JP3078800B1 - Method for producing negative electrode for non-aqueous secondary battery - Google Patents
Method for producing negative electrode for non-aqueous secondary batteryInfo
- Publication number
- JP3078800B1 JP3078800B1 JP11176606A JP17660699A JP3078800B1 JP 3078800 B1 JP3078800 B1 JP 3078800B1 JP 11176606 A JP11176606 A JP 11176606A JP 17660699 A JP17660699 A JP 17660699A JP 3078800 B1 JP3078800 B1 JP 3078800B1
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- JP
- Japan
- Prior art keywords
- negative electrode
- binder
- coating film
- silicon
- secondary battery
- 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.)
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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
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- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
【要約】
【課題】 ケイ素を負極活物質とし、高容量で優れたサ
イクル特性を与える非水系二次電池負極の製造方法を提
供する。
【解決手段】 ケイ素を含む負極材料と加熱処理により
難黒鉛化性炭素を形成するバインダーとからなる塗膜を
集電体上に形成し、非酸化性雰囲気下で焼結し、集電体
と一体化する。An object of the present invention is to provide a method for producing a negative electrode for a non-aqueous secondary battery, which uses silicon as a negative electrode active material and provides high capacity and excellent cycle characteristics. SOLUTION: A coating film comprising a negative electrode material containing silicon and a binder which forms non-graphitizable carbon by heat treatment is formed on a current collector, and sintered under a non-oxidizing atmosphere to form a coating film. Integrate.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ケイ素を活物質と
する焼結体を電極材料として用いる高容量で優れたサイ
クル特性を与える非水系二次電池用負極の製造方法に関
する。The present invention relates to a method for producing a negative electrode for a non-aqueous secondary battery which provides a high capacity and excellent cycle characteristics using a sintered body containing silicon as an active material as an electrode material.
【０００２】[0002]
【従来の技術】携帯電話やノ−トパソコン等の普及に伴
って、リチウムイオンを挿入放出可能な正極活物質及び
負極活物質を含む高容量なリチウム二次電池が注目され
ている。負極活物質として焼成炭素質材料を用いる負極
が実用化されているが、一層の高容量を有する負極活物
質が求められている。2. Description of the Related Art With the spread of portable telephones, notebook personal computers and the like, high-capacity lithium secondary batteries containing a positive electrode active material and a negative electrode active material capable of inserting and releasing lithium ions have been receiving attention. A negative electrode using a calcined carbonaceous material has been put to practical use as a negative electrode active material, but a negative electrode active material having a higher capacity is required.
【０００３】そこで、焼成炭素質材料より高容量が期待
できるケイ素を負極活物質として用い、負極を構成する
試みがなされている。例えば、特開平７-２９６０２号
公報には、ＬｉxＳｉ(０≦ｘ≦５）を負極活物質として
用い、導電材のグラファイトとバインダ−を加え成型し
てペレットとし、導電性接着剤を集電体として負極を製
造する方法が、また特開平５-７４４６３号公報には、
シリコン単結晶を活物質として用いニッケルメッシュで
鋏むことにより負極を製造する方法が開示されている。[0003] Attempts have been made to construct a negative electrode using silicon, which can be expected to have a higher capacity than a fired carbonaceous material, as the negative electrode active material. For example, Japanese Patent Application Laid-Open No. 7-29602 discloses that Li x Si (0 ≦ x ≦ 5) is used as a negative electrode active material, graphite and a binder as conductive materials are added to form a pellet, and a conductive adhesive is collected. A method for producing a negative electrode as an electric body is disclosed in JP-A-5-74463.
A method of manufacturing a negative electrode by using silicon single crystal as an active material and scissoring it with a nickel mesh has been disclosed.
【０００４】また、本出願人は、ＷＯ９８／２４１３５
号公報において、ケイ素と炭素質材料との複合体からな
る焼結体を負極に用いることを提案している。ケイ素又
はその化合物と、加熱処理により炭化可能な有機材料及
び／又は炭素材料とを非酸化性雰囲気下で加熱すること
により、ケイ素と炭素質材料が複合した焼結体が得られ
る。[0004] The applicant of the present invention has published WO 98/24135.
Japanese Patent Application Laid-Open Publication No. H11-216, proposes to use a sintered body composed of a composite of silicon and a carbonaceous material for a negative electrode. By heating silicon or its compound and an organic material and / or a carbon material that can be carbonized by heat treatment in a non-oxidizing atmosphere, a sintered body in which silicon and a carbonaceous material are combined can be obtained.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、ケイ素
を活物質に用いた負極は、充放電初期には高容量を与え
る反面、充放電の繰り返しに伴う容量の低下があり、高
性能化のためにはより一層のサイクル特性の向上が望ま
れている。However, while the negative electrode using silicon as an active material provides a high capacity at the beginning of charge and discharge, the capacity is reduced due to the repetition of charge and discharge. It is desired to further improve the cycle characteristics.
