JP2001167755A - Negative electrode material for use in non-aqueous secondary battery and method of producing the same - Google Patents
Negative electrode material for use in non-aqueous secondary battery and method of producing the sameInfo
- Publication number
- JP2001167755A JP2001167755A JP34749199A JP34749199A JP2001167755A JP 2001167755 A JP2001167755 A JP 2001167755A JP 34749199 A JP34749199 A JP 34749199A JP 34749199 A JP34749199 A JP 34749199A JP 2001167755 A JP2001167755 A JP 2001167755A
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- Prior art keywords
- negative electrode
- electrode material
- secondary battery
- water
- natural graphite
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Classifications
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、初期の充放電ロス
が低減し、従って初期の充放電効率が良好である非水系
二次電池用の負極材に関するものである。また、そのよ
うな負極材を製造する工業的に有利な方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode material for a non-aqueous secondary battery in which the initial charge / discharge loss is reduced and the initial charge / discharge efficiency is good. The invention also relates to an industrially advantageous method for producing such a negative electrode material.
【０００２】[0002]
【従来の技術】近年、電子機器の小型化の観点から、鉛
蓄電池やニッカド電池に代わる高容量電池、特にリチウ
ム二次電池が注目され、実用化されている。リチウム二
次電池の中でも、負極に天然黒鉛または人造黒鉛などの
炭素材料を用いたものは、安全性、高容量、高電圧の点
で有利である。2. Description of the Related Art In recent years, from the viewpoint of miniaturization of electronic equipment, high-capacity batteries, particularly lithium secondary batteries, which replace lead-acid batteries or nickel-cadmium batteries have attracted attention and have been put to practical use. Among the lithium secondary batteries, those using a carbon material such as natural graphite or artificial graphite for the negative electrode are advantageous in terms of safety, high capacity, and high voltage.
【０００３】天然黒鉛または人造黒鉛を用いたリチウム
二次電池用負極材については、たとえば次のような出願
がなされている。For example, the following application has been filed for a negative electrode material for a lithium secondary battery using natural graphite or artificial graphite.
【０００４】（１）特開平６−２９０７８１号公報 リチウムイオンを吸蔵放出可能な負極材料として天然黒
鉛が使用されたリチウム二次電池において、前記天然黒
鉛が、１８００℃以上の温度で加熱処理されたものであ
るリチウム二次電池が示されている。(1) JP-A-6-290781 In a lithium secondary battery using natural graphite as a negative electrode material capable of inserting and extracting lithium ions, the natural graphite is heated at a temperature of 1800 ° C. or more. Is shown.
【０００５】（２）特開平８−２１３０２０号公報 鱗片状天然黒鉛をジェットミル粉砕した粒度１〜１００
μm 、純度９０％以上の黒鉛であって、この粉砕黒鉛を
充放電電圧0.02〜0.5 V の条件で充放電試験したときの
２回目以降の充放電容量が２５０mAh/g 以上である二次
電池の電極材料が示されている。(2) Japanese Patent Application Laid-Open No. 8-213020 JP-A-8-213020 Particle size 1 to 100 obtained by jet-milling flaky natural graphite.
μm, a graphite having a purity of 90% or more, and having a charge / discharge capacity of 250 mAh / g or more for the second and subsequent times when a charge / discharge test is performed on the ground graphite under conditions of a charge / discharge voltage of 0.02 to 0.5 V. Electrode materials are shown.
【０００６】（３）特開平８−２９８１１７号公報 ジェットミル粉砕され、純度が99.9％以上で、粒度が１
〜１００μm の高純度鱗片状天然黒鉛であって、充放電
電圧0.02〜0.5 V の条件で充放電試験したときの２回目
以降の充放電容量が３００mAh/g 以上である二次電池の
電極材料が示されている。(3) JP-A-8-298117 JP-A-8-298117 Jet mill pulverization, purity 99.9% or more, particle size 1
The electrode material of a secondary battery, which is a high-purity flaky natural graphite having a charge capacity of 300 mAh / g or more when subjected to a charge / discharge test under a condition of a charge / discharge voltage of 0.02 to 0.5 V, is 300 mAh / g or more. It is shown.
【０００７】（４）特開平８−２９８１１６号公報 原油精製工程で発生した減圧蒸留残渣油を過熱水蒸気に
より部分的に熱分解したときの缶残である粘結材を原料
とし、該粘結材をコークス化可能な温度で黒鉛化するこ
とにより得た人造黒鉛の粉体を、二次電池の電極材料と
して用いてなる二次電池の電極材料が示されている。(4) Japanese Patent Application Laid-Open No. Hei 8-298116 The binder obtained as a residue when the vacuum distillation residue generated in the crude oil refining process is partially thermally decomposed by superheated steam is used as a raw material. There is shown an electrode material for a secondary battery using artificial graphite powder obtained by graphitizing at a temperature capable of coking as an electrode material for a secondary battery.
