JP6511726B2 - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery - Google Patents
Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery Download PDFInfo
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- JP6511726B2 JP6511726B2 JP2014092065A JP2014092065A JP6511726B2 JP 6511726 B2 JP6511726 B2 JP 6511726B2 JP 2014092065 A JP2014092065 A JP 2014092065A JP 2014092065 A JP2014092065 A JP 2014092065A JP 6511726 B2 JP6511726 B2 JP 6511726B2
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- negative electrode
- electrode material
- lithium ion
- ion secondary
- secondary battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池に関する。 The present invention relates to a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
現在、リチウムイオン二次電池の負極材料には主に黒鉛が用いられているが、黒鉛は放電容量に３７２ｍＡｈ/ｇという理論的な容量限界があることが知られている。近年、携帯電話、ノートパソコン、タブレット端末等のモバイル機器の高性能化に伴い、リチウムイオン二次電池の高容量化の要求が強くなっており、リチウムイオン二次電池の更なる高容量化を達成可能な負極材料が求められている。
そこで、理論容量が高く、リチウムイオンを吸蔵及び放出可能な元素(以下、「特定元素」ともいう。また、該特定元素を含んでなるものを、「特定元素体」ともいう)を用いた負極材料の開発が活発化している。
At present, graphite is mainly used as a negative electrode material of a lithium ion secondary battery, but it is known that graphite has a theoretical capacity limit of 372 mAh / g in discharge capacity. In recent years, with the advancement of mobile devices such as mobile phones, notebook computers, tablet terminals, etc., the demand for higher capacity lithium ion secondary batteries has become stronger, and further higher capacity lithium ion secondary batteries There is a need for an achievable negative electrode material.
Therefore, an anode having a high theoretical capacity and capable of absorbing and desorbing lithium ions (hereinafter, also referred to as a "specific element", and an element including the specific element is also referred to as a "specific element body") Development of materials is intensifying.
上記特定元素としては、ケイ素、錫、鉛、アルミニウム等がよく知られている。その中でも特定元素体の一つであるケイ素酸化物は、他の特定元素からなる負極材料よりも容量が高く、安価、加工性が良好である等といった利点があり、これを用いた負極材の研究が特に盛んである。 As the above-mentioned specific element, silicon, tin, lead, aluminum and the like are well known. Among them, silicon oxide, which is one of the specific element bodies, has advantages such as higher capacity, lower cost, better processability, etc. than negative electrode materials consisting of other specific elements. Research is particularly active.
一方、これら特定元素体は、充電によって合金化した際に、大きく体積膨張することが知られている。このような体積膨張は、特定元素体自身を微細化し、更にこれらを用いた負極材料もその構造が破壊されて導電性が切断される。そのため、サイクル経過によって容量が著しく低下することが課題となっている。 On the other hand, these specific element bodies are known to undergo large volume expansion when alloyed by charging. Such volume expansion refines the specific element body itself, and further, the structure of the negative electrode material using them is broken and the conductivity is cut. Therefore, it is an issue that the capacity is significantly reduced as the cycle progresses.
この課題に対し、例えば、特許文献１では、Ｘ線回折において、Ｓｉ（１１１）に帰属される回折ピークが観察され、その回折線の半価幅をもとにシェーラー法により求めたケイ素の結晶の大きさが１〜５００ｎｍである、ケイ素の微結晶がケイ素系化合物に分散した構造を有する粒子の表面を炭素でコーティングしてなることを特徴とする非水電解質二次電池負極材用導電性ケイ素複合体が開示されている。
特許文献１の技術によれば、ケイ素微結晶又は微粒子を不活性で強固な物質、例えば、二酸化ケイ素に分散し、更に、この表面の少なくとも一部に導電性を賦与するための炭素を融着させることによって、表面の導電性はもちろん、リチウムの吸蔵及び放出に伴う体積変化に対して安定な構造となり、結果として、長期安定性、初期効率が改善されるとされている。
To solve this problem, for example, in Patent Document 1, a diffraction peak belonging to Si (111) is observed in X-ray diffraction, and a crystal of silicon obtained by the Scheller method based on the half-value width of the diffraction line. The conductive material for a non-aqueous electrolyte secondary battery negative electrode material, characterized in that the surface of a particle having a structure in which silicon microcrystals are dispersed in a silicon-based compound is 1 to 500 nm in size and coated with carbon. Silicon composites are disclosed.
According to the technique of Patent Document 1, silicon microcrystalline or fine particles are dispersed in an inert strong substance such as silicon dioxide, and further, carbon is fused to impart conductivity to at least a part of the surface. As a result, the surface conductivity becomes stable as well as the structure is stable against the volume change associated with lithium absorption and release, and as a result, the long-term stability and the initial efficiency are improved.
また、特許文献２では、リチウムイオンを吸蔵、放出し得る材料の表面を黒鉛皮膜で被覆した導電性粉末であり、黒鉛被覆量が３〜４０重量％、ＢＥＴ比表面積が２〜３０ｍ２／ｇであって、該黒鉛皮膜が、ラマン分光スペクトルより、ラマンシフトが１３３０ｃｍ−１と１５８０ｃｍ−１付近にグラファイト構造特有のスペクトルを有することを特徴とする非水電解質二次電池用負極材が開示されている。
特許文献２の技術によれば、リチウムイオンを吸蔵、放出し得る材料の表面に被覆する黒鉛皮膜の物性を特定範囲に制御することで、市場の要求する特性レベルに到達し得るリチウムイオン二次電池の負極が得られるとされている。
Moreover, in patent document 2, it is electroconductive powder which coat | covered the surface of the material which can occlude and discharge | release lithium ion with a graphite film, 3 to 40 weight% of graphite coverages, and 2-30 m < 2 > / g of BET specific surface areas. a is, graphite coating, according to the Raman spectrum, the Raman shift is the negative electrode material for a nonaqueous electrolyte secondary battery characterized by having a spectrum of graphite structure-specific are disclosed in the vicinity of 1330 cm -1 and 1580 cm -1 ing.
According to the technology of Patent Document 2, by controlling the physical properties of the graphite film coated on the surface of the material capable of absorbing and releasing lithium ions within a specific range, it is possible to reach the characteristic level required by the market by lithium ion secondary It is supposed that the negative electrode of the battery is obtained.
また、特許文献３では、非水電解質を用いる二次電池用の負極に用いられる負極材料であって、該負極材料は、一般式ＳｉＯｘで表される酸化ケイ素粒子の表面上に炭素皮膜が被覆されたものであり、かつ前記炭素皮膜は熱プラズマ処理されたものであることを特徴とする非水電解質二次電池用負極材料が開示されている。
特許文献３の技術によれば、酸化ケイ素の欠点である電極の膨張と、ガス発生による電池の膨張を解決し、サイクル特性に優れた非水電解質二次電池負極用として有効な負極材料が得られるとされている。
Further, in Patent Document 3, a negative electrode material used for a negative electrode for a secondary battery using a non-aqueous electrolyte, wherein the negative electrode material has a carbon film on the surface of silicon oxide particles represented by the general formula SiO x A negative electrode material for a non-aqueous electrolyte secondary battery is disclosed, which is coated, and the carbon film has been subjected to thermal plasma treatment.
According to the technique of Patent Document 3, the expansion of the electrode which is a defect of silicon oxide and the expansion of the battery due to gas generation are solved, and a negative electrode material effective for the non-aqueous electrolyte secondary battery negative electrode excellent in cycle characteristics is obtained. It is supposed to be
しかしながら、特定元素体の一つであるケイ素酸化物を負極材料として使用した場合、初期の充放電効率が低く、実際の電池に適用した際に正極の電池容量を過剰に必要とするため、従来の技術においても、高容量というケイ素酸化物の特徴を実際のリチウムイオン二次電池へ充分には活かしきれなかった。また、今後、モバイル機器等の高性能化に適したリチウムイオン二次電池へ適用するための負極材料としては、単に多くのリチウムイオンを貯蔵できる（充電容量が高い）だけではなく、貯蔵したリチウムイオンをより多く放出できることが必要となる。従って、リチウムイオン二次電池の更なる性能向上に貢献する負極材料としては、初期の放電容量の向上と初期の充放電効率の向上との両立が重要となる。
これに加え、リチウムイオン二次電池の更なる性能向上に貢献する負極材料としては、初期の特性のみならず、繰り返し充放電による容量の低下を抑えることも重要であり、サイクル特性の向上も求められる。そして、充放電後の回復率等を指標とするリチウムイオン二次電池の寿命の更なる向上も求められる。
本発明は、上記要求に鑑みなされたものであり、初期の放電容量、初期の充放電効率、サイクル特性、及び寿命に優れるリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池を提供することを課題とする。
However, when silicon oxide, which is one of the specific element bodies, is used as a negative electrode material, the initial charge and discharge efficiency is low, and when applied to an actual battery, the battery capacity of the positive electrode is required excessively. Also in the technology of the above, the characteristics of silicon oxide of high capacity could not be fully utilized for the actual lithium ion secondary battery. In addition, as a negative electrode material to be applied to lithium ion secondary batteries suitable for higher performance in mobile devices and the like from now on, it is possible to store not only lithium ions that can be stored a lot (high charging capacity), but also stored lithium It needs to be able to release more ions. Therefore, as a negative electrode material that contributes to the further performance improvement of the lithium ion secondary battery, it is important to simultaneously improve the initial discharge capacity and the initial charge / discharge efficiency.
In addition to this, as a negative electrode material that contributes to the further performance improvement of lithium ion secondary batteries, it is important not only to reduce initial characteristics but also to suppress the decrease in capacity due to repeated charge and discharge. Be And further improvement of the life of a lithium ion secondary battery which makes a recovery rate etc. after charge and discharge an index is also called for.
This invention is made in view of the said request | requirement, the negative electrode material for lithium ion secondary batteries which is excellent in the initial stage discharge capacity, the initial stage charge / discharge efficiency, cycling characteristics, and the lifetime, a negative electrode for lithium ion secondary batteries, and lithium An object is to provide an ion secondary battery.
前記課題を解決するための具体的手段は以下の通りである。 The specific means for solving the said subject are as follows.