【０００６】そこで、本発明は、ケイ素を負極活物質と
し、高容量で優れたサイクル特性を与える非水系二次電
池負極の製造方法を提供することを目的とした。Accordingly, it is an object of the present invention to provide a method for producing a negative electrode of a non-aqueous secondary battery which uses silicon as a negative electrode active material and provides high capacity and excellent cycle characteristics.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
め、本発明の非水系二次電池用負極の製造方法は、ケイ
素を含む負極材料と加熱処理により難黒鉛化性炭素を形
成するバインダーとからなる塗膜を集電体上に形成し、
非酸化性雰囲気下で焼結し、集電体と一体することを特
徴とする。In order to achieve the above object, a method for producing a negative electrode for a non-aqueous secondary battery according to the present invention comprises a negative electrode material containing silicon and a binder for forming non-graphitizable carbon by heat treatment. Formed on the current collector, consisting of
It is characterized by being sintered under a non-oxidizing atmosphere and integrated with a current collector.
【０００８】本発明の製造方法においては、バインダー
は難黒鉛化性であり、体積変化の少ない非晶質炭素とな
るため、塗膜の形状を維持しながら焼結させることがで
きる。さらに非晶質炭素が焼結体内部に導電性ネットワ
ークを形成するため、焼結体の導電性を向上させること
ができる。また、集電体と塗膜とが密着した状態でバイ
ンダーが固相炭化するため、集電体と焼結体との密着性
が向上し、集電体と焼結体間の接触抵抗の低減が可能と
なる。In the production method of the present invention, since the binder is hardly graphitizable and becomes amorphous carbon with little change in volume, it can be sintered while maintaining the shape of the coating film. Further, since the amorphous carbon forms a conductive network inside the sintered body, the conductivity of the sintered body can be improved. In addition, since the binder is solidified and carbonized in a state where the current collector and the coating film are in close contact with each other, the adhesion between the current collector and the sintered body is improved, and the contact resistance between the current collector and the sintered body is reduced. Becomes possible.
【０００９】ここで、本発明における「加熱処理により
難黒鉛化性炭素を形成するバインダー」について詳述す
る。大谷らの著作「炭素繊維」（近代編集社刊）によれ
ば、「一般的にみて、ピッチコークスのように、液状を
経由して炭素化するものは易黒鉛化性炭素となり、フェ
ノールホルムアルデヒド樹脂や木材のような三次元的な
高分子物が溶融することなく炭素化したものが難黒鉛化
性炭素となる。」こと、そして、５００℃程度以下の温
度領域における炭素化でできた層構造は、より高温での
熱処理によっても基本的に引き継がれ、２０００℃程度
の高温処理により、初めてＸ線回折パラメータの上では
っきりとした違いになって現れること（同著図１．２
１）が知られている。すなわち、２０００℃程度の高温
処理をしたものでなければ、難黒鉛化性炭素であるか易
黒鉛化性炭素であるかを識別するのは困難であるが、難
黒鉛化性炭素になるかどうかは、基本的にそれぞれの原
料の本性によって決まるものである。Here, the "binder forming non-graphitizable carbon by heat treatment" in the present invention will be described in detail. According to Otani et al.'S book "Carbon Fibers" (published by Modern Editors, Inc.), "Pitch coke, such as pitch coke, is generally graphitizable carbon via liquid, and phenol formaldehyde resin A three-dimensional polymer such as wood or wood that is carbonized without melting becomes non-graphitizable carbon. ”And a layer structure formed by carbonization in a temperature range of about 500 ° C. or less. Is basically inherited even by heat treatment at a higher temperature, and appears for the first time as a clear difference in X-ray diffraction parameters by a high temperature treatment of about 2000 ° C. (FIG.
1) is known. That is, it is difficult to distinguish between non-graphitizable carbon and non-graphitizable carbon unless it has been subjected to a high-temperature treatment of about 2000 ° C. Is basically determined by the nature of each raw material.
【００１０】もちろん、炭素化条件を変えることによっ
てある程度意識的に制御可能であるが、例えば、ピッチ
を原料として難黒鉛化性炭素を得るには、塩素ガスを吹
き込みながら加熱するとか、イオウを５％程度以上添加
するなどの特殊な方法によらなければならないことが知
られている。逆に、本来は固相経由で炭素化する材料を
用いて易黒鉛化性炭素にするには、延伸などの操作によ
って、分子の配向性が顕著に変えられる場合などに限ら
れることが知られている。Of course, it is possible to consciously control the carbonization conditions to some extent by changing the carbonization conditions. For example, in order to obtain non-graphitizable carbon using pitch as a raw material, heating is performed while blowing chlorine gas or sulfur is blown. It is known that a special method such as addition of about% or more must be used. Conversely, it is known that the use of a material that is originally carbonized via a solid phase to make it easily graphitizable carbon is limited to cases where the orientation of molecules is significantly changed by an operation such as stretching. ing.
