07-21 | 2009-11-19 | Kyoritsu Kagaku Sangyo Kk | Adhesive for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same |
| JP2015220037A (en) * | 2014-05-15 | 2015-12-07 | 国立大学法人 名古屋工業大学 | Method for manufacturing air electrode using nitrogen-containing natural organic matter |
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| Publication number | Publication date |
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