（１）ケイ素酸化物粒子と、前記ケイ素酸化物粒子の表面の一部又は全部に存在する炭素の単体と、前記炭素の単体が表面に存在したケイ素酸化物粒子の表面に付着する粒状黒鉛及びカーボンブラックよりなる群から選択される一種の導電性粒子と、前記導電性粒子が表面に付着したケイ素酸化物粒子の表面の一部又は全部に存在する有機物と、を含むリチウムイオン二次電池用負極材料。
（２）前記導電性粒子が、少なくとも前記粒状黒鉛を含む（１）に記載のリチウムイオン二次電池用負極材料。
（３）前記粒状黒鉛が、扁平状黒鉛である（２）に記載のリチウムイオン二次電池用負極材料。
（４）前記導電性粒子の含有率が、１．０質量％〜１０．０質量％である（１）〜（３）のいずれか１項に記載のリチウムイオン二次電池用負極材料。
（５）前記有機物が、多糖、ゼラチン、カゼイン及び水溶性ポリエーテルからなる群より選ばれる少なくとも１つである第一成分と、単糖、二糖、オリゴ糖、アミノ酸、没食子酸、タンニン、サッカリン、サッカリンの塩及びブチンジオールからなる群より選ばれる少なくとも１つである第二成分とを含む（１）〜（４）のいずれか１項に記載のリチウムイオン二次電池用負極材料。
（６）前記炭素の単体の含有率が、前記ケイ素酸化物と前記炭素の単体の合計量の０．５質量％〜１０．０質量％である（１）〜（５）のいずれか１項に記載のリチウムイオン二次電池用負極材料。
（７）ＣｕＫα線を線源とするＸ線回折スペクトルにおいてＳｉ（１１１）に帰属される回折ピークを有し、前記回折ピークから算出されるケイ素の結晶子の大きさが、２．０ｎｍ〜８．０ｎｍである（１）〜（６）のいずれか１項に記載のリチウムイオン二次電池用負極材料。
（８）集電体と、前記集電体上に設けられた、（１）〜（７）のいずれか１項に記載のリチウムイオン二次電池用負極材料を含む負極材層と、を有するリチウムイオン二次電池用負極。
（９）正極と、（８）に記載のリチウムイオン二次電池用負極と、電解質と、を備えるリチウムイオン二次電池。
(1) Silicon oxide particles, simple substance of carbon present on part or all of the surface of the silicon oxide particles, granular graphite attached to the surface of silicon oxide particles on which the single substance of the carbon is present on the surface, For a lithium ion secondary battery, including one kind of conductive particles selected from the group consisting of carbon black, and an organic substance present on a part or all of the surface of silicon oxide particles having the conductive particles attached to the surface Negative electrode material.
(2) The negative electrode material for a lithium ion secondary battery according to (1), wherein the conductive particles contain at least the particulate graphite.
(3) The negative electrode material for a lithium ion secondary battery according to (2), wherein the particulate graphite is flat graphite.
(4) The negative electrode material for a lithium ion secondary battery according to any one of (1) to (3), wherein the content of the conductive particles is 1.0% by mass to 10.0% by mass.
(5) The first component, wherein the organic substance is at least one selected from the group consisting of polysaccharides, gelatin, casein and water-soluble polyether, and monosaccharides, disaccharides, oligosaccharides, amino acids, gallic acid, tannins, saccharin A negative electrode material for a lithium ion secondary battery according to any one of (1) to (4), comprising a second component which is at least one selected from the group consisting of a salt of saccharin and a butyne diol.
(6) Any one of the items (1) to (5), wherein the content of the single substance of the carbon is 0.5 mass% to 10.0 mass% of the total amount of the single substance of the silicon oxide and the carbon. The negative electrode material for lithium ion secondary batteries as described in 4.
(7) It has a diffraction peak attributed to Si (111) in an X-ray diffraction spectrum using a CuKα ray as a radiation source, and the size of the crystallite of silicon calculated from the diffraction peak is 2.0 nm to 8 The negative electrode material for a lithium ion secondary battery according to any one of (1) to (6), which has a thickness of 0 nm.
(8) A current collector, and a negative electrode material layer including the negative electrode material for a lithium ion secondary battery according to any one of (1) to (7), provided on the current collector. Negative electrode for lithium ion secondary battery.
(9) A lithium ion secondary battery comprising a positive electrode, the negative electrode for a lithium ion secondary battery according to (8), and an electrolyte.
本発明によれば、初期の放電容量、初期の充放電効率、サイクル特性、及び寿命に優れるリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池を提供することができる。 According to the present invention, a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery which are excellent in initial discharge capacity, initial charge and discharge efficiency, cycle characteristics and life are provided. Can.
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
更に、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
The numerical range shown using "-" in this specification shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively.
Furthermore, in the present specification, the amount of each component in the composition is the amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. It means the total amount.
＜リチウムイオン二次電池用負極材料＞
本発明のリチウムイオン二次電池用負極材料（以下、「負極材料」と略称する場合がある）は、ケイ素酸化物粒子と、ケイ素酸化物粒子の表面の一部又は全部に存在する炭素の単体と、炭素の単体が表面に存在したケイ素酸化物粒子（以下、炭素の単体が表面に存在したケイ素酸化物粒子を「ＳｉＯ−Ｃ粒子」と略称する場合がある）の表面に付着する粒状黒鉛及びカーボンブラックからなる群から選択される一種の導電性粒子と、導電性粒子が表面に付着したケイ素酸化物粒子（以下、炭素の単体が表面に存在し、更に導電性粒子が表面に付着したケイ素酸化物粒子を「ＣＰ／ＳｉＯ−Ｃ粒子」と称する場合がある）の表面の一部又は全部に存在する有機物と、を含む。
<Anode material for lithium ion secondary battery>
The negative electrode material for lithium ion secondary batteries of the present invention (hereinafter sometimes referred to as “negative electrode material”) may be a single substance of silicon oxide particles and carbon present on part or all of the surface of silicon oxide particles. And particulate graphite attached to the surface of silicon oxide particles (hereinafter, silicon oxide particles having carbon single particles on the surface may be abbreviated as "SiO-C particles") having carbon single particles on the surface. And conductive particles selected from the group consisting of and carbon black, and silicon oxide particles having conductive particles attached to the surface (hereinafter, single carbon is present on the surface, and further conductive particles are attached to the surface And the organic matter present on a part or all of the surface of the silicon oxide particles may be referred to as "CP / SiO-C particles".
本発明の負極材料は、炭素の単体がケイ素酸化物粒子の表面に存在することにより、リチウムイオンの吸蔵及び放出に伴うケイ素酸化物粒子の膨張及び収縮を緩和することができるとともに、単位質量あたりのケイ素酸化物粒子の容量低下を抑えることができるため、初期の放電容量及び初期の充放電効率に優れる。これに加え、ＳｉＯ−Ｃ粒子の表面にさらに粒状黒鉛又はカーボンブラックが付着することにより、ＳｉＯ−Ｃ粒子の表面に導電性の突起構造が付与される。このため、ケイ素酸化物粒子が膨張及び収縮しても、隣り合う負極材料同士の導通が図られ易くなる。また、負極材料全体の抵抗値の低減化も図られる。その結果、繰り返し充放電による容量の低下を抑えられ、サイクル特性にも優れる。 In the negative electrode material of the present invention, expansion and contraction of silicon oxide particles accompanying absorption and release of lithium ions can be alleviated by the presence of a single substance of carbon on the surface of silicon oxide particles, and per unit mass. Since the capacity reduction of the silicon oxide particles can be suppressed, the initial discharge capacity and the initial charge / discharge efficiency are excellent. In addition to this, the particulate graphite or carbon black further adheres to the surface of the SiO-C particles, whereby the conductive protrusion structure is imparted to the surface of the SiO-C particles. Therefore, even if the silicon oxide particles expand and contract, conduction between adjacent negative electrode materials can be easily achieved. In addition, the resistance value of the entire negative electrode material can be reduced. As a result, the decrease in capacity due to repeated charge and discharge can be suppressed, and the cycle characteristics are also excellent.
更に、本発明の負極材料は、ＣＰ／ＳｉＯ−Ｃ粒子の表面の一部又は全部に有機物が存在することにより、負極材料の比表面積が低下し、電解液との反応が抑制されるため、充放電後の維持率及び回復率が向上すると考えられる。その結果、寿命も優れたものとなる。 Furthermore, in the negative electrode material of the present invention, the presence of the organic substance on a part or all of the surface of the CP / SiO-C particles reduces the specific surface area of the negative electrode material and suppresses the reaction with the electrolyte. It is believed that the maintenance rate and recovery rate after charge and discharge are improved. As a result, the life is also excellent.
（ケイ素酸化物粒子）
本発明の負極材料は、ケイ素酸化物粒子を含む。ケイ素酸化物粒子を構成するケイ素酸化物は、ケイ素元素を含む酸化物であればよく、一酸化ケイ素（酸化ケイ素ともいう）、二酸化ケイ素、亜酸化ケイ素等が挙げられる。これらは一種単独で使用してもよく、複数種を組み合わせて使用してもよい。
ケイ素酸化物の中で、酸化ケイ素及び二酸化ケイ素は、一般的には、それぞれ一酸化ケイ素（ＳｉＯ）及び二酸化ケイ素（ＳｉＯ２）として表されるが、表面状態（例えば、酸化皮膜の存在）又は化合物の生成状況によって、含まれる元素の実測値（又は換算値）として組成式ＳｉＯｘ（ｘは０＜ｘ≦２）で表される場合があり、この場合も本発明のケイ素酸化物とする。なお、ｘの値は、例えば、不活性ガス融解−非分散型赤外線吸収法にてケイ素酸化物中に含まれる酸素を定量することにより算出することができる。また、本発明の負極材料の製造工程中に、ケイ素酸化物の不均化反応（２ＳｉＯ→Ｓｉ＋ＳｉＯ２）を伴う場合は、化学反応上、ケイ素及び二酸化ケイ素（場合によって酸化ケイ素）を含む状態で表される場合があり、この場合も本発明に係るケイ素酸化物とする。
なお、酸化ケイ素は、例えば、二酸化ケイ素と金属ケイ素との混合物を加熱して生成した一酸化ケイ素の気体を冷却及び析出させる公知の昇華法にて得ることができる。また、酸化ケイ素、一酸化ケイ素等として市場から入手することができる。
(Silicon oxide particles)
The negative electrode material of the present invention contains silicon oxide particles. The silicon oxide which comprises a silicon oxide particle should just be an oxide containing a silicon element, and silicon monoxide (it is also mentioned a silicon oxide), a silicon dioxide, a silicon suboxide, etc. are mentioned. These may be used singly or in combination of two or more.