【０００８】（５）特開平１１−１６７９２０号公報 ピッチ系材料に代表される炭素前駆体(A) と黒鉛材(B)
とを混合後、不活性ガス雰囲気中にて１０００〜３００
０℃で熱処理すること、およびその熱処理後の混合物に
占める炭素前駆体(A) 由来の熱処理物の比率が１〜７０
重量％である非水系二次電池用負極材の製造法が示され
ている。(5) JP-A-11-167920 A carbon precursor (A) represented by a pitch-based material and a graphite material (B)
And then mixed in an inert gas atmosphere at 1000 to 300
Heat-treating at 0 ° C., and the ratio of the heat-treated product derived from carbon precursor (A) to the mixture after the heat-treatment is 1 to 70.
A method for producing a negative electrode material for a non-aqueous secondary battery in a weight percentage of 2 is shown.
【０００９】（６）特開平１１−２６３６１２号公報 鱗片状天然黒鉛粒子を球形に近づくように改質した球形
化粒子であって、特定の円形度、破断面外観、Ｘ線回折
法におけるピーク強度比を有する鱗片状天然黒鉛改質粒
子を電極材料とする二次電池が示されている。(6) Japanese Unexamined Patent Application Publication No. 11-263612 Spherical particles obtained by modifying flaky natural graphite particles so as to approximate a spherical shape, having a specific circularity, fractured surface appearance, and peak intensity in X-ray diffraction. A secondary battery using flaky natural graphite modified particles having a specific ratio as an electrode material is shown.
【００１０】（７）特開平１０−２５５８００号公報 無定形無機物質固体が表面に付着している黒鉛粒子から
なるリチウム二次電池用負極材が示されている。無定形
無機物質の例はシリカやホウ酸リチウムなど、黒鉛粒子
の例は天然黒鉛または膨張黒鉛である。(7) Japanese Patent Application Laid-Open No. 10-255800 A negative electrode material for a lithium secondary battery comprising graphite particles having an amorphous inorganic substance solid adhered to the surface is disclosed. Examples of amorphous inorganic substances are silica and lithium borate, and examples of graphite particles are natural graphite or expanded graphite.
【００１１】（８）特開平１１−１１１２９２号公報 フリーラジカルと反応するマスキング剤（不飽和結合を
有する単量体、ラジカル重合開始剤など）と、所定の粒
径範囲の黒鉛粒子とを反応させるようにしたリチウムイ
オン二次電池負極用黒鉛材の製造方法が示されている。(8) JP-A-11-111292 A masking agent (a monomer having an unsaturated bond, a radical polymerization initiator, etc.) which reacts with free radicals is reacted with graphite particles having a predetermined particle size range. A method for producing such a graphite material for a negative electrode of a lithium ion secondary battery is shown.
【００１２】（９）特開平１１−２４０１０９号公報 非電解液を用いると共に炭素材を負極材料とするリチウ
ムイオン二次電池用負極を製造する方法において、平均
粒子径１〜５０μm の黒鉛粒子を核として、該黒鉛粒子
の表面を化学蒸着処理法により炭素層で被覆することに
より黒鉛−炭素複合材を形成するようにしたリチウムイ
オン二次電池用負極の製造方法が示されている。ここで
化学蒸着処理法とは、黒鉛粒子を加熱しながら、そこに
有機物の蒸気を導入し、黒鉛表面で有機物蒸気を炭化沈
着させる方法である。(9) JP-A-11-240109 In a method of manufacturing a negative electrode for a lithium ion secondary battery using a non-electrolyte solution and using a carbon material as a negative electrode material, graphite particles having an average particle diameter of 1 to 50 μm are nucleated. Discloses a method for producing a negative electrode for a lithium ion secondary battery in which a graphite-carbon composite material is formed by coating the surface of the graphite particles with a carbon layer by a chemical vapor deposition method. Here, the chemical vapor deposition method is a method in which an organic vapor is introduced into a graphite particle while heating the graphite particle to carbonize and deposit the organic vapor on the graphite surface.
【００１３】上記のうち（１）は天然黒鉛を高温処理す
るもの、（２）〜（３）は鱗片状天然黒鉛の粉砕手段に
着目したもの、（４）は人造黒鉛の原料源として特殊な
粘結材に着目したもの、（５）は黒鉛を他の炭素材で装
飾したもの、（６）は鱗片状天然黒鉛粒子を球形に改質
したもの、（７）は黒鉛粒子を無定形無機物質固体で装
飾したもの、（８）は黒鉛粒子をマスキング剤で装飾し
たもの、（９）は黒鉛粒子を化学蒸着処理法による炭素
層で装飾したものである。なお上記のうち（２）〜
（６）は、本出願人の出願にかかるものである。Of the above, (1) is for treating natural graphite at a high temperature, (2) to (3) are for focusing on means for pulverizing flaky natural graphite, and (4) is a special raw material source for artificial graphite. Focusing on binders, (5) is graphite decorated with another carbon material, (6) is flake shaped natural graphite particles modified to spherical shape, (7) is graphite particles made of amorphous inorganic material (8) is a graphite particle decorated with a masking agent, and (9) is a graphite particle decorated with a carbon layer by a chemical vapor deposition method. In addition, (2)-
(6) is related to the application of the present applicant.