【００１１】具体的に、本発明において用いる「加熱処
理により難黒鉛化性炭素を形成するバインダー」として
は、例えば、フェノール樹脂、フラン樹脂、ウレタン樹
脂、エポキシ樹脂、ポリイミド樹脂、メラミン樹脂、尿
素樹脂等の熱硬化性樹脂、砂糖、デンプン、セルロース
誘導体等の糖類、ポリ塩化ビニリデン、ポリフッ化ビニ
リデン等のビニリデン樹脂、ゼラチン等の誘導タンパク
質や天然タンパク質、その他ポリアクリロニトリル等が
挙げられる。この中でも、特に、フェノール樹脂、フラ
ン樹脂、ビニリデン樹脂、糖類、ポリアクリロニトリル
及びゼラチンが好ましい。Specifically, the "binder forming non-graphitizable carbon by heat treatment" used in the present invention includes, for example, phenol resin, furan resin, urethane resin, epoxy resin, polyimide resin, melamine resin, urea resin And the like, sugars such as sugar, starch and cellulose derivatives, vinylidene resins such as polyvinylidene chloride and polyvinylidene fluoride, derived proteins such as gelatin, natural proteins, and other polyacrylonitriles. Among them, phenol resins, furan resins, vinylidene resins, sugars, polyacrylonitrile and gelatin are particularly preferred.
【００１２】また、本発明の製造方法において、上記バ
インダーの焼結後の残存率は５重量％以上、より好まし
くは１０重量％以上である。残存率が５重量％以上であ
れば、焼結体と集電体との間の接触抵抗低減に十分な密
着性が確保できる。ここで、残存率は、加熱処理前の重
量に対する加熱処理後の重量の比で表される。In the production method of the present invention, the residual ratio of the binder after sintering is at least 5% by weight, more preferably at least 10% by weight. When the residual ratio is 5% by weight or more, sufficient adhesion can be ensured for reducing the contact resistance between the sintered body and the current collector. Here, the residual ratio is represented by a ratio of the weight after the heat treatment to the weight before the heat treatment.
【００１３】[0013]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明に用いるケイ素としては、結晶質、非晶質のいず
れも用いる事ができ、ケイ素を含む化合物の形で用いて
も良い。ケイ素化合物としては、酸化ケイ素などの無機
ケイ素化合物や、シリコーン樹脂、含ケイ素高分子化合
物などの有機ケイ素化合物様の非酸化性雰囲気で分解又
は還元されてケイ素に変化し得る材料が挙げられる。こ
れらの中でも、特にケイ素粉末（単体）が好ましい。ケ
イ素粉末の純度は特に限定されるものではないが、十分
な容量を得るためケイ素含有率９０重量％以上であるこ
とが好ましく、経済性から９９．９９９重量％以下のも
のが好ましい。ケイ素粉末の粒子径は特に限定されない
が、ハンドリングや原料価格、負極材料の均一性の観点
から、平均粒子径０．０１μｍ以上１００μｍ以下のも
のが好適に用いられる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the silicon used in the present invention, either crystalline or amorphous silicon can be used, and it may be used in the form of a compound containing silicon. Examples of the silicon compound include inorganic silicon compounds such as silicon oxide, and materials that can be decomposed or reduced into silicon by being decomposed or reduced in a non-oxidizing atmosphere like an organic silicon compound such as a silicone resin or a silicon-containing polymer compound. Among these, silicon powder (single) is particularly preferred. The purity of the silicon powder is not particularly limited, but is preferably 90% by weight or more for obtaining a sufficient capacity, and preferably 99.999% by weight or less from the viewpoint of economy. Although the particle diameter of the silicon powder is not particularly limited, an average particle diameter of 0.01 μm or more and 100 μm or less is preferably used from the viewpoint of handling, raw material cost, and uniformity of the negative electrode material.
【００１４】また、本発明に用いる負極材料には、ケイ
素以外に、炭素材料又は熱処理で炭化する材料をも用い
るのが望ましい。ここで用いる炭素材料としては、コー
クス、ガラス状炭素、黒鉛、ピッチの炭化物及びこれら
の混合物が挙げられる。As the negative electrode material used in the present invention, it is desirable to use a carbon material or a material which is carbonized by heat treatment, in addition to silicon. Examples of the carbon material used here include coke, glassy carbon, graphite, carbide of pitch, and a mixture thereof.
【００１５】また、熱処理で炭化する材料としては、易
黒鉛化性炭素になるものを用いることができる。具体的
には、ナフタレンやアセナフチレン等の縮合系多環炭化
水素化合物又はその誘導体、あるいは上記化合物の混合
物を主成分とするピッチ、さらに熱処理で易黒鉛化性炭
素となる樹脂等が挙げられるが、ピッチが好ましい。な
お、熱処理で難黒鉛化炭素となる材料は、塗膜中に含ま
れる場合には、本発明で言うバインダーとなる。Further, as a material to be carbonized by the heat treatment, a material that becomes graphitizable carbon can be used. Specifically, a condensed polycyclic hydrocarbon compound such as naphthalene or acenaphthylene or a derivative thereof, or a pitch containing a mixture of the above compounds as a main component, and a resin that becomes easily graphitizable carbon by further heat treatment, etc. Pitch is preferred. In addition, the material which becomes non-graphitizable carbon by heat treatment becomes a binder referred to in the present invention when included in the coating film.