Among silicon oxides, silicon oxide and silicon dioxide are generally represented as silicon monoxide (SiO) and silicon dioxide (SiO 2 ), respectively, but with surface states (eg the presence of oxide films) or Depending on the formation state of the compound, it may be represented by the composition formula SiOx (x is 0 <x ≦ 2) as an actual measurement value (or a conversion value) of the contained element, and in this case also the silicon oxide of the present invention. The value of x can be calculated, for example, by quantifying oxygen contained in silicon oxide by the inert gas melting-non-dispersive infrared absorption method. In addition, when disproportionation reaction of silicon oxide (2SiO → Si + SiO 2 ) is involved in the manufacturing process of the negative electrode material of the present invention, the chemical reaction includes silicon and silicon dioxide (in some cases silicon oxide) In some cases, the silicon oxide according to the present invention is used.
The silicon oxide can be obtained, for example, by a known sublimation method in which a gas of silicon monoxide formed by heating a mixture of silicon dioxide and metal silicon is cooled and deposited. In addition, it can be obtained from the market as silicon oxide, silicon monoxide and the like.
ケイ素酸化物粒子は、ケイ素酸化物中にケイ素の結晶子が分散した構造を有することが好ましい。ケイ素酸化物粒子中にケイ素の結晶子が分散した構造となる場合、ＣｕＫα線を線源とする粉末Ｘ線回折（ＸＲＤ）測定を行ったとき、２θ＝２８．４°付近にＳｉ（１１１）に帰属される回折ピークが観察される。ケイ素酸化物粒子中にケイ素の結晶子が存在すると、初期の放電容量の高容量化と良好な初期の充放電効率が得られやすい。 The silicon oxide particles preferably have a structure in which crystallites of silicon are dispersed in silicon oxide. In the case of a structure in which crystallites of silicon are dispersed in silicon oxide particles, when powder X-ray diffraction (XRD) measurement using a CuKα ray as a radiation source is performed, Si (111) around 2θ = 28.4 ° The diffraction peak attributed to is observed. If silicon crystallites are present in the silicon oxide particles, it is easy to obtain an increase in initial discharge capacity and a good initial charge / discharge efficiency.
ケイ素の結晶子の大きさは８．０ｎｍ以下であることが好ましく、より好ましくは、６．０ｎｍ以下である。結晶子の大きさが８．０ｎｍ以下の場合には、ケイ素酸化物粒子中でケイ素の結晶子が局在化しにくくなるため、ケイ素酸化物粒子内でリチウムイオンが拡散しやすく、良好な充電容量が得られやすい。
また、ケイ素の結晶子の大きさは２．０ｎｍ以上であることが好ましく、より好ましくは、３．０ｎｍ以上である。結晶子の大きさが２．０ｎｍ以上の場合には、リチウムイオンとケイ素酸化物との反応が制御され、良好な充放電効率が得られやすい。
The size of the crystallite of silicon is preferably 8.0 nm or less, more preferably 6.0 nm or less. When the size of the crystallite is 8.0 nm or less, the crystallites of silicon are less likely to be localized in the silicon oxide particles, so lithium ions are easily diffused in the silicon oxide particles, and the charge capacity is good. Is easy to obtain.
In addition, the size of the crystallite of silicon is preferably 2.0 nm or more, more preferably 3.0 nm or more. When the size of the crystallite is 2.0 nm or more, the reaction between the lithium ion and the silicon oxide is controlled, and good charge / discharge efficiency can be easily obtained.
ケイ素の結晶子の大きさは、波長０．１５４０５６ｎｍのＣｕＫα線を線源とする粉末Ｘ線回折分析で得られるＳｉ（１１１）に帰属される２θ＝２８．４°付近の回折ピークの半値幅から、Ｓｃｈｅｒｒｅｒの式を用いて求めることができる。 The size of the crystallite of silicon is the half-width of the diffraction peak near 2θ = 28.4 ° attributed to Si (111) obtained by powder X-ray diffraction analysis using a CuKα ray with a wavelength of 0.154056 nm as a radiation source Thus, it can be obtained using Scherrer's equation.
ケイ素酸化物粒子中にケイ素の結晶子が分散した構造は、例えば、ケイ素酸化物粒子を不活性雰囲気下で７００℃〜１３００℃の温度域で熱処理して不均化することにより作製することができる。また、後述の炭素の単体をケイ素酸化物粒子に付与するための熱処理における加熱温度を調整することにより作製することができる。なお、熱処理時の加熱温度が高くなるほど、また、加熱時間が長くなるほど、ケイ素の結晶子の大きさが大きくなる傾向がある。 The structure in which crystallites of silicon are dispersed in silicon oxide particles can be produced, for example, by heat-treating the silicon oxide particles in a temperature range of 700 ° C. to 1300 ° C. in an inert atmosphere to disproportionate. it can. Moreover, it can produce by adjusting the heating temperature in the heat processing for providing the below-mentioned single-piece | unit of carbon to a silicon oxide particle. In addition, as the heating temperature at the time of heat treatment becomes higher and the heating time becomes longer, the size of the crystallite of silicon tends to be larger.
ケイ素酸化物粒子は、数ｃｍ角程度の大きさの塊状のケイ素酸化物を準備した場合には、粉砕し、分級して製造することができる。詳しくは、まず、微粉砕機に投入できる大きさまで粉砕する一次粉砕及び分級を行い、これを微粉砕機により二次粉砕することが好ましい。二次粉砕により得られるケイ素酸化物粒子の平均粒子径は、最終的な所望の負極材料の大きさに合わせて、０．１μｍ〜２０μｍであることが好ましく、０．５μｍ〜１０μｍであることがより好ましい。平均粒子径は、粒度分布の体積累積５０％粒径（Ｄ５０％）である。以下、平均粒子径の表記において同様である。平均粒子径の測定には、レーザー回折粒度分布計等の既知の方法を採用することができる。 The silicon oxide particles can be manufactured by crushing and classification when preparing massive silicon oxide having a size of several cm square. Specifically, it is preferable to first perform primary pulverization and classification to a size that can be introduced into the pulverizer, and then to perform secondary pulverization using the pulverizer. The average particle size of the silicon oxide particles obtained by the secondary pulverization is preferably 0.1 μm to 20 μm according to the size of the final desired negative electrode material, and 0.5 μm to 10 μm. More preferable. The average particle size is a 50% volume cumulative particle size (D 50%) of the particle size distribution. Hereinafter, the same applies to the description of the average particle size. For the measurement of the average particle size, known methods such as a laser diffraction particle size distribution analyzer can be adopted.
（炭素の単体）
本発明の負極材料は、ケイ素酸化物粒子の表面の一部又は全部に存在する炭素の単体を含む。ここで、炭素の単体とは、ケイ素酸化物粒子の表面の一部又は全部に付着した、特定の形状を有さない無定形炭素を示す。具体的には、例えば、炭素の単体とは、ケイ素酸化物粒子の表面の一部又は全部に膜状に存在した無定形炭素を示す。
(Single substance of carbon)
The negative electrode material of the present invention contains a single substance of carbon present on part or all of the surface of silicon oxide particles. Here, the simple substance of carbon shows amorphous carbon attached to a part or all of the surface of silicon oxide particles and not having a specific shape. Specifically, for example, the simple substance of carbon indicates amorphous carbon which is present in the form of a film on part or all of the surface of silicon oxide particles.
炭素の単体の含有率は、ケイ素酸化物粒子と炭素の単体の合計量中に０．５質量％〜１０．０質量％であることが好ましい。このような構成とすることにより、初期の放電容量及び初期の充放電効率がより向上する傾向にある。炭素の単体の含有率は、１．０質量％〜９．０質量％がより好ましく、２．０質量％〜８．０質量％が更に好ましく、３．０質量％〜７．０質量％が特に好ましい。 The content of single carbon is preferably 0.5% by mass to 10.0% by mass in the total amount of the silicon oxide particles and the single carbon. With such a configuration, the initial discharge capacity and the initial charge / discharge efficiency tend to be further improved. As for the content rate of a single substance of carbon, 1.0 mass%-9.0 mass% are more preferable, 2.0 mass%-8.0 mass% are still more preferable, 3.0 mass%-7.0 mass% are Particularly preferred.
炭素の単体は、低結晶性であることが好ましい。低結晶性とは、下記に示す方法で得られるＲ値が０．５以上であることを意味する。
炭素の単体は、励起波長５３２ｎｍのレーザーラマン分光測定により求めたプロファイルの中で、１３６０ｃｍ−１付近に現れるピークの強度をＩｄ、１５８０ｃｍ−１付近に現れるピークの強度をＩｇとし、その両ピークの強度比Ｉｄ／Ｉｇ（Ｄ／Ｇとも表記する）をＲ値とした際、そのＲ値が０．５〜１．５あることが好ましく、０．７〜１．３であることがより好ましく、０．８〜１．２であることが更に好ましい。Ｒ値が０．５〜１．５であると、炭素結晶子が乱配向した低結晶性炭素で粒子表面が被覆されるため、電解液との反応性が低減でき、サイクル特性が改善する傾向がある。
The simple substance of carbon is preferably low in crystallinity. The low crystallinity means that the R value obtained by the following method is 0.5 or more.
Single carbon in a profile obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, the intensity of the peak appearing the intensity of the peak appearing in the vicinity of 1360 cm -1 Id, in the vicinity of 1580 cm -1 and Ig, the both peaks When the intensity ratio Id / Ig (also represented as D / G) is an R value, the R value is preferably 0.5 to 1.5, and more preferably 0.7 to 1.3, More preferably, it is 0.8 to 1.2. When the R value is 0.5 to 1.5, the particle surface is coated with low crystalline carbon in which carbon crystallites are randomly oriented, so that the reactivity with the electrolytic solution can be reduced, and the cycle characteristics tend to be improved. There is.