【００１４】[0014]
【発明が解決しようとする課題】一般に、黒鉛材を用い
た二次電池の負極材料は、充放電容量は大きいものの、
充電時の電解液の分解などの副反応により、初期の充放
電効率が悪いという問題がある。すなわち、初回の充放
電時において、充電されたリチウムイオンが完全には放
電されず、充放電ロスを生ずるのである。充放電ロスは
電池容量の低下を惹き起こし、またサイクル特性、保存
特性などの性能にも悪影響を及ぼす。Generally, a negative electrode material of a secondary battery using a graphite material has a large charge / discharge capacity,
There is a problem that the initial charge / discharge efficiency is poor due to side reactions such as decomposition of the electrolyte during charging. That is, during the first charge / discharge, the charged lithium ions are not completely discharged, and charge / discharge loss occurs. The charge / discharge loss causes a decrease in battery capacity, and also adversely affects performance such as cycle characteristics and storage characteristics.
【００１５】充放電ロスを低減するためには、炭素材の
比表面積を低減することが有効であると考えられるが、
そのためには、微粉を除去したり、他の炭素原料と複合
化して熱処理したりするなどの手段を講じる必要があ
り、材料の歩留まりや熱処理コストなどの点で工業的方
法としてはさらに改良を図ることが望まれる。上に例示
した従来技術によってもそれなりの改善は図られるが、
工程操作がかなり複雑となるため、より実用性に富む工
業的方法を見い出すことが強く要請される。In order to reduce charge / discharge loss, it is considered effective to reduce the specific surface area of the carbon material.
For this purpose, it is necessary to take measures such as removing fine powder or complexing with other carbon raw materials and heat-treating them, and further improve the industrial method in terms of material yield and heat treatment costs. It is desired. Although some improvements can be achieved by the prior art illustrated above,
Due to the considerable complexity of the process operations, there is a strong demand to find more practical industrial methods.
【００１６】本発明は、このような背景下において、実
用性ある充電容量および放電容量を有しているのみなら
ず、初期の充放電ロスが小さく、従って初期の充放電効
率が良好である非水系二次電池用負極材を提供するこ
と、およびそのような負極材を製造する工業的に有利な
方法を提供することを目的とするものである。Under such circumstances, the present invention not only has a practical charge capacity and a discharge capacity but also has a small initial charge / discharge loss, and thus has a good initial charge / discharge efficiency. It is an object of the present invention to provide a negative electrode material for an aqueous secondary battery and to provide an industrially advantageous method for producing such a negative electrode material.
【００１７】[0017]
【課題を解決するための手段】本発明の非水系二次電池
用負極材は、水溶性高分子材料(P) を負極材料(E) に担
持させてなるものである。The negative electrode material for a non-aqueous secondary battery of the present invention comprises a water-soluble polymer material (P) supported on a negative electrode material (E).
【００１８】本発明の非水系二次電池用負極材の製造法
は、水溶性高分子材料(P) の水溶液を負極材料(E) と接
触させ、該負極材料(E) に前記水溶性高分子材料(P) を
担持させることを特徴とするものである。In the method for producing a negative electrode material for a non-aqueous secondary battery according to the present invention, an aqueous solution of a water-soluble polymer material (P) is brought into contact with a negative electrode material (E), and the water-soluble high-molecular material (E) is added to the negative electrode material (E). It is characterized by supporting a molecular material (P).
【００１９】[0019]
【発明の実施の形態】以下本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００２０】負極材料(E) としては、天然黒鉛や人造黒
鉛の粒子が好適に使用される。これらの黒鉛粒子の粒度
に特に限定はないものの、平均粒子径で 0.1〜５００μ
m 、好ましくは１〜２００μm 、殊に５〜１００μm 、
なかんずく１０〜８０μm の範囲から選択するのが実際
的である。As the negative electrode material (E), particles of natural graphite or artificial graphite are preferably used. Although the particle size of these graphite particles is not particularly limited, the average particle size is 0.1 to 500 μm.
m, preferably 1 to 200 μm, especially 5 to 100 μm,
In particular, it is practical to choose from a range of 10 to 80 μm.
【００２１】水溶性高分子材料(P) としては、好適に
は、カルボキシメチルセルロース、ヒドロキシメチルセ
ルロース、ヒドロキシエチルセルロース、メチルセルロ
ース、エチルセルロース、アルギン酸、アルギン酸アル
キレングリコールエステル、キサンタンガム、アラビア
ガム、カードラン、プルラン、カラギーナン、グアーガ
ム、ローカストビーンガム、トラガントガム、寒天、ク
インスシード（マルメロ）、コンニャクマンナン、ペク
チン、ゼラチン、カゼイン、ニカワ、フノリをはじめと
する植物、微生物、動物由来の多糖類系またはタンパク
質系の水溶性高分子があげられる。塩の形をとりうるも
のは、水溶性塩の形態でもよい。As the water-soluble polymer material (P), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, alginic acid, alkylene glycol alginates, xanthan gum, gum arabic, curdlan, pullulan, carrageenan, Guar gum, locust bean gum, tragacanth gum, agar, quince seed (quince), konjac mannan, pectin, gelatin, casein, glue, funori and other plants, microorganisms, animal-derived polysaccharide-based or protein-based water-soluble polymers Is raised. What can take the form of a salt may be in the form of a water-soluble salt.