【００１６】本発明の加熱処理により難黒鉛化性炭素を
形成するバインダーに、塗膜と集電体との密着性を向上
させる目的で、ポリマーや可塑剤を添加しても良い。こ
の目的で添加するポリマーとしては、例えばフェノール
樹脂、フラン樹脂、ポリアクリロニトリルにはポリビニ
ルブチラール、ポリエステル、そしてアクリル樹脂等
を、砂糖にはポリエチレンイミン等を、ゼラチンにはポ
リエチレングリコール等を用いることができる。また、
可塑剤としては、例えば、ポリビニルブチラールを添加
した時にはフタル酸エステルやアジピン酸エステル等
を、バインダーとしてゼラチンを用いた場合にはグリセ
リン等を用いることができる。A polymer or a plasticizer may be added to the binder for forming the non-graphitizable carbon by the heat treatment in the present invention for the purpose of improving the adhesion between the coating film and the current collector. As the polymer to be added for this purpose, for example, phenol resin, furan resin, polyvinyl butylal, polyester, and acrylic resin for polyacrylonitrile, polyethylene imine and the like for sugar, polyethylene glycol and the like for gelatin can be used. . Also,
As the plasticizer, for example, phthalic acid ester or adipic acid ester can be used when polyvinyl butyral is added, and glycerin or the like can be used when gelatin is used as a binder.
【００１７】また、本発明のバインダーであるゼラチン
と砂糖とを混合して用いても良い。砂糖と混合すること
により、可塑剤を添加しなくても、ゼラチンを可塑化で
きる。Further, a mixture of gelatin and sugar as the binder of the present invention may be used. By mixing with sugar, gelatin can be plasticized without adding a plasticizer.
【００１８】本発明の製造方法において、塗膜を集電体
上に形成する場合には、特に限定されないが、塗膜の均
一性確保の観点から、負極材料とバインダーとを湿式混
合した塗液を塗布する方法が望ましい。また、塗液を集
電体上に直接塗布して塗膜を形成しても良いし、あるい
は他の基体上に塗布して形成した塗膜を剥離して集電体
に貼り付けても良い。剥離した塗膜を集電体に貼り付け
る場合、剥離し易い基体に塗液を塗布して塗膜化するの
が望ましい。塗液に含まれる溶剤、バインダー及び負極
活物質等との適合性により、基体を選択することができ
る。剥離剤処理したＰＥＴ製フィルムがこの目的の基体
に好適に用いられる。剥離した塗膜と集電体との貼り合
わせは、単に圧着のみで行なっても良いし、接着剤等を
用いて接着しても良い。In the production method of the present invention, when the coating film is formed on the current collector, there is no particular limitation, but from the viewpoint of ensuring the uniformity of the coating film, a coating liquid obtained by wet mixing the negative electrode material and the binder. Is preferred. Further, the coating liquid may be applied directly on the current collector to form a coating film, or the coating film formed by applying the coating liquid on another substrate may be peeled off and attached to the current collector. . When attaching the peeled coating film to the current collector, it is preferable to apply a coating liquid to a substrate that is easily peeled to form a coating film. A substrate can be selected depending on compatibility with a solvent, a binder, a negative electrode active material, and the like contained in the coating liquid. A PET film that has been treated with a release agent is suitably used for the substrate for this purpose. The peeling of the coating film and the current collector may be performed simply by pressure bonding, or may be performed using an adhesive or the like.
【００１９】また、負極材料とバインダーとを均一に混
合する目的で、予めバインダーを均一に溶解もしくは分
散させた液体と、負極材料とを混合するのが望ましい。
バインダーの溶液もしくは分散液の調製には、バインダ
ーや別に添加するポリマー及び可塑剤の溶解性や分散
性、負極材料の分散性や溶解性、並びに塗膜の乾燥速度
等に応じて、任意の溶剤や水を用いることができる。ま
た、塗液中の負極材料の分散性を向上させる目的で、分
散剤を添加しても良い。For the purpose of uniformly mixing the negative electrode material and the binder, it is desirable to mix a liquid in which the binder is uniformly dissolved or dispersed in advance with the negative electrode material.
In preparing the binder solution or dispersion, any solvent may be used depending on the solubility and dispersibility of the binder and the polymer and plasticizer to be added separately, the dispersibility and solubility of the negative electrode material, and the drying speed of the coating film. Or water can be used. A dispersant may be added for the purpose of improving the dispersibility of the negative electrode material in the coating liquid.
【００２０】また、負極材料とバインダーとを湿式混合
して塗液を得るには、塗液調製の常用手段である各種分
散機、すなわち、ロールミル、ボールミル、アトライタ
ー、サンドミル、ディスパーサー、ジェットミル及び超
音波分散機等を用いることができる。In order to obtain a coating liquid by wet mixing the negative electrode material and the binder, various dispersers which are commonly used for preparing a coating liquid, that is, roll mills, ball mills, attritors, sand mills, dispersers, jet mills And an ultrasonic dispersing machine.