ここで、１３６０ｃｍ−１付近に現れるピークとは、通常、炭素の単体の非晶質構造に対応すると同定されるピークであり、例えば、１３００ｃｍ−１〜１４００ｃｍ−１に観測されるピークを意味する。また、１５８０ｃｍ−１付近に現れるピークとは、通常、黒鉛結晶構造に対応すると同定されるピークであり、例えば、１５３０ｃｍ−１〜１６３０ｃｍ−１に観測されるピークを意味する。
なお、Ｒ値はラマンスペクトル測定装置（例えば、ＮＳＲ−１０００型、日本分光株式会社）を用い、測定範囲（８３０ｃｍ−１〜１９４０ｃｍ−１）に対して１０５０ｃｍ−１〜１７５０ｃｍ−１をベースラインとして求めることができる。
Here, the peak appearing in the vicinity of 1360 cm −1 is usually a peak identified as corresponding to the amorphous structure of a single carbon, and means, for example, a peak observed in 1300 cm −1 to 1400 cm −1 . Also, the peak appearing near 1580 cm -1, generally a peak identified as corresponding to the graphite crystal structure, for example, refers to peaks observed at 1530cm -1 ~1630cm -1.
Incidentally, R value Raman spectrum measuring apparatus (e.g., NSR-1000 type, manufactured by JASCO Corporation) was used, the 1050cm -1 ~1750cm -1 as a baseline for the measurement range (830cm -1 ~1940cm -1) It can be asked.
ケイ素酸化物粒子の表面に炭素の単体を付与する方法としては、特に制限はなく、湿式混合法、乾式混合法、化学蒸着法等の方法が挙げられる。均一かつ反応系の制御が容易で、負極材料の形状が維持できるといった点から、湿式混合法又は乾式混合法が好ましい。 There is no restriction | limiting in particular as a method of providing single-piece | unit of carbon to the surface of a silicon oxide particle, Methods, such as a wet mixing method, a dry mixing method, a chemical vapor deposition method, are mentioned. A wet mixing method or a dry mixing method is preferable in terms of uniformity and easy control of the reaction system, and the shape of the negative electrode material can be maintained.
湿式混合法の場合は、例えば、ケイ素酸化物粒子と、炭素源を溶媒に溶解させた溶液と、を混合し、炭素源の溶液をケイ素酸化物粒子の表面に付着させ、必要に応じて溶媒を除去し、その後、不活性雰囲気下で熱処理することにより炭素源を炭素化させて炭素の単体を付与することができる。なお、炭素源が溶媒に溶解しない等の場合は、炭素源を分散媒中に分散させた分散液とすることもできる。 In the case of the wet mixing method, for example, silicon oxide particles and a solution in which a carbon source is dissolved in a solvent are mixed, a solution of the carbon source is attached to the surface of the silicon oxide particles, The carbon source can be carbonized to give a simple substance of carbon by heat treatment under an inert atmosphere. In the case where the carbon source is not dissolved in the solvent, for example, the carbon source may be dispersed in a dispersion medium.
乾式混合法の場合は、例えば、ケイ素酸化物粒子と炭素源とをそれぞれ固体の状態で混合し混合物とし、この混合物を不活性雰囲気下で熱処理することにより炭素源を炭素化させて、ケイ素酸化物粒子の表面に炭素の単体を付与することができる。なお、ケイ素酸化物粒子と炭素源とを混合する際、力学的エネルギーを加える処理（例えば、メカノケミカル処理）を施してもよい。
化学蒸着法の場合は、公知の方法が適用でき、例えば、炭素源を気化させたガスを含む雰囲気中でケイ素酸化物粒子を熱処理することで、ケイ素酸化物粒子の表面に炭素の単体を付与することができる。
In the case of the dry mixing method, for example, silicon oxide particles and a carbon source are mixed in the solid state respectively to form a mixture, and the mixture is heat-treated under an inert atmosphere to carbonize the carbon source to obtain silicon oxide. A simple substance of carbon can be applied to the surface of the object particle. In addition, when mixing a silicon oxide particle and a carbon source, you may perform the process (for example, mechanochemical process) which adds mechanical energy.
In the case of the chemical vapor deposition method, known methods can be applied, for example, heat treatment of silicon oxide particles in an atmosphere containing a gas obtained by vaporizing a carbon source to apply a single substance of carbon to the surface of silicon oxide particles. can do.
前記方法にて、ケイ素酸化物粒子の表面に炭素の単体を付与する場合、炭素源としては、特に制限はなく、熱処理により炭素の単体を残し得る化合物であればよい。具体的には、フェノール樹脂、スチレン樹脂、ポリビニルアルコール、ポリ塩化ビニル、ポリ酢酸ビニル、ポリブチラール等の高分子化合物；エチレンヘビーエンドピッチ、石炭系ピッチ、石油ピッチ、コールタールピッチ、アスファルト分解ピッチ、ポリ塩化ビニル等を熱分解して生成するＰＶＣピッチ、ナフタレン等を超強酸存在下で重合させて作製されるナフタレンピッチ等のピッチ類；デンプン、セルロース等の多糖類；などが挙げられる。これら炭素源は、１種単独で又は２種類以上を組み合わせて使用してもよい。 When a simple substance of carbon is applied to the surface of silicon oxide particles by the above method, the carbon source is not particularly limited as long as it is a compound which can leave a simple substance of carbon by heat treatment. Specifically, polymer compounds such as phenol resin, styrene resin, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, and polybutyral; ethylene heavy end pitch, coal pitch, petroleum pitch, coal tar pitch, asphalt decomposition pitch, Pitches such as naphthalene pitch produced by polymerizing polyvinyl chloride etc. by thermal decomposition of PVC pitch, naphthalene etc. in the presence of super acid; polysaccharides such as starch, cellulose etc .; You may use these carbon sources individually by 1 type or in combination of 2 or more types.
化学蒸着法によってケイ素酸化物粒子の表面に炭素の単体を付与する場合、炭素源としては、脂肪族炭化水素、芳香族炭化水素、脂環族炭化水素等のうち、気体状又は容易に気体化可能な化合物を用いることが好ましい。具体的には、メタン、エタン、プロパン、トルエン、ベンゼン、キシレン、スチレン、ナフタレン、クレゾール、アントラセン、これらの誘導体等が挙げられる。これら炭素源は、１種単独で又は２種類以上を組み合わせて使用してもよい。 When a simple substance of carbon is applied to the surface of silicon oxide particles by a chemical vapor deposition method, as a carbon source, among aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons and the like, gaseous or easily gasified It is preferred to use possible compounds. Specifically, methane, ethane, propane, toluene, benzene, xylene, styrene, naphthalene, cresol, anthracene, derivatives thereof and the like can be mentioned. You may use these carbon sources individually by 1 type or in combination of 2 or more types.
炭素源を炭素化するための熱処理温度は、炭素源が炭素化する温度であれば特に制限されず、７００℃以上であることが好ましく、８００℃以上であることがより好ましく、９００℃以上であることが更に好ましい。また、炭素の単体を低結晶性とする観点及びケイ素の結晶子を所望の大きさで生成させる観点からは、１３００℃以下であることが好ましく、１２００℃以下であることがより好ましく、１１００℃以下であることが更に好ましい。 The heat treatment temperature for carbonizing the carbon source is not particularly limited as long as the carbon source carbonizes, and is preferably 700 ° C. or more, more preferably 800 ° C. or more, and 900 ° C. or more It is further preferred that Further, from the viewpoint of making the single substance of carbon low in crystallinity and the viewpoint of forming crystallites of silicon in a desired size, it is preferably 1300 ° C. or less, more preferably 1200 ° C. or less, 1100 ° C. It is more preferable that it is the following.
熱処理時間は、用いる炭素源の種類やその付与量によって適宜選択され、例えば、１時間〜１０時間が好ましく、２時間〜７時間がより好ましい。 The heat treatment time is appropriately selected depending on the type of carbon source to be used and the amount thereof applied, and for example, 1 hour to 10 hours is preferable, and 2 hours to 7 hours is more preferable.
なお、熱処理は、窒素、アルゴン等の不活性雰囲気下で行うことが好ましい。熱処理装置は、加熱機構を有する反応装置を用いれば特に限定されず、連続法、回分法等での処理が可能な加熱装置などが挙げられる。具体的には、流動層反応炉、回転炉、竪型移動層反応炉、トンネル炉、バッチ炉等をその目的に応じ適宜選択することができる。 The heat treatment is preferably performed in an inert atmosphere such as nitrogen or argon. The heat treatment apparatus is not particularly limited as long as a reaction apparatus having a heating mechanism is used, and examples thereof include a heating apparatus capable of processing by a continuous method, a batch method, and the like. Specifically, a fluidized bed reactor, a rotary furnace, a vertical moving bed reactor, a tunnel furnace, a batch furnace and the like can be appropriately selected according to the purpose.
熱処理により得られた熱処理物は個々の粒子が凝集している場合があるため、解砕処理することが好ましい。また、所望の平均粒子径への調整が必要な場合は更に粉砕処理を行ってもよい。 The heat-treated product obtained by the heat treatment may preferably be crushed because individual particles may be agglomerated. Further, when adjustment to a desired average particle size is required, further pulverization may be performed.
（導電性粒子）
本発明の負極材料は、ＳｉＯ−Ｃ粒子の表面に粒状黒鉛及びカーボンブラックよりなる群から選択される一種の導電性粒子が付着している。ＳｉＯ−Ｃ粒子の表面には、粒状黒鉛及びカーボンブラックの少なくとも一方が付着していればよく、サイクル特性の向上の観点から、粒状黒鉛が付着していることが好ましい。
(Conductive particles)
In the negative electrode material of the present invention, a kind of conductive particles selected from the group consisting of granular graphite and carbon black adheres to the surface of SiO-C particles. It is preferable that at least one of granular graphite and carbon black be attached to the surface of the SiO-C particles, and from the viewpoint of improvement of the cycle characteristics, the granular graphite be attached.