【００２２】水溶性高分子材料(P) は、多糖類系または
タンパク質系の水溶性高分子のほか、ポリビニルアルコ
ールのような合成系の水溶性高分子であってもよい。The water-soluble polymer material (P) may be a polysaccharide-based or protein-based water-soluble polymer or a synthetic water-soluble polymer such as polyvinyl alcohol.
【００２３】本発明の非水系二次電池用負極材は、上述
の水溶性高分子材料(P) の水溶液を、上述のような負極
材料(E) と接触させた後、乾燥して、該負極材料(E) に
担持させることにより得られる。The negative electrode material for a non-aqueous secondary battery of the present invention is prepared by bringing the above-mentioned aqueous solution of the water-soluble polymer material (P) into contact with the above-mentioned negative electrode material (E) and then drying it. It is obtained by being supported on the negative electrode material (E).
【００２４】上記の水溶性高分子材料(P) の担持量は、
負極材料(E) に対し0.05〜 2.0重量％であることが望ま
しく、その担持量が余りに少ないときは所期の効果が充
分には奏されず、一方その担持量が余りに多いときに
は、充放電量の低下を招くのでかえってマイナスとな
る。水溶性高分子材料(P) の担持量の好ましい範囲は、
下限が 0.1重量％、殊に 0.2重量％、なかんずく 0.3重
量％、上限が 1.8重量％、殊に 1.5重量％、なかんずく
1.3重量％である。The amount of the water-soluble polymer material (P) supported is
It is desirable that the amount is 0.05 to 2.0% by weight based on the negative electrode material (E). When the supported amount is too small, the intended effect is not sufficiently exhibited. Instead, it becomes negative. The preferred range of the amount of the water-soluble polymer material (P) supported is
Lower limit is 0.1% by weight, especially 0.2% by weight, especially 0.3% by weight, upper limit is 1.8% by weight, especially 1.5% by weight, especially
1.3% by weight.
【００２５】本発明においては、上記の水溶性高分子材
料(P) が担持された負極材料(E) を、非水系二次電池用
の負極材、殊に非水系リチウム二次電池用の負極材とし
て用いる。In the present invention, the negative electrode material (E) supporting the water-soluble polymer material (P) is used as a negative electrode material for a non-aqueous secondary battery, in particular, a negative electrode for a non-aqueous lithium secondary battery. Used as a material.
【００２６】リチウム二次電池における正極材料として
は、改質MnO2、LiCoO2、LiNiO2、LiNi1-yCoyO2、LiMn
O2、LiMn2O4 、LiFeO2などが用いられる。電解液として
は、エチレンカーボネートなどの有機溶媒や、該有機溶
媒とジメチルカーボネート、ジエチルカーボネート、
１，２−ジメトキシエタン、１，２−ジエトキシメタ
ン、エトキシメトキシエタンなどの低沸点溶媒との混合
溶媒に、LiPF6 、LiBF4 、LiClO4、LiCF3SO3などの電解
液溶質を溶解した溶液が用いられる。[0026] As the positive electrode material in a lithium secondary battery, reforming MnO 2, LiCoO 2, LiNiO 2 , LiNi 1-y Co y O 2, LiMn
O 2 , LiMn 2 O 4 , LiFeO 2 and the like are used. As the electrolytic solution, an organic solvent such as ethylene carbonate, and the organic solvent and dimethyl carbonate, diethyl carbonate,
Electrolyte solutes such as LiPF 6 , LiBF 4 , LiClO 4 , and LiCF 3 SO 3 were dissolved in a mixed solvent with a low-boiling solvent such as 1,2-dimethoxyethane, 1,2-diethoxymethane, and ethoxymethoxyethane. A solution is used.
【００２７】〈作用〉リチウム二次電池の充放電反応
は、たとえば下記の通りであり、リチウムイオンが正極
と負極の間を行き来する。左辺→右辺の反応が充電反
応、右辺→左辺への反応が放電反応である。 6C ＋ LiCoO2 ＝ C6Li ＋ CoO2 <Operation> The charge / discharge reaction of the lithium secondary battery is, for example, as follows, and lithium ions move between the positive electrode and the negative electrode. The reaction from the left side to the right side is a charging reaction, and the reaction from the right side to the left side is a discharging reaction. 6C + LiCoO 2 = C 6 Li + CoO 2
【００２８】本発明の非水系二次電池用負極材料は、黒
鉛粒子に代表される負極材料(E) に特定の水溶性高分子
材料(P) が担持されているため、実用性ある充電容量お
よび放電容量を有しているのみならず、初期の充放電ロ
スが小さく、従って初期の充放電効率が良好であるとい
う特長を有する。In the negative electrode material for a non-aqueous secondary battery of the present invention, a specific water-soluble polymer material (P) is supported on the negative electrode material (E) typified by graphite particles. In addition to having a discharge capacity, an initial charge / discharge loss is small, so that the initial charge / discharge efficiency is good.