【００２１】また、塗液を集電体あるいはその他基体上
に塗布するには、例えば、グラビアコーター、ダイコー
ター、ディップコーター、ブレードコーター、スピンコ
ーター及びスプレーコーター等の各種塗工機を用いるこ
とができる。In order to apply the coating liquid on the current collector or other substrate, various coating machines such as a gravure coater, a die coater, a dip coater, a blade coater, a spin coater and a spray coater may be used. it can.
【００２２】また、塗布した塗液を乾燥して塗膜を形成
するには、熱風乾燥機が乾燥効率の点で好ましいが、こ
れに限定されることなくその他各種の乾燥方法を用いる
ことができる。In order to form a coating film by drying the applied coating liquid, a hot air drier is preferable in terms of drying efficiency, but the drying method is not limited thereto, and various other drying methods can be used. .
【００２３】また、塗膜の均一性及び密度を向上させる
ため、必要に応じて、集電体上に形成された塗膜を、例
えば、ロールプレス機や平板プレス機等のプレス機で圧
縮することが望ましい。Further, in order to improve the uniformity and density of the coating film, the coating film formed on the current collector is compressed by a press machine such as a roll press machine or a flat press machine, if necessary. It is desirable.
【００２４】また、集電体に用いる導電性金属には、ス
テンレス、銅族及び白金族から選ばれたいずれか一つの
金属を用いる事ができるが、還元され易く、導電性が高
く、さらに安価である銅が望ましい。そして、導電性金
属には箔又はメッシュのいずれを用いても良いが、厚さ
は３〜１００μｍが望ましい。As the conductive metal used for the current collector, any one metal selected from stainless steel, copper group and platinum group can be used, but it is easily reduced, has high conductivity, and is inexpensive. Is desirable. Either a foil or a mesh may be used for the conductive metal, but the thickness is desirably 3 to 100 μm.
【００２５】また、塗膜を燒結する温度は、用いる導電
性金属の融点以下が望ましく、例えば銅を用いる場合に
は、融点１０８３℃以下、好ましくは５００〜１０００
℃である。ここで、焼結は窒素雰囲気下、アルゴン雰囲
気下等の非酸化性雰囲気下で行う。The temperature for sintering the coating film is desirably not higher than the melting point of the conductive metal used. For example, when copper is used, the melting point is not higher than 1083 ° C., preferably 500 to 1000.
° C. Here, the sintering is performed in a non-oxidizing atmosphere such as a nitrogen atmosphere or an argon atmosphere.
【００２６】本発明の正極活物質として用いられる正極
材料は、従来公知の何れの材料も使用でき、例えば、Ｌ
ｉxＣｏＯ2，ＬｉxＮｉＯ2，ＭｎＯ2，ＬｉxＭｎＯ2，
ＬｉxＭｎ2Ｏ4，ＬｉxＭｎ2-yＯ4，α−Ｖ2Ｏ5，ＴｉＳ
2等が挙げられる。As the cathode material used as the cathode active material of the present invention, any conventionally known materials can be used.
i x CoO 2, Li x NiO 2, MnO 2, Li x MnO 2,
Li x Mn 2 O 4 , Li x Mn 2-y O 4 , α-V 2 O 5 , TiS
And the like.
【００２７】本発明に使用される非水電解質は、エチレ
ンカーボネート、ジメチルカーボネート等の有機溶媒
に、ＬｉＰＦ6等のリチウム化合物を溶解させた非水電
解液、又は高分子にリチウム化合物を固溶或いはリチウ
ム化合物を溶解させた有機溶媒を保持させた高分子固体
電解質を用いることができる。The non-aqueous electrolyte used in the present invention is a non-aqueous electrolyte in which a lithium compound such as LiPF 6 is dissolved in an organic solvent such as ethylene carbonate or dimethyl carbonate, or a solid solution of a lithium compound in a polymer. A polymer solid electrolyte holding an organic solvent in which a lithium compound is dissolved can be used.
【００２８】[0028]
【実施例】実施例１．負極の作製 〈原料粉末の調製〉ケイ素粉末（平均粒子径１μｍ、純
度９９％、高純度化学研究所（株）製）８０重量部（以
下、重量部を部と略す）とグラファイト及びピッチ樹脂
との混合粉末（グラファイト９０部／ピッチ樹脂１０
部、大阪化成（株）製）２０部とを混合し、窒素雰囲気
下１１００℃で３時間焼成後、振動ミルで５分間粉砕
し、原料粉末を得た。[Embodiment 1] Preparation of negative electrode < Preparation of raw material powder> 80 parts by weight of silicon powder (average particle diameter 1 μm, purity 99%, manufactured by Kojundo Chemical Laboratory Co., Ltd.) (hereinafter, part by weight is abbreviated as “part”), graphite and pitch resin Powder mixture (graphite 90 parts / pitch resin 10)
And 20 parts of Osaka Chemical Co., Ltd.), and the mixture was fired at 1100 ° C. for 3 hours in a nitrogen atmosphere, and then pulverized with a vibration mill for 5 minutes to obtain a raw material powder.