粒状黒鉛は、人造黒鉛、天然黒鉛、ＭＣ（メソフェーズカーボン）等の粒子が挙げられる。 Examples of particulate graphite include particles of artificial graphite, natural graphite, MC (mesophase carbon) and the like.
粒状黒鉛は、電池容量及び充放電効率がともに向上する点から、ケイ素酸化物粒子の表面に存在する炭素の単体よりも結晶性が高いことが好ましい。具体的には、球状黒鉛は、学振法に基づいて測定して得られる平均面間隔（ｄ００２）の値が０．３３５ｎｍ〜０．３４７ｎｍが好ましく、０．３３５ｎｍ〜０．３４５ｎｍがより好ましく、０．３３５ｎｍ〜０．３４０ｎｍが更に好ましく、０．３３５ｎｍ〜０．３３７ｎｍが特に好ましい。球状黒鉛の平均面間隔を０．３４７ｎｍ以下とすると、粒状黒鉛の結晶性が高く、電池容量及び充放電効率がともに向上する傾向がある。一方、黒鉛結晶の理論値は０．３３５ｎｍであることから、球状黒鉛の平均面間隔がこの値に近いと、電池容量及び充放電効率がともに向上する傾向がある。 The granular graphite preferably has higher crystallinity than a single substance of carbon present on the surface of the silicon oxide particles, from the viewpoint that both the battery capacity and the charge and discharge efficiency are improved. Specifically, the spherical graphite preferably has an average interplanar spacing (d 002 ) value of 0.335 nm to 0.347 nm, more preferably 0.335 nm to 0.345 nm, which is obtained by measurement based on the Gakushin method. 0.335 nm to 0.340 nm is more preferable, and 0.335 nm to 0.337 nm is particularly preferable. When the average interplanar spacing of the spherical graphite is 0.347 nm or less, the crystallinity of the granular graphite tends to be high, and both the battery capacity and the charge / discharge efficiency tend to be improved. On the other hand, since the theoretical value of the graphite crystal is 0.335 nm, when the average interplanar spacing of the spherical graphite is close to this value, both the battery capacity and the charge / discharge efficiency tend to be improved.
粒状黒鉛は、扁平状黒鉛、及び球状黒鉛のいずれであってもよく、サイクル特性を向上する点から、扁平状黒鉛であることが好ましい。 The particulate graphite may be any of flat graphite and spherical graphite, and is preferably flat graphite from the viewpoint of improving cycle characteristics.
扁平状黒鉛は、長軸と短軸を有し、完全な球状でない形状であって、鱗状、鱗片状、一部の塊状等の形状の黒鉛の粒子である。 Flat graphite is a particle of graphite having a major axis and a minor axis and having a shape that is not completely spherical, and has a shape such as a scale shape, a scaly shape, or a part of a block shape.
扁平状黒鉛のアスペクト比に特に制限はないが、粒子間の導電が取り易くなり、サイクル特性を向上する点から、３以上であることが好ましく、５以上であることがより好ましい。 The aspect ratio of the flat graphite is not particularly limited, but it is preferably 3 or more, more preferably 5 or more, from the viewpoint of facilitating conductivity between particles and improving cycle characteristics.
なお、扁平状黒鉛のアスペクト比は、扁平状黒鉛の長軸方向の長さをＡ、扁平状黒鉛の短軸方向の長さ（扁平状黒鉛の厚み方向の長さ）をＢとしたときにＡ／Ｂで表される。扁平状黒鉛のアスペクト比は、顕微鏡で扁平状黒鉛を拡大し、任意に１０個の扁平状黒鉛を選択して、それぞれのＡ／Ｂを測定し、それらの測定値の算術平均値をとったものである。 When the aspect ratio of the flat graphite is A, the length of the flat graphite in the long axis direction is A, and the length of the flat graphite in the short axis direction (the length in the thickness direction of the flat graphite) is B. It is represented by A / B. The aspect ratio of the flat graphite expanded the flat graphite with a microscope, selected 10 flat graphite arbitrarily, measured each A / B, and took the arithmetic mean value of those measurement values It is a thing.
扁平状黒鉛は、１個の一次粒子からなる単数粒子、及び複数個の一次粒子を造粒した造粒粒子のいずれであってもよい。また、扁平状黒鉛は、多孔質状の黒鉛粒子であってもよい。 Flat graphite may be any of single particles consisting of one primary particle and granulated particles obtained by granulating a plurality of primary particles. The flat graphite may be porous graphite particles.
カーボンブラックとしては、アセチレンブラック、ケッチェンブラック、サーマルブラック、ファーネスブラック等が挙げられる。これらの中も、導電性の観点からアセチレンブラックが好ましい。 Examples of carbon black include acetylene black, ketjen black, thermal black and furnace black. Among these, acetylene black is preferable from the viewpoint of conductivity.
導電性粒子の含有率（ＳｉＯ−Ｃ粒子に対する量）は、サイクル特性を向上させる点から、ＳｉＯ−Ｃ粒子に対して１．０質量％〜１０．０質量％が好ましく、２．０質量％〜９．０質量％がより好ましく、３．０質量％〜８．０質量％が更に好ましい。 The content of conductive particles (the amount relative to SiO-C particles) is preferably 1.0% by mass to 10.0% by mass, and 2.0% by mass with respect to SiO-C particles, from the viewpoint of improving cycle characteristics. -9.0 mass% is more preferable, and 3.0 mass%-8.0 mass% is still more preferable.
導電性粒子の含有率は、炭素の単体も含めて、高周波焼成−赤外分析法によって求めることができる。高周波焼成−赤外分析法においては、例えば、炭素硫黄同時分析装置（ＣＳＬＳ６００、ＬＥＣＯジャパン合同会社）を用いることができる。 The content rate of the conductive particles can be determined by high-frequency firing-infrared analysis, including the simple substance of carbon. In the induction baking-infrared analysis method, for example, a carbon-sulfur simultaneous analyzer (CSLS600, LECO Japan Ltd.) can be used.
導電性粒子をＳｉＯ−Ｃ粒子の表面に付着（例えば複合化）する方法としては、特に制限されないが、湿式法、及び乾式法が挙げられる。 The method for attaching (for example, complexing) the conductive particles to the surface of the SiO-C particles is not particularly limited, and examples thereof include a wet method and a dry method.
湿式法には、例えば、次に示す方法がある。まず、攪拌式のホモジナイザー、ビーズミル、ボールミル等の周知の分散機を利用して、分散媒に導電性粒子を分散させた粒子分散液を調製する。次に、得られた粒子分散液に、ＳｉＯ−Ｃ粒子を添加した後、攪拌式のホモジナイザー、ビーズミル、ボールミル等の周知の分散機を利用して撹拌する。そして、導電性粒子及びＳｉＯ−Ｃ粒子が分散された粒子分散液から、乾燥器等を利用して分散媒を除去する。これにより、導電性粒子をＳｉＯ−Ｃ粒子の表面に付着（例えば複合化）することができる。
ここで、分散媒としては、水、アルコール等の有機溶剤などを用いることができる。また、粒子分散液には、導電性粒子の分散性を高め、ＳｉＯ−Ｃ粒子の表面への導電性粒子の均一な付着を実現する点から、分散剤を添加してもよい。分散剤は使用する分散媒に応じて適宜選択することができる。分散剤は、例えば、水系であればカルボキシメチルセルロースが分散安定性に優れ、好ましい。
The wet method includes, for example, the following method. First, a particle dispersion liquid in which conductive particles are dispersed in a dispersion medium is prepared using a known dispersing machine such as a stirring type homogenizer, a bead mill, a ball mill or the like. Next, SiO-C particles are added to the obtained particle dispersion, and then stirred using a known dispersing machine such as a stirring homogenizer, bead mill, ball mill or the like. Then, the dispersion medium is removed from the particle dispersion liquid in which the conductive particles and the SiO-C particles are dispersed, using a drier or the like. Thereby, the conductive particles can be attached (eg, complexed) to the surface of the SiO-C particles.
Here, as the dispersion medium, organic solvents such as water and alcohol can be used. In addition, a dispersant may be added to the particle dispersion in order to enhance the dispersibility of the conductive particles and to achieve uniform adhesion of the conductive particles to the surface of the SiO-C particles. A dispersing agent can be suitably selected according to the dispersion medium to be used. As the dispersant, for example, in the case of an aqueous system, carboxymethylcellulose is preferable because of its excellent dispersion stability.
乾式法には、例えば、ケイ素酸化物粒子に炭素の単体を付与する際に、導電性粒子を同時に添加する方法がある。具体的には、例えば、ケイ素酸化物粒子と炭素源とを混合する際、導電性粒子も共に混合し、力学的エネルギーを加える処理（例えば、メカノケミカル処理）を施す。これにより、導電性粒子をＳｉＯ−Ｃ粒子の表面に付着（例えば複合化）することができる。 In the dry method, for example, there is a method of simultaneously adding conductive particles when applying a single substance of carbon to silicon oxide particles. Specifically, for example, when silicon oxide particles and a carbon source are mixed, conductive particles are also mixed together, and a process (e.g., mechanochemical process) of applying mechanical energy is performed. Thereby, the conductive particles can be attached (eg, complexed) to the surface of the SiO-C particles.
以上の工程を経て、ＳｉＯ−Ｃ粒子の表面に導電性粒子が付着したＣＰ／ＳｉＯ−Ｃ粒子が得られる。なお、粒子分散液から分散媒を除去した後、必要に応じて、篩機等を利用して、得られたＣＰ／ＳｉＯ−Ｃ粒子の分級処理を行ってもよい。 Through the above steps, CP / SiO-C particles in which conductive particles adhere to the surface of the SiO-C particles are obtained. In addition, after removing the dispersion medium from the particle dispersion, if necessary, the obtained CP / SiO-C particles may be classified using a sieve machine or the like.
（有機物）
本発明の負極材料は、ＳｉＯ−Ｃ粒子の表面の一部又は全部に存在している有機物を含む。有機物を含むことにより、負極材料の比表面積が低下し、電解液との反応が抑制されるため、充放電後の回復率が向上すると考えられる。
(organic matter)
The negative electrode material of the present invention contains an organic substance present in part or all of the surface of the SiO-C particles. By containing the organic substance, the specific surface area of the negative electrode material is reduced, and the reaction with the electrolytic solution is suppressed, so it is considered that the recovery rate after charge and discharge is improved.