【００２９】[0029]
【実施例】次に実施例をあげて本発明をさらに説明す
る。以下「部」とあるのは重量部である。The present invention will be further described with reference to the following examples. Hereinafter, "parts" refers to parts by weight.
【００３０】《実施例１〜４、比較例１》 〈負極材〉 実施例１ 水溶性高分子材料(P) の一例としてカルボキシメチルセ
ルロースを用い、負極材料(E) の一例として平均粒子径
２７μm の天然黒鉛粒子を用いた。カルボキシメチルセ
ルロース（Ｎａ塩） 0.1部を純水１００部に溶解し、こ
の水溶液中に天然黒鉛粒子１００部を投入してスラリー
とした。このスラリーを撹拌しながら、乾燥機中で１０
０℃で乾燥して水分を揮散させた後、解砕して、１５０
メッシュの篩を通過させた。これにより、天然黒鉛粒子
にカルボキシメチルセルロースが0.1重量％（天然黒鉛
に対し）担持された負極材が得られた。<< Examples 1 to 4, Comparative Example 1 >><Negative Electrode Material> Example 1 Carboxymethyl cellulose was used as an example of the water-soluble polymer material (P), and an average particle diameter of 27 μm was used as an example of the negative electrode material (E). Natural graphite particles were used. 0.1 part of carboxymethyl cellulose (Na salt) was dissolved in 100 parts of pure water, and 100 parts of natural graphite particles were charged into this aqueous solution to form a slurry. This slurry is stirred in a dryer for 10 minutes.
After drying at 0 ° C. to evaporate the water, it is crushed and
It was passed through a mesh sieve. As a result, a negative electrode material in which carboxymethyl cellulose was supported on natural graphite particles by 0.1% by weight (based on natural graphite) was obtained.
【００３１】実施例２ 実施例１と同様にして、天然黒鉛粒子にカルボキシメチ
ルセルロースが 0.5重量％（天然黒鉛粒子に対し）担持
された負極材を得た。Example 2 In the same manner as in Example 1, a negative electrode material in which carboxymethyl cellulose was supported on natural graphite particles by 0.5% by weight (based on the natural graphite particles) was obtained.
【００３２】実施例３ 実施例１と同様にして、天然黒鉛粒子にカルボキシメチ
ルセルロースが 1.0重量％（天然黒鉛粒子に対し）担持
された負極材を得た。Example 3 In the same manner as in Example 1, a negative electrode material in which carboxymethyl cellulose was supported on natural graphite particles by 1.0% by weight (based on the natural graphite particles) was obtained.
【００３３】実施例４ 実施例１と同様にして、天然黒鉛粒子にカルボキシメチ
ルセルロースが 1.5重量％（天然黒鉛粒子に対し）担持
された負極材を得た。Example 4 In the same manner as in Example 1, a negative electrode material in which carboxymethyl cellulose was supported on natural graphite particles by 1.5% by weight (based on the natural graphite particles) was obtained.
【００３４】比較例１ 実施例１における平均粒子径２７μm の天然黒鉛粒子
を、そのまま負極材として用いた。Comparative Example 1 Natural graphite particles having an average particle diameter of 27 μm in Example 1 were used as they were as a negative electrode material.
【００３５】〈試験方法〉ポリビニリデンフルオライド
（バインダー）５部をＮ−メチルピロリドン中に溶解さ
せた溶液中に、実施例１〜４、比較例１で得た負極材１
００部を加えたものを銅箔上に塗布、乾燥して、試験電
極を作製した。<Test Method> A negative electrode material 1 obtained in Examples 1 to 4 and Comparative Example 1 was placed in a solution in which 5 parts of polyvinylidene fluoride (binder) was dissolved in N-methylpyrrolidone.
The test electrode was prepared by applying the solution to which 00 parts had been added on a copper foil and drying it.
【００３６】この試験電極を用い、また対極として金属
リチウムシートを用いて、２極式セルを組み立てた。電
解液としては、1M-LiPF6/(EC+DMC(1:1))（つまり、エチ
レンカーボネートとジメチルカーボネートとの容積比で
１：１の混合溶媒にLiPF6 を１Ｍの割合で溶解したも
の）を用いた。A bipolar cell was assembled using this test electrode and a lithium metal sheet as a counter electrode. As the electrolyte, 1M-LiPF 6 / (EC + DMC (1: 1)) (that is, LiPF 6 dissolved at a ratio of 1M in a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1) ) Was used.
【００３７】充電については、0.2mA/cm2 の電流値で 0
Vまで充電した後、 0 Vの定電圧電流値が0.01mA/cm2と
なるまで行った。放電は、0.2mA/cm2 の電流値で 1 Vま
で行った。As for charging, a current value of 0.2 mA / cm 2
After charging to V, the test was performed until the constant voltage current value of 0 V became 0.01 mA / cm 2 . Discharging was performed up to 1 V at a current value of 0.2 mA / cm 2 .