【００２９】〈バインダーの分析〉バインダーのポリフ
ッ化ビニリデン（呉羽化学（株）製）を窒素雰囲気下で
熱重量分析したところ、８００℃における重量残存率は
２５％であった。<Analysis of Binder> A thermogravimetric analysis of a binder polyvinylidene fluoride (produced by Kureha Chemical Co., Ltd.) under a nitrogen atmosphere showed that the weight residual ratio at 800 ° C. was 25%.
【００３０】〈塗液の調製〉原料粉末３０部に、ポリフ
ッ化ビニリデンのＮ−メチル−２−ピロリドン溶液（１
０％）７０部を加え、振動ミルで１０分間混合して塗液
とした。<Preparation of Coating Liquid> 30 parts of the raw material powder was added to a solution of polyvinylidene fluoride in N-methyl-2-pyrrolidone (1
(0%) and mixed with a vibration mill for 10 minutes to obtain a coating liquid.
【００３１】〈塗膜の作製〉アプリケータ（ギャップ５
００μｍ）を用いて、塗液を銅箔（厚さ３０μｍ）上に
塗布し、８０℃で３０分間乾燥後、直径２ｃｍの円形に
裁断して、平板プレス機で１．５ｔ／ｃｍ2の圧力をか
けて圧着し、塗膜を得た。<Preparation of Coating Film> Applicator (gap 5
The coating solution was applied on a copper foil (thickness: 30 μm) using a dry press at 80 ° C. for 30 minutes, cut into a circular shape having a diameter of 2 cm, and pressed at a pressure of 1.5 t / cm 2 with a flat plate press. And pressed to obtain a coating film.
【００３２】〈塗膜の焼成〉塗膜を、窒素雰囲気下８０
０℃で３時間焼成して、負極とした。<Firing of the coating film>
It was fired at 0 ° C. for 3 hours to obtain a negative electrode.
【００３３】負極の評価 コバルト酸リチウム８８部、アセチレンブラック６部及
びポリテトラフルオロエチレン樹脂６部からなる混合物
を１ｔ／ｃｍ2の圧力で成型し、直径２ｃｍの円盤状の
正極を得た。 Evaluation of Negative Electrode A mixture comprising 88 parts of lithium cobaltate, 6 parts of acetylene black and 6 parts of polytetrafluoroethylene resin was molded at a pressure of 1 t / cm 2 to obtain a disk-shaped positive electrode having a diameter of 2 cm.
【００３４】電解液には、エチレンカーボネートとジメ
チルカーボネートとの体積比１：１の混合溶媒にＬｉＰ
Ｆ6を１ｍｏｌ／ｌの濃度に溶解したもの（三菱化学
（株）製）、セパレータには厚さ２５μｍの多孔性ポリ
エチレンフィルム（旭化成(株）製）、そして上記正極
及び負極を用いてコイン電池を作製した。そして、３６
時間室温でエージング後、２ｍＡの定電流で充放電試験
を行った。結果を表１に示す。The electrolytic solution was prepared by adding LiP to a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1.
F (manufactured by Mitsubishi Chemical Corporation) 6 which was dissolved in a concentration of 1 mol / l, porous polyethylene film having a thickness of 25μm as a separator (manufactured by Asahi Kasei Corporation), and the coin battery using the positive electrode and the negative electrode Was prepared. And 36
After aging at room temperature for a time, a charge / discharge test was performed at a constant current of 2 mA. Table 1 shows the results.
【００３５】実施例２．ポリアクリロニトリル（分子量
１５万、ポリサイエンス社製試薬）を実施例１と同様の
方法で熱重量分析した。８００℃における重量残存率は
３５％であった。Embodiment 2 FIG. Polyacrylonitrile (molecular weight: 150,000, reagent manufactured by Polyscience) was subjected to thermogravimetric analysis in the same manner as in Example 1. The weight retention rate at 800 ° C. was 35%.
【００３６】バインダーとして、このポリアクリロニト
リルを用い、ポリアクリロニトリル６部及びポリビニル
ブチラール（積水化学(株）製）２部をＮ−メチル−２
−ピロリドン６０部で希釈して原料粉末３２部に加えた
以外は実施例１と同様の方法で負極を作製し、コイン電
池を作製した。充放電試験の結果を表１に示す。Using this polyacrylonitrile as a binder, 6 parts of polyacrylonitrile and 2 parts of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd.) were mixed with N-methyl-2.
-A negative electrode was prepared in the same manner as in Example 1 except that the mixture was diluted with 60 parts of pyrrolidone and added to 32 parts of the raw material powder, to prepare a coin battery. Table 1 shows the results of the charge / discharge test.
【００３７】実施例３．フェノール−ホルムアルデヒド
樹脂（レゾール型、粘度５０Ｐａ・ｓ）を実施例１と同
様の方法で熱重量分析した。８００℃における重量残存
率は６０％であった。Embodiment 3 FIG. Phenol-formaldehyde resin (resole type, viscosity 50 Pa · s) was subjected to thermogravimetric analysis in the same manner as in Example 1. The weight retention at 800 ° C. was 60%.