有機物の含有率は、負極材料全体中に０．１質量％〜２．０質量％であることが好ましい。前記の範囲内であると、導電性の低下を抑制しつつ充放電後の回復率の向上の効果が充分得られる傾向にある。負極材料全体中の有機物の含有率は、０．２質量％〜１．５質量％であることが好ましく、０．３質量％〜１．０質量％であることがより好ましい。 It is preferable that the content rate of organic substance is 0.1 mass%-2.0 mass% in the whole negative electrode material. It exists in the tendency for the effect of the improvement of the recovery rate after charge / discharge to be acquired sufficiently, suppressing the electroconductive fall as it is in the said range. It is preferable that it is 0.2 mass%-1.5 mass%, and, as for the content rate of the organic substance in the whole negative electrode material, it is more preferable that it is 0.3 mass%-1.0 mass%.
負極材料が有機物を有しているか否かは、例えば、充分に乾燥させた負極材を有機物が分解する温度以上でありかつ炭素の単体及び導電性粒子が分解する温度よりも低い温度（例えば３００℃）に加熱して、有機物が分解した後の負極材料の質量を測定することで確認することができる。具体的には、加熱前の負極材料の質量をＡｇ、加熱後の負極材料の質量をＢｇとした場合に｛（Ａ−Ｂ）／Ａ｝×１００で表される質量の変化率が０．１％以上であると、負極材料が有機物を含んでいると判断することができる。
変化率は０．１〜２．０％であることが好ましく、０．３〜１．０％であることがより好ましい。変化率が０．１％以上であると充分な量の有機物がＣＰ／ＳｉＯ−Ｃ粒子の表面に存在しており、本発明の効果が充分得られる傾向にある。
Whether or not the negative electrode material has an organic substance is, for example, a temperature which is equal to or higher than the temperature at which the organic substance decomposes the sufficiently dried negative electrode material and lower than the temperature at which the carbon single substance and the conductive particles are decomposed. It can be confirmed by measuring the mass of the negative electrode material after heating to ° C. and decomposition of the organic matter. Specifically, when the mass of the negative electrode material before heating is Ag, and the mass of the negative electrode material after heating is Bg, the rate of change of mass represented by {(A−B) / A} × 100 is 0. It can be determined that the negative electrode material contains an organic substance at 1% or more.
The rate of change is preferably 0.1 to 2.0%, more preferably 0.3 to 1.0%. If the rate of change is 0.1% or more, a sufficient amount of organic matter is present on the surface of the CP / SiO-C particles, and the effect of the present invention tends to be sufficiently obtained.
有機物は、第一成分として多糖、ゼラチン、カゼイン及び水溶性ポリエーテルからなる群より選ばれる１つ以上と、第二成分として単糖、二糖、オリゴ糖、アミノ酸、没食子（もっしょくし）酸、タンニン、サッカリン、サッカリンの塩及びブチンジオールからなる群より選ばれる１つ以上とを含むことが好ましい。本発明において多糖は単糖分子が１０個以上結合した構造を有する化合物を意味し、オリゴ糖は単糖分子が３個〜１０個結合した構造を有する化合物を意味する。 The organic substance is one or more selected from the group consisting of polysaccharides, gelatin, casein and water-soluble polyether as a first component, and monosaccharides, disaccharides, oligosaccharides, amino acids, gallic acid (resorcous acid), as a second component. It is preferable to include one or more selected from the group consisting of tannin, saccharin, a salt of saccharin and butynediol. In the present invention, a polysaccharide means a compound having a structure in which 10 or more monosaccharide molecules are linked, and an oligosaccharide means a compound having a structure in which 3 to 10 monosaccharide molecules are linked.
多糖として具体的には、デンプン、デンプンの誘導体、デキストリン、デキストリンの誘導体、シクロデキストリン、セルロースの誘導体、アルギン酸、アルギン酸の誘導体、プルラン、グリコーゲン、アガロース、カラギーナン、ペクチン、リグニンの誘導体、キシログルカン等を挙げることができる。
単糖として具体的には、アラビノース、グルコース、マンノース、ガラクトース等を挙げることができる。
二糖として具体的には、スクロース、マルトース、ラクトース、セロビオース、トレハロース等を挙げることができる。
オリゴ糖として具体的には、ラフィノース、スタキオース、マルトトリオース等を挙げることができる。
アミノ酸として具体的には、グリシン、アラニン、バリン、ロイシン、イソロイシン、セリン、トレオニン、システイン、シスチン、メチオニン、アスパラギン酸、グルタミン酸、リシン、アルギニン、フェニルアラニン、チロシン、ヒスチジン、トリプトファン、プロリン、オキシプロリン、グリシルグリシン等を挙げることができる。
タンニンとして具体的には、茶カテキン、柿カテキン等を挙げることができる。
Specific examples of polysaccharides include starch, derivatives of starch, dextrin, derivatives of dextrin, cyclodextrin, derivatives of cellulose, alginic acid, derivatives of alginic acid, pullulan, glycogen, agarose, carrageenan, pectin, derivatives of lignin, xyloglucan etc. It can be mentioned.
Specific examples of monosaccharides include arabinose, glucose, mannose and galactose.
Specific examples of disaccharides include sucrose, maltose, lactose, cellobiose, trehalose and the like.
Specific examples of oligosaccharides include raffinose, stachyose, maltotriose and the like.
Specifically, as amino acids, glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline, glyol And so forth.
Specific examples of tannins include tea catechins and persimmon catechins.
第一成分は多糖の少なくとも１種を含むことが好ましく、デンプン、デキストリン及びプルランからなる群より選択される少なくとも１種がより好ましい。第一成分は、負極材料の表面の一部又は全部を被覆するように存在することでその比表面積を低下させると考えられる。その結果、負極材料と電解液との反応が抑制され、リチウムイオン二次電池の寿命の向上に寄与すると考えられる。 The first component preferably contains at least one polysaccharide, and more preferably at least one selected from the group consisting of starch, dextrin and pullulan. The first component is considered to reduce its specific surface area by being present so as to cover part or all of the surface of the negative electrode material. As a result, the reaction between the negative electrode material and the electrolytic solution is suppressed, which is considered to contribute to the improvement of the life of the lithium ion secondary battery.
第二成分は二糖及び単糖からなる群より選択される少なくとも１種を含むことが好ましく、マルトース、ラクトース、トレハロース及びグルコースからなる群より選択される少なくとも１種を含むことがより好ましい。第二成分は、第一成分中に取り込まれ、第一成分から形成される沈殿膜の水又は電解液への溶解性を抑制すると考えられる。 The second component preferably comprises at least one selected from the group consisting of disaccharides and monosaccharides, and more preferably comprises at least one selected from the group consisting of maltose, lactose, trehalose and glucose. The second component is considered to be incorporated into the first component and to suppress the solubility of the precipitate film formed from the first component in water or an electrolyte.
有機物が第一成分と第二成分とを含む場合、その質量比（第一成分：第二成分）は１：１〜２５：１であることが好ましく、３：１〜２０：１であることがより好ましく、５：１〜１５：１であることがさらに好ましい。質量比が上記の範囲内であると、貯蔵特性の維持率及び回復率が改善する傾向がある。 When the organic matter contains the first component and the second component, the mass ratio (first component: second component) is preferably 1: 1 to 25: 1, and 3: 1 to 20: 1. Is more preferably 5: 1 to 15: 1. When the mass ratio is in the above range, the retention rate and recovery rate of the storage characteristics tend to be improved.
有機物をＣＰ／ＳｉＯ−Ｃ粒子の表面の一部又は全部に存在させる方法は特に制限されない。例えば、有機物を溶解又は分散させた液体にＣＰ／ＳｉＯ−Ｃ粒子を入れ、必要に応じて撹拌することにより、有機物をＣＰ／ＳｉＯ−Ｃ粒子に付着させることができる。その後、有機物が付着したＣＰ／ＳｉＯ−Ｃ粒子を液体から取り出し、必要に応じて乾燥することで、有機物が表面に付着したＣＰ／ＳｉＯ−Ｃ粒子を得ることができる。
撹拌時の水溶液の温度は特に制限されず、例えば５℃〜９５℃から選択することができる。乾燥時の温度は特に制限されず、例えば５０℃〜２００℃から選択することができる。水溶液中の有機物の含有率は特に制限されず、例えば０．１質量％〜２０質量％から選択することができる。
The method for causing the organic matter to be present on part or all of the surface of the CP / SiO-C particles is not particularly limited. For example, the CP / SiO-C particles can be attached to the CP / SiO-C particles by putting the CP / SiO-C particles in a liquid in which the organic material is dissolved or dispersed and stirring as necessary. Thereafter, the CP / SiO-C particles to which the organic matter is attached are taken out of the liquid and dried as needed, whereby CP / SiO-C particles to which the organic matter is attached can be obtained.
The temperature of the aqueous solution at the time of stirring is not particularly limited, and can be selected, for example, from 5 ° C to 95 ° C. The temperature at the time of drying is not particularly limited, and can be selected, for example, from 50 ° C to 200 ° C. The content of the organic substance in the aqueous solution is not particularly limited, and can be selected, for example, from 0.1% by mass to 20% by mass.
以下、本発明の負極材料の一例について図面を参照して説明する。
図１〜図３は、本発明の負極材料の構成の例を示す概略断面図である。
図１では、炭素の単体１０がケイ素酸化物粒子２０の表面全体を被覆している。図２では、炭素の単体１０がケイ素酸化物粒子２０の表面全体を被覆しているが、均一には覆っていない。また、図３では、炭素の単体１０がケイ素酸化物粒子２０の表面に部分的に存在し、一部でケイ素酸化物粒子２０の表面が露出している。そして、図１〜図３では、この状態で炭素の単体１０が表面に存在するケイ素酸化物粒子２０（ＳｉＯ−Ｃ粒子）の表面に導電性粒子１４が付着している。さらに、この導電性粒子１４が付着したケイ素酸化物粒子２０（ＣＰ／ＳｉＯ−Ｃ粒子）が有機物１６で被覆されている。
なお、図１〜図３では、ケイ素酸化物粒子２０の形状は、模式的に球状（断面形状としては円）で表されているが、球状、ブロック状、鱗片状、断面形状が多角形の形状（角のある形状）等のいずれであってもよい。また、図１〜３では、導電性粒子１４の形状は扁平状で表されているが、これに限られるわけではない。また、図１〜図３では、炭素の単体１０が表面に存在するケイ素酸化物粒子２０（ＳｉＯ−Ｃ粒子）の表面の全部が有機物１６で被覆されているが、これに限られず、表面の一部が被覆されていてもよい。
Hereinafter, an example of the negative electrode material of the present invention will be described with reference to the drawings.