【００３８】〈条件および結果〉天然黒鉛粒子に対する
カルボキシメチルセルロースの担持量と、各サンプルの
１回目の充電容量、放電容量、充放電ロス（充電容量−
放電容量）、初期効率（１００×放電容量／充電容量）
の測定結果とを表１に示す。充電容量、放電容量、充放
電ロス、初期効率の各欄、および総合評価の欄には、実
用性の観点から、好ましいものの順に、○、□、△の符
号を付してある。<Conditions and Results> The amount of carboxymethylcellulose supported on natural graphite particles and the first charge capacity, discharge capacity, charge / discharge loss (charge capacity−
Discharge capacity), initial efficiency (100 × discharge capacity / charge capacity)
Table 1 shows the measurement results. In the columns of charge capacity, discharge capacity, charge / discharge loss, initial efficiency, and the column of total evaluation, symbols of ○, □, and Δ are assigned in the order of preference from the viewpoint of practicality.
【００３９】[0039]
【表１】 担持量 充電容量 放電容量 充放電ロス 初期効率 総合 (wt%) (mAh/g) (mAh/g) (mAh/g) (%) 評価 実施例１ 0.1 ○ 405 ○ 366 □ 39 □ 90.4 □ 実施例２ 0.5 ○ 396 ○ 362 ○ 34 ○ 91.4 ○ 実施例３ 1.0 ○ 395 ○ 361 ○ 34 ○ 91.4 ○ 実施例４ 1.5 □ 384 □ 350 ○ 34 ○ 91.1 □ 比較例１ - ○ 407 ○ 366 △ 41 △ 89.9 △ （注）天然黒鉛粒子の平均粒子径は２７μm [Table 1] Loaded capacity Charge capacity Discharge capacity Charge / discharge loss Initial efficiency Total(wt%) (mAh / g) (mAh / g) (mAh / g) (%) Evaluation Example 1 0.1 ○ 405 ○ 366 □ 39 □ 90.4 □ Example 2 0.5 ○ 396 ○ 362 ○ 34 ○ 91.4 ○ Example 3 1.0 ○ 395 ○ 361 ○ 34 ○ 91.4 ○Example 4 1.5 □ 384 □ 350 ○ 34 ○ 91.1 □ Comparative Example 1-○ 407 ○ 366 △ 41 △ 89.9 △ (Note) The average particle size of natural graphite particles is 27 μm
【００４０】現在においては二次電池の性能の向上の努
力は限界近くにまで来ており、それをさらに一段と向上
させることは容易ではない。表１において（後述の表２
においても）、比較例に比しての実施例の充放電ロスお
よび初期効率の数値は、一見するとそれほど大きくはな
いように見えるが、事実は電池性能のさらなる向上の点
で目覚ましいものがある。At present, efforts to improve the performance of secondary batteries are approaching their limits, and it is not easy to further improve them. In Table 1 (see Table 2 below)
), The values of the charge-discharge loss and the initial efficiency of the example as compared with the comparative example do not seem to be so large at first glance, but in fact, there is a remarkable point in further improving the battery performance.
【００４１】《実施例５〜９、比較例２》 〈負極材〉 実施例５ 水溶性高分子材料(P) の一例としてカルボキシメチルセ
ルロースを用い、負極材料(E) の一例として平均粒子径
４５μm の天然黒鉛粒子を用いた。カルボキシメチルセ
ルロース（Ｎａ塩） 0.5部を純水１００部に溶解し、こ
の水溶液中に天然黒鉛粒子１００部を投入してスラリー
とした。このスラリーを撹拌しながら、乾燥機中で１０
０℃で乾燥して水分を揮散させた後、解砕して、１５０
メッシュの篩を通過させた。これにより、天然黒鉛粒子
にカルボキシメチルセルロースが0.5重量％（天然黒鉛
に対し）担持された負極材が得られた。Examples 5 to 9 and Comparative Example 2 <Negative Electrode Material> Example 5 Carboxymethyl cellulose was used as an example of the water-soluble polymer material (P), and an average particle diameter of 45 μm was used as an example of the negative electrode material (E). Natural graphite particles were used. 0.5 part of carboxymethylcellulose (Na salt) was dissolved in 100 parts of pure water, and 100 parts of natural graphite particles were charged into this aqueous solution to form a slurry. This slurry is stirred in a dryer for 10 minutes.
After drying at 0 ° C. to evaporate the water, it is crushed and
It was passed through a mesh sieve. As a result, a negative electrode material in which carboxymethylcellulose was supported on natural graphite particles by 0.5% by weight (based on natural graphite) was obtained.
【００４２】実施例６ 水溶性高分子材料(P) としてペクチンを用いたほかは実
施例５と同様にして、天然黒鉛粒子にペクチンが 0.5重
量％（天然黒鉛粒子に対し）担持された負極材を得た。Example 6 In the same manner as in Example 5 except that pectin was used as the water-soluble polymer material (P), a negative electrode material in which pectin was supported on natural graphite particles by 0.5% by weight (based on natural graphite particles) I got
【００４３】実施例７ 水溶性高分子材料(P) としてアルギン酸（Ｎａ塩）を用
いたほかは実施例５と同様にして、天然黒鉛粒子にアル
ギン酸が 0.5重量％（天然黒鉛粒子に対し）担持された
負極材を得た。Example 7 In the same manner as in Example 5 except that alginic acid (Na salt) was used as the water-soluble polymer material (P), 0.5% by weight (based on natural graphite particles) of alginic acid was supported on natural graphite particles. The obtained negative electrode material was obtained.