【００３８】バインダーとして、このフェノール−ホル
ムアルデヒド樹脂を用い、フェノール−ホルムアルデヒ
ド樹脂７．５部及び実施例２で用いたポリビニルブチラ
ール５部をエタノール５０部に溶解させて、原料粉末３
７．５部に加えた以外は、実施例１と同様の方法で負極
を作製し、そしてコイン電池を作製した。充放電試験の
結果を表１に示す。This phenol-formaldehyde resin was used as a binder, and 7.5 parts of the phenol-formaldehyde resin and 5 parts of the polyvinyl butyral used in Example 2 were dissolved in 50 parts of ethanol.
A negative electrode was produced in the same manner as in Example 1 except that 7.5 parts was added, and a coin battery was produced. Table 1 shows the results of the charge / discharge test.
【００３９】ゼラチン（新田ゼラチン(株）製）を実施
例１と同様の方法で熱重量分析した。８００℃における
重量残存率は２０％であった。Gelatin (manufactured by Nitta Gelatin Co., Ltd.) was subjected to thermogravimetric analysis in the same manner as in Example 1. The weight retention rate at 800 ° C. was 20%.
【００４０】バインダーとして、このゼラチンを用い、
ゼラチン１２．５部及びグリセリン（和光純薬（株）製
試薬）２．５部を水５０部に溶解させて原料粉末３５部
に加えた以外は、実施例１と同様の方法で負極を作製
し、そしてコイン電池を作製した。充放電試験の結果を
表１に示す。Using this gelatin as a binder,
A negative electrode was prepared in the same manner as in Example 1 except that 12.5 parts of gelatin and 2.5 parts of glycerin (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 50 parts of water and added to 35 parts of the raw material powder. And a coin battery was fabricated. Table 1 shows the results of the charge / discharge test.
【００４１】実施例５．グラニュー糖（台糖(株）製）
を実施例１と同様の方法で熱重量分析した。８００℃に
おける重量残存率は１７％であった。Embodiment 5 FIG. Granulated sugar (Taito Co., Ltd.)
Was subjected to thermogravimetric analysis in the same manner as in Example 1. The weight retention rate at 800 ° C. was 17%.
【００４２】バインダーとして、このグラニュー糖を用
い、グラニュー糖１１部を水４４部に溶解させて３０％
ポリエチレンイミン水溶液（日本触媒(株）製）１０部
と共に、原料粉末３５部に加えた以外は、実施例１と同
様の方法で負極を作製し、そしてコイン電池を作製し
た。充放電試験の結果を表１に示す。Using this granulated sugar as a binder, 11 parts of granulated sugar was dissolved in 44 parts of water, and 30%
A negative electrode was produced in the same manner as in Example 1 except that 35 parts of the raw material powder was added together with 10 parts of a polyethyleneimine aqueous solution (manufactured by Nippon Shokubai Co., Ltd.), and a coin battery was produced. Table 1 shows the results of the charge / discharge test.
【００４３】難黒鉛化性炭素となる材料をバインダーに
用いた場合、実施例１〜５に示すように、電池の容量は
高く、充放電に伴う容量の低下は非常に小さかった。When a material which becomes non-graphitizable carbon was used as the binder, as shown in Examples 1 to 5, the capacity of the battery was high, and the decrease in capacity due to charge / discharge was very small.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【発明の効果】以上の説明から明らかなように、ケイ素
を含む負極材料と加熱処理により難黒鉛化性炭素を形成
するバインダーとからなる塗膜を集電体上に形成し、非
酸化性雰囲気下で焼結し、集電体と一体化することによ
り、高容量で、優れたサイクル特性を与える非水系二次
電池用負極の製造方法を提供できる。As is apparent from the above description, a coating film comprising a negative electrode material containing silicon and a binder for forming non-graphitizable carbon by heat treatment is formed on a current collector, and a non-oxidizing atmosphere is formed. By sintering below and integrating with a current collector, it is possible to provide a method for producing a negative electrode for a non-aqueous secondary battery which has high capacity and excellent cycle characteristics.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｈ０１Ｍ 4/70 Ｈ０１Ｍ 4/70 Ｚ (56)参考文献 特開 平11−339778（ＪＰ，Ａ) 特許2948205（ＪＰ，Ｂ１) 特許2948206（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 - 4/04 H01M 4/36 - 4/62 H01M 10/40 Continuation of front page (51) Int.Cl. 7 Identification symbol FI // H01M4 / 70 H01M4 / 70Z (56) References JP-A-11-339778 (JP, A) Patent 2948205 (JP, B1) Patent 2948206 (JP, B1) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/02-4/04 H01M 4/36-4/62 H01M 10/40
Claims (3)
難黒鉛化性炭素を形成するバインダーとからなる塗膜を
集電体上に形成し、非酸化性雰囲気下で焼結し、集電体
と一体化する非水系二次電池用負極の製造方法。1. A method comprising: forming a coating film comprising a negative electrode material containing silicon and a binder which forms non-graphitizable carbon by heat treatment on a current collector, and sintering in a non-oxidizing atmosphere; A method for producing a negative electrode for a non-aqueous secondary battery, which is integrated with a negative electrode.