1 to 3 are schematic cross-sectional views showing examples of the configuration of the negative electrode material of the present invention.
In FIG. 1, a single carbon 10 covers the entire surface of the silicon oxide particles 20. In FIG. 2, the single carbon 10 covers the entire surface of the silicon oxide particles 20 but does not cover uniformly. Further, in FIG. 3, a single carbon 10 is partially present on the surface of the silicon oxide particle 20, and the surface of the silicon oxide particle 20 is partially exposed. In FIGS. 1 to 3, the conductive particles 14 are attached to the surface of the silicon oxide particles 20 (SiO-C particles) on the surface of which a single carbon 10 is present in this state. Furthermore, the silicon oxide particles 20 (CP / SiO-C particles) to which the conductive particles 14 are attached are coated with the organic matter 16.
In FIGS. 1 to 3, the shape of the silicon oxide particle 20 is schematically represented by a spherical shape (circle as a cross-sectional shape), but it is spherical, block-like, scaly-like, or polygonal in cross-sectional shape It may be any shape (shape with corners) or the like. Moreover, although the shape of the electroconductive particle 14 is represented by flat shape in FIGS. 1-3, it is not necessarily restricted to this. Moreover, although the whole surface of the silicon oxide particle 20 (SiO-C particle | grains) in which the simple substance 10 of carbon exists on the surface is coat | covered with the organic substance 16 in FIGS. 1-3, it is not restricted to this. A part may be coated.
図４は、図１〜図３の負極材料の一部を拡大した断面図であり、図４（Ａ）では負極材料における炭素の単体１０の形状の一態様を説明し、図４（Ｂ）では負極材料における炭素の単体１０の形状の他の態様を説明する。図１〜図３の場合、図４（Ａ）に示すように炭素の単体１０が全体的に炭素で構成されていても、図４（Ｂ）で示すように炭素の単体１０が粒子１２で構成されていてもよい。なお、図４（Ｂ）では炭素の単体１０において粒子１２の輪郭形状が残った状態で示しているが、粒子１２同士が結合していてもよい。粒子１２同士が結合した場合には、炭素の単体１０が全体的に炭素で構成されることがあるが、炭素の単体１０の一部において空隙が内包される場合がある。このように炭素の単体１０の一部に空隙が内包されていてもよい。 FIG. 4 is an enlarged cross-sectional view of a part of the negative electrode material of FIGS. 1 to 3, and FIG. 4 (A) illustrates one mode of the shape of carbon single body 10 in the negative electrode material. Now, another aspect of the shape of the carbon single body 10 in the negative electrode material will be described. In the case of FIGS. 1 to 3, even if the single carbon 10 is entirely composed of carbon as shown in FIG. 4 (A), the single carbon 10 is particles 12 as shown in FIG. 4 (B). It may be configured. Although FIG. 4B shows the state in which the contour shape of the particles 12 remains in the single carbon 10, the particles 12 may be bonded to each other. When the particles 12 are bonded to each other, the carbon simple substance 10 may be entirely composed of carbon, but a part of the carbon simple substance 10 may contain a void. Thus, a void may be contained in part of the single carbon 10.
本発明の負極材料の体積基準の平均粒子径Ｄ５０％は、０．１μｍ〜２０μｍであることが好ましく、０．５μｍ〜１０μｍであることがより好ましい。平均粒子径が２０μｍ以下の場合、負極内での負極材料の分布が均一化し、更には、充放電時の膨張及び収縮が均一化することでサイクル特性の低下が抑えられる。また、平均粒子径が０．１μｍ以上の場合には、負極密度が大きくなりやすく、高容量化しやすい。 The volume-based average particle diameter D50% of the negative electrode material of the present invention is preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 10 μm. When the average particle size is 20 μm or less, the distribution of the negative electrode material in the negative electrode becomes uniform, and further, the expansion and contraction during charge and discharge become uniform, whereby the deterioration of the cycle characteristics can be suppressed. When the average particle size is 0.1 μm or more, the density of the negative electrode tends to be large, and the capacity tends to be high.
本発明の負極材料の比表面積は、０．１ｍ２/ｇ〜１５ｍ２/ｇであることが好ましく、０．５ｍ２/ｇ〜１０ｍ２/ｇであることがより好ましく、１．０ｍ２/ｇ〜７．０ｍ２/ｇであることが更に好ましく、１．０ｍ２/ｇ〜３．０ｍ２/ｇであることが特により好ましい。比表面積が１５ｍ２/ｇ以下の場合、得られるリチウムイオン二次電池の初回の不可逆容量の増加が抑えられる。更には、負極を作製する際に結着剤の使用量の増加が抑えられる。比表面積が０．１ｍ２/ｇ以上の場合、負極材料と電解液との接触面積が増加し、充放電効率が増大する。比表面積の測定には、ＢＥＴ法（窒素ガス吸着法）等の既知の方法を採用することができる。 The specific surface area of the negative electrode material of the present invention is preferably 0.1m 2 / g~15m 2 / g, more preferably 0.5m 2 / g~10m 2 / g, 1.0m 2 / more preferably g~7.0m is 2 / g, it is more particularly preferred is 1.0m 2 /g~3.0m 2 / g. When the specific surface area is 15 m 2 / g or less, the increase in initial irreversible capacity of the obtained lithium ion secondary battery can be suppressed. Furthermore, the increase in the amount of binder used can be suppressed when producing the negative electrode. When the specific surface area is 0.1 m 2 / g or more, the contact area between the negative electrode material and the electrolytic solution is increased, and the charge and discharge efficiency is increased. For the measurement of the specific surface area, known methods such as BET method (nitrogen gas adsorption method) can be adopted.
また、本発明の負極材料は、有機物の含有率が０．１質量％〜２．０質量％であり、導電性粒子の含有率が１．０質量％〜１０．０質量％であり、炭素の単体の含有率が０．５質量％〜１０．０質量％であり、ケイ素の結晶子の大きさが２．０ｎｍ〜８．０ｎｍであることが好ましく、有機物の含有率が０．２質量％〜１．５質量％であり、導電性粒子の含有率が２．０質量％〜９．０質量％であり、炭素の単体の含有率が１．０質量％〜９．０質量％であり、ケイ素の結晶子の大きさが３．０ｎｍ〜６．０ｎｍであることがより好ましい。 In the negative electrode material of the present invention, the content of organic matter is 0.1% by mass to 2.0% by mass, the content of conductive particles is 1.0% by mass to 10.0% by mass, and carbon It is preferable that the content of the single substance is 0.5 mass% to 10.0 mass%, and the size of the crystallite of silicon is 2.0 nm to 8.0 nm, and the content ratio of the organic substance is 0.2 mass. % To 1.5% by mass, the content of conductive particles is 2.0% to 9.0% by mass, and the content of carbon alone is 1.0% to 9.0% by mass. More preferably, the crystallite size of silicon is 3.0 nm to 6.0 nm.
本発明の負極材料は、必要に応じて、リチウムイオン二次電池の負極の活物質として従来知られている炭素系負極材料と併用してもよい。併用する炭素系負極材料の種類に応じて、充放電効率の向上、サイクル特性の向上、電極の膨張抑制効果等が得られる。
従来知られている炭素系負極材料としては、鱗片状天然黒鉛、鱗片状天然黒鉛を球形化した球状天然黒鉛等の天然黒鉛類、人造黒鉛、非晶質炭素などが挙げられる。また、これらの炭素系負極材料は、その表面の一部又は全部に更に炭素を有していてもよい。これら炭素系負極材料の１種又は２種以上を、本発明の負極材料に混合して使用してもよい。
The negative electrode material of the present invention may be used in combination with a carbon-based negative electrode material conventionally known as an active material of a negative electrode of a lithium ion secondary battery, if necessary. Depending on the type of carbon-based negative electrode material to be used in combination, improvement in charge / discharge efficiency, improvement in cycle characteristics, expansion suppression effect of the electrode, etc. can be obtained.
Conventionally known carbon-based negative electrode materials include scaly natural graphite, natural graphites such as spherical natural graphite obtained by spheroidizing scaly natural graphite, artificial graphite, and amorphous carbon. In addition, these carbon-based negative electrode materials may further have carbon on part or all of the surface thereof. One or more of these carbon-based negative electrode materials may be mixed with the negative electrode material of the present invention and used.
本発明の負極材料を炭素系負極材料と併用して使用する場合、本発明の負極材料（Ａ）と炭素系負極材料（Ｂ）との比率（Ａ：Ｂ）は、目的に応じて適宜調整することが可能である。例えば、電極の膨張抑制効果の観点からは、質量基準で、０．１：９９．９〜２０：８０であることが好ましく、０．５：９９．５〜１５：８５であることがより好ましく、１：９９〜１０：９０であることが更に好ましい。 When the negative electrode material of the present invention is used in combination with a carbon-based negative electrode material, the ratio (A: B) of the negative electrode material (A) of the present invention to the carbon-based negative electrode material (B) is appropriately adjusted according to the purpose. It is possible. For example, from the viewpoint of the expansion suppression effect of the electrode, it is preferably 0.1: 99.9 to 20:80 on a mass basis, and more preferably 0.5: 99.5 to 15:85. More preferably, 1:99 to 10:90.