【００４４】実施例８ 水溶性高分子材料(P) としてゼラチンを用いたほかは実
施例５と同様にして、天然黒鉛粒子にゼラチンが 0.5重
量％（天然黒鉛粒子に対し）担持された負極材を得た。Example 8 In the same manner as in Example 5 except that gelatin was used as the water-soluble polymer material (P), a negative electrode material in which 0.5% by weight of gelatin was supported on natural graphite particles (based on natural graphite particles) I got
【００４５】実施例９ 水溶性高分子材料(P) としてポリビニルアルコールを用
いたほかは実施例５と同様にして、天然黒鉛粒子にポリ
ビニルアルコールが 0.5重量％（天然黒鉛粒子に対し）
担持された負極材を得た。Example 9 In the same manner as in Example 5 except that polyvinyl alcohol was used as the water-soluble polymer material (P), 0.5% by weight of polyvinyl alcohol was added to natural graphite particles (based on natural graphite particles).
A supported negative electrode material was obtained.
【００４６】比較例２ 実施例５における平均粒子径４５μm の天然黒鉛粒子
を、そのまま負極材として用いた。Comparative Example 2 Natural graphite particles having an average particle size of 45 μm in Example 5 were used as they were as a negative electrode material.
【００４７】〈試験方法、条件と結果〉実施例１と同様
にして試験を行った。条件と結果を表２に示す。<Test Method, Conditions and Results> A test was conducted in the same manner as in Example 1. Table 2 shows the conditions and results.
【００４８】[0048]
【表２】 担持量 充電容量 放電容量 充放電ロス 初期効率 総合 (wt%) (mAh/g) (mAh/g) (mAh/g) (%) 評価 実施例５ 0.5 ○ 385 ○ 358 ○ 27 ○ 93.0 ○ 実施例６ 0.5 ○ 381 ○ 352 ○〜□ 29 ○〜□ 92.4 ○〜□ 実施例７ 0.5 ○ 385 ○ 358 ○ 27 ○ 93.0 ○ 実施例８ 0.5 ○ 382 ○ 355 ○ 27 ○ 92.9 ○ 実施例９ 0.5 ○ 384 ○ 356 ○ 28 ○〜□ 92.7 ○〜□ 比較例２ - ○ 389 ○ 356 △ 33 △ 91.5 △ （注）天然黒鉛粒子の平均粒子径は４５μm [Table 2] Loaded capacity Charge capacity Discharge capacity Charge / discharge loss Initial efficiency Overall (wt%) (mAh / g) (mAh / g) (mAh / g) (%) Evaluation Example 5 0.5 ○ 385 ○ 358 ○ 27 ○ 93.0 ○ Example 6 0.5 ○ 381 ○ 352 ○ 〜 □ 29 ○ 〜 □ 92.4 ○ 〜 □ Example 7 0.5 ○ 385 ○ 358 ○ 27 ○ 93.0 ○ Example 8 0.5 ○ 382 ○ 355 ○ 27 ○ 92.9 ○ Example 9 0.5 ○ 384 ○ 356 ○ 28 ○ ～ □ 92.7 ○ ～ □ Comparative Example 2-○ 389 ○ 356 △ 33 △ 91.5 △ (Note) The average particle size of natural graphite particles is 45μm
【００４９】[0049]
【発明の効果】本発明の非水系二次電池用負極材は、実
用性ある充電容量および放電容量を有しているのみなら
ず、初期の充放電ロスが小さく、従って初期の充放電効
率が良好である。The negative electrode material for a non-aqueous secondary battery of the present invention not only has a practical charge capacity and a discharge capacity, but also has a small initial charge / discharge loss, and thus has a low initial charge / discharge efficiency. Good.
【００５０】加えて本発明にあっては、その非水系二次
電池用負極材の製造を、単に多糖類系、タンパク質系、
ポリビニアルコール系などの水溶性高分子材料(P) の水
溶液を負極材料(E) と接触させて担持させることにより
行うものであるため、製造工程がシンプルであり、原料
コストも小さく、工業的方法として極めてすぐれてい
る。In addition, in the present invention, the production of the negative electrode material for a non-aqueous secondary battery is simply carried out by using a polysaccharide-based, protein-based,
Since the process is carried out by bringing an aqueous solution of a water-soluble polymer material (P) such as a polyvinyl alcohol-based material into contact with and supporting the negative electrode material (E), the manufacturing process is simple, raw material costs are small, and industrial It is a very good method.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H003 AA02 BA03 BB01 BB11 BC01 BD04 5H014 AA02 BB06 BB08 EE01 EE08 HH01 5H029 AJ03 AK02 AK03 AL06 AL07 AM03 AM04 AM05 AM07 CJ08 CJ22 DJ08 EJ12 HJ01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H003 AA02 BA03 BB01 BB11 BC01 BD04 5H014 AA02 BB06 BB08 EE01 EE08 HH01 5H029 AJ03 AK02 AK03 AL06 AL07 AM03 AM04 AM05 AM07 CJ08 CJ22 DJ08 EJ12 HJ01
Claims (5)
持させてなる非水系二次電池用負極材。1. A negative electrode material for a non-aqueous secondary battery comprising a water-soluble polymer material (P) supported on a negative electrode material (E).