ラン樹脂、ビニリデン樹脂、糖類、ポリアクリロニトリ
ル及びゼラチンからなる群から選ばれた少なくとも１種
である請求項１記載の非水系二次電池用負極の製造方
法。2. The method according to claim 1, wherein the binder is at least one selected from the group consisting of a phenol resin, a furan resin, a vinylidene resin, a saccharide, a polyacrylonitrile, and a gelatin. Method.
量％以上である請求項１又は２に記載の非水系二次電池
用負極の製造方法。3. The method for producing a negative electrode for a non-aqueous secondary battery according to claim 1, wherein the residual ratio of the binder after sintering is 5% by weight or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11176606A JP3078800B1 (en) | 1999-06-23 | 1999-06-23 | Method for producing negative electrode for non-aqueous secondary battery |
| US09/600,176 US6413672B1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| EP99973178A EP1054462A4 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| PCT/JP1999/006776 WO2000033404A1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| KR1020007008486A KR100609862B1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11176606A JP3078800B1 (en) | 1999-06-23 | 1999-06-23 | Method for producing negative electrode for non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3078800B1 true JP3078800B1 (en) | 2000-08-21 |
| JP2001006682A JP2001006682A (en) | 2001-01-12 |
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ID=16016519
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|---|---|---|---|
| JP11176606A Expired - Fee Related JP3078800B1 (en) | 1998-12-03 | 1999-06-23 | Method for producing negative electrode for non-aqueous secondary battery |
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| JP (1) | JP3078800B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3895932B2 (en) | 2001-01-17 | 2007-03-22 | 三洋電機株式会社 | Negative electrode for lithium secondary battery and method for producing the same |
| JP4033720B2 (en) * | 2002-06-19 | 2008-01-16 | 三洋電機株式会社 | Negative electrode for lithium secondary battery and lithium secondary battery |
| JP4614625B2 (en) * | 2002-09-30 | 2011-01-19 | 三洋電機株式会社 | Method for manufacturing lithium secondary battery |
| JP2005268120A (en) * | 2004-03-19 | 2005-09-29 | Sanyo Electric Co Ltd | Lithium secondary battery and its manufacturing method |
| JP4550640B2 (en) * | 2005-03-30 | 2010-09-22 | シャープ株式会社 | Lithium secondary battery, positive electrode plate for lithium secondary battery, and production method thereof |
| KR20090109570A (en) * | 2007-02-06 | 2009-10-20 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Electrodes including novel binders and methods of making and using the same |
| KR101090598B1 (en) * | 2009-03-16 | 2011-12-08 | 주식회사 엘지화학 | Binder of anode for secondary battery and secondary battery using the same |
| US9553303B2 (en) | 2010-01-18 | 2017-01-24 | Enevate Corporation | Silicon particles for battery electrodes |
| US11380890B2 (en) | 2010-01-18 | 2022-07-05 | Enevate Corporation | Surface modification of silicon particles for electrochemical storage |
| KR102098547B1 (en) * | 2010-01-18 | 2020-04-08 | 에네베이트 코포레이션 | Composite material film for electrochemical storage |
| US20170040598A1 (en) | 2015-08-07 | 2017-02-09 | Enevate Corporation | Surface modification of silicon particles for electrochemical storage |
| US10461366B1 (en) | 2010-01-18 | 2019-10-29 | Enevate Corporation | Electrolyte compositions for batteries |
| CN103053048A (en) * | 2010-08-02 | 2013-04-17 | 日产自动车株式会社 | Negative electrode for lithium-ion secondary battery, and manufacturing method for same |
| US9583757B2 (en) | 2010-12-22 | 2017-02-28 | Enevate Corporation | Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells |
| US10388943B2 (en) | 2010-12-22 | 2019-08-20 | Enevate Corporation | Methods of reducing occurrences of short circuits and/or lithium plating in batteries |
| JP6382649B2 (en) | 2013-09-20 | 2018-08-29 | 株式会社東芝 | Negative electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte battery, battery pack, and vehicle |
| US20180287129A1 (en) * | 2017-03-28 | 2018-10-04 | Enevate Corporation | Methods of forming carbon-silicon composite material on a current collector |
| JP6184385B2 (en) | 2014-09-19 | 2017-08-23 | 株式会社東芝 | Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and battery pack |
| GB201522446D0 (en) * | 2015-12-18 | 2016-02-03 | Norwegian Univ Sci & Tech Ntnu | Anode |
| US11101465B2 (en) | 2017-03-28 | 2021-08-24 | Enevate Corporation | Reaction barrier between electrode active material and current collector |
| KR20230113850A (en) | 2017-12-07 | 2023-08-01 | 에네베이트 코포레이션 | Composite comprising silicon carbide and carbon particles |
| US11133498B2 (en) | 2017-12-07 | 2021-09-28 | Enevate Corporation | Binding agents for electrochemically active materials and methods of forming the same |
| US10686214B2 (en) | 2017-12-07 | 2020-06-16 | Enevate Corporation | Sandwich electrodes and methods of making the same |
| US20230163309A1 (en) | 2021-11-22 | 2023-05-25 | Enevate Corporation | Silicon based lithium ion battery and improved cycle life of same |
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