＜リチウムイオン二次電池用負極＞
本発明のリチウムイオン二次電池用負極（以下「負極」と略称する場合がある）は、集電体と、集電体上に設けられた本発明のリチウムイオン二次電池用負極材料を含む負極材層と、を有する。例えば、本発明のリチウムイオン二次電池用負極は、本発明のリチウムイオン二次電池用負極材料、有機結着剤、溶剤又は水等の溶媒、及び必要により増粘剤、導電助剤、従来知られている炭素系負極材料等を混合した塗布液を調製し、この塗布液を集電体に塗布した後、溶剤又は水を乾燥し、加圧成形して負極材層を形成することにより得られる。一般に、有機結着剤、溶媒等と混練して、シート状、ペレット状等の形状に成形される。
<Anode for lithium ion secondary battery>
The negative electrode for a lithium ion secondary battery of the present invention (hereinafter sometimes referred to as "negative electrode") includes a current collector and the negative electrode material for a lithium ion secondary battery of the present invention provided on the current collector. And a negative electrode material layer. For example, the negative electrode for a lithium ion secondary battery of the present invention comprises the negative electrode material for a lithium ion secondary battery of the present invention, an organic binder, a solvent or a solvent such as water, and optionally a thickener, a conductive auxiliary, A coating solution is prepared by mixing known carbon-based negative electrode materials and the like, and the coating solution is applied to a current collector, and then the solvent or water is dried and pressure-formed to form a negative electrode material layer. can get. Generally, it is kneaded with an organic binder, a solvent and the like to be formed into a sheet, a pellet and the like.
有機結着剤としては、特に限定されず、スチレン−ブタジエン共重合体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、（メタ）アクリロニトリル、ヒドロキシエチル（メタ）アクリレート等のエチレン性不飽和カルボン酸エステルと、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエチレン性不飽和カルボン酸と、を共重合して得られる（メタ）アクリル共重合体；ポリ弗化ビニリデン、ポリエチレンオキサイド、ポリエピクロルヒドリン、ポリホスファゼン、ポリアクリロニトリル、ポリイミド、ポリアミドイミド等の高分子化合物；などが挙げられる。なお、「（メタ）アクリレート」とは、「アクリレート」及びそれに対応する「メタクリレート」を意味する。「（メタ）アクリル共重合体」等の他の類似の表現においても同様である。 The organic binder is not particularly limited, and styrene-butadiene copolymer; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, hydroxyethyl (meth) acrylate, etc. (Meth) acrylic copolymer obtained by copolymerizing ethylenic unsaturated carboxylic acid ester and ethylenic unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid; Polymer compounds such as vinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polyimide, polyamideimide, and the like. In addition, "(meth) acrylate" means "acrylate" and the corresponding "methacrylate." The same applies to other similar expressions such as "(meth) acrylic copolymer".
これらの有機結着剤は、それぞれの物性によって、水に分散、若しくは溶解したもの、又は、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等の有機溶剤に溶解したものがある。これらの中でも、密着性に優れることから、主骨格がポリアクリロニトリル、ポリイミド又はポリアミドイミドである有機結着剤が好ましく、後述するように負極作製時の熱処理温度が低く、電極の柔軟性が優れることから、主骨格がポリアクリロニトリルである有機結着剤が更に好ましい。ポリアクリロニトリルを主骨格とする有機結着剤としては、例えば、ポリアクリロニトリル骨格に、接着性を付与するアクリル酸及び柔軟性を付与する直鎖エーテル基を付加した製品（ＬＳＲ７（商品名）、日立化成株式会社等）が使用できる。 These organic binders may be dispersed or dissolved in water, or may be dissolved in an organic solvent such as N-methyl-2-pyrrolidone (NMP), depending on their physical properties. Among these, an organic binder having a main skeleton of polyacrylonitrile, polyimide or polyamideimide is preferable because of its excellent adhesion, and as described later, the heat treatment temperature at the time of negative electrode preparation is low, and the flexibility of the electrode is excellent. Thus, organic binders having a main skeleton of polyacrylonitrile are more preferable. As an organic binder having a polyacrylonitrile as a main skeleton, for example, a product obtained by adding an acrylic acid which imparts adhesiveness and a linear ether group which imparts flexibility to a polyacrylonitrile skeleton (LSR 7 (trade name), Hitachi Chemical Industries, Ltd. etc. can be used.
リチウムイオン二次電池負極材料の負極材層中の有機結着剤の含有比率は、０．１質量％〜２０質量％であることが好ましく、０．２質量％〜２０質量％であることがより好ましく、０．３質量％〜１５質量％であることが更に好ましい。
有機結着剤の含有比率が０．１質量％以上であることで、密着性が良好で、充放電時の膨張及び収縮によって負極が破壊されることが抑制される。一方、２０質量％以下であることで、電極抵抗が大きくなることを抑制できる。
The content ratio of the organic binder in the negative electrode material layer of the lithium ion secondary battery negative electrode material is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 20% by mass More preferably, the content is 0.3% by mass to 15% by mass.
When the content ratio of the organic binder is 0.1% by mass or more, adhesion is good, and destruction of the negative electrode due to expansion and contraction during charge and discharge can be suppressed. On the other hand, it can suppress that electrode resistance becomes large because it is 20 mass% or less.
更に、粘度を調整するための増粘剤として、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸（塩）、酸化スターチ、リン酸化スターチ、カゼイン等を、前述した有機結着剤と共に使用してもよい。
有機結着剤の混合の際に必要に応じて溶剤を用いてもよい。溶剤としては、特に制限されず、Ｎ−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、γ−ブチロラクトン等が用いられる。
Furthermore, as the thickener for adjusting the viscosity, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein, etc. are the organic binders described above. May be used with
A solvent may be used as needed in mixing the organic binder. The solvent is not particularly limited, and N-methylpyrrolidone, dimethylacetamide, dimethylformamide, γ-butyrolactone or the like is used.
なお、塗布液には導電助剤を添加してもよい。導電助剤としては、カーボンブラック、アセチレンブラック、導電性を示す酸化物、導電性を示す窒化物等が挙げられる。これらの導電助剤は１種単独で又は２種類以上を組み合わせて使用してもよい。導電助剤の含有率は、負極材層（１００質量％）中０．１質量％〜２０質量％であることが好ましい。 In addition, you may add a conductive support agent to a coating liquid. Examples of the conductive additive include carbon black, acetylene black, oxides exhibiting conductivity, nitrides exhibiting conductivity, and the like. You may use these conductive support agents individually by 1 type or in combination of 2 or more types. It is preferable that the content rate of a conductive support agent is 0.1 mass%-20 mass% in a negative electrode material layer (100 mass%).
また、集電体の材質は、特に限定されず、例えば、アルミニウム、銅、ニッケル、チタン、ステンレス鋼、ポーラスメタル（発泡メタル）及びカーボンペーパーが挙げられる。集電体の形状としては、特に限定されず、例えば、箔状、穴開け箔状及びメッシュ状が挙げられる。 Further, the material of the current collector is not particularly limited, and examples thereof include aluminum, copper, nickel, titanium, stainless steel, porous metal (foam metal) and carbon paper. The shape of the current collector is not particularly limited, and examples thereof include a foil shape, a perforated foil shape and a mesh shape.
塗布液を集電体に塗布する方法としては、特に限定されず、メタルマスク印刷法、静電塗装法、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法等が挙げられる。塗布後は、必要に応じて平板プレス、カレンダーロール等による加圧処理を行うことが好ましい。
また、シート状、ペレット状等の形状に成形された塗布液と集電体との一体化は、例えば、ロールによる一体化、プレスによる一体化及びこれらの組み合わせによる一体化により行うことができる。
The method for applying the coating solution to the current collector is not particularly limited, and metal mask printing, electrostatic coating, dip coating, spray coating, roll coating, doctor blade, gravure coating, screen printing Law etc. are mentioned. After application, it is preferable to carry out pressure treatment with a flat press, a calender roll, etc., as necessary.
Further, the integration of the coating liquid and the current collector, which are formed into a sheet shape, a pellet shape, or the like, can be performed, for example, by integration with a roll, integration with a press, or integration with a combination thereof.
集電体上に形成された負極材層又は集電体と一体化した負極材層は、用いた有機結着剤に応じて熱処理することが好ましい。例えば、ポリアクリロニトリルを主骨格とした有機結着剤を用いる場合は、１００℃〜１８０℃で熱処理することが好ましく、ポリイミド又はポリアミドイミドを主骨格とした有機結着剤を用いる場合には、１５０℃〜４５０℃で熱処理することが好ましい。
この熱処理により溶媒の除去及び有機結着剤の硬化による高強度化が進み、負極材料間の密着性及び負極材料と集電体との間の密着性が向上できる。なお、これらの熱処理は、処理中の集電体の酸化を防ぐため、ヘリウム、アルゴン、窒素等の不活性雰囲気又は真空雰囲気で行うことが好ましい。
It is preferable that the negative electrode material layer formed on the current collector or the negative electrode material layer integrated with the current collector be heat-treated in accordance with the used organic binder. For example, in the case of using an organic binder having polyacrylonitrile as a main skeleton, heat treatment at 100 ° C. to 180 ° C. is preferable, and in the case of using an organic binder having a polyimide or polyamideimide as a main skeleton, 150 It is preferable to heat-process at -450 degreeC.
The heat treatment promotes the removal of the solvent and the hardening of the organic binder to increase the strength, and the adhesion between the negative electrode material and the adhesion between the negative electrode material and the current collector can be improved. Note that these heat treatments are preferably performed in an inert atmosphere such as helium, argon, or nitrogen, or in a vacuum atmosphere, in order to prevent oxidation of the current collector during processing.
また、熱処理する前に、負極はプレス（加圧処理）しておくことが好ましい。加圧処理することで電極密度を調整することができる。本発明のリチウムイオン二次電池用負極では、電極密度が１．４ｇ／ｃｍ３〜１．９ｇ／ｃｍ３であることが好ましく、１．５ｇ／ｃｍ３〜１．８５ｇ／ｃｍ３であることがより好ましく、１．６ｇ／ｃｍ３〜１．８ｇ／ｃｍ３であることが更に好ましい。電極密度については、その値が高いほど負極の体積容量が向上する傾向があり、また、負極材料間の密着性及び負極材料と集電体との間の密着性が向上する傾向がある。 Moreover, it is preferable to press (pressurize) the negative electrode before heat treatment. The