料(E) に対し0.05〜 2.0重量％である請求項１記載の非
水系二次電池用負極材。2. The negative electrode material for a non-aqueous secondary battery according to claim 1, wherein the amount of the water-soluble polymer material (P) supported is 0.05 to 2.0% by weight based on the negative electrode material (E).
パク質系またはポリビニルアルコール系の水溶性高分子
である請求項１記載の非水系二次電池用負極材。3. The negative electrode material for a non-aqueous secondary battery according to claim 1, wherein the water-soluble polymer material (P) is a polysaccharide-based, protein-based or polyvinyl alcohol-based water-soluble polymer.
載の非水系二次電池用負極材。4. The negative electrode material for a non-aqueous secondary battery according to claim 1, wherein the negative electrode material (E) is graphite particles.
(E) と接触させ、該負極材料(E) に前記水溶性高分子材
料(P) を担持させることを特徴とする非水系二次電池用
負極材の製造法。5. An aqueous solution of a water-soluble polymer material (P) is used as a negative electrode material.
(E), and the negative electrode material (E) carries the water-soluble polymer material (P) thereon. A method for producing a negative electrode material for a non-aqueous secondary battery, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34749199A JP2001167755A (en) | 1999-12-07 | 1999-12-07 | Negative electrode material for use in non-aqueous secondary battery and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34749199A JP2001167755A (en) | 1999-12-07 | 1999-12-07 | Negative electrode material for use in non-aqueous secondary battery and method of producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2001167755A true JP2001167755A (en) | 2001-06-22 |
Family
ID=18390592
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246020A (en) * | 2001-02-13 | 2002-08-30 | Sony Corp | Active material and non-aqueous electrolyte battery using the same, and battery producing method |
| EP1381098A1 (en) * | 2002-07-08 | 2004-01-14 | Shin-Kobe Electric Machinery Co., Ltd. | Non-aqueous electrolytic solution secondary battery |
| KR100910032B1 (en) | 2007-10-30 | 2009-07-30 | 한국기초과학지원연구원 | Method for fabrication of cationized ferritins on metal/Si substrate |
| JP2011150866A (en) * | 2010-01-21 | 2011-08-04 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
| JP2011198710A (en) * | 2010-03-23 | 2011-10-06 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode material, and nonaqueous secondary battery |
| JP2012094497A (en) * | 2010-09-27 | 2012-05-17 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode material, and nonaqueous secondary battery |
| JP2013157339A (en) * | 2013-05-23 | 2013-08-15 | Jfe Chemical Corp | Negative electrode mixture for lithium ion secondary battery |
| WO2016052715A1 (en) * | 2014-10-03 | 2016-04-07 | 学校法人 関西大学 | Binder, use thereof and method for producing electrode |
| JP2016066755A (en) * | 2014-09-25 | 2016-04-28 | 学校法人 関西大学 | Binder, electrode and electrochemical capacitor |
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1999
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246020A (en) * | 2001-02-13 | 2002-08-30 | Sony Corp | Active material and non-aqueous electrolyte battery using the same, and battery producing method |
| EP1381098A1 (en) * | 2002-07-08 | 2004-01-14 | Shin-Kobe Electric Machinery Co., Ltd. | Non-aqueous electrolytic solution secondary battery |
| KR100910032B1 (en) | 2007-10-30 | 2009-07-30 | 한국기초과학지원연구원 | Method for fabrication of cationized ferritins on metal/Si substrate |
| JP2011150866A (en) * | 2010-01-21 | 2011-08-04 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
| JP2011198710A (en) * | 2010-03-23 | 2011-10-06 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode material, and nonaqueous secondary battery |
| JP2012094497A (en) * | 2010-09-27 | 2012-05-17 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode material, and nonaqueous secondary battery |
| JP2013157339A (en) * | 2013-05-23 | 2013-08-15 | Jfe Chemical Corp | Negative electrode mixture for lithium ion secondary battery |
| JP2016066755A (en) * | 2014-09-25 | 2016-04-28 | 学校法人 関西大学 | Binder, electrode and electrochemical capacitor |
| WO2016052715A1 (en) * | 2014-10-03 | 2016-04-07 | 学校法人 関西大学 | Binder, use thereof and method for producing electrode |
| CN108511740A (en) * | 2017-03-13 | 2018-09-07 | 万向二三股份公司 | A kind of high-specific-capacity silicon carbon electrode coating preparation method |
| JP2019160614A (en) * | 2018-03-14 | 2019-09-19 | Tdk株式会社 | Lithium ion secondary battery |
| JP7059711B2 (en) | 2018-03-14 | 2022-04-26 | Tdk株式会社 | Lithium ion secondary battery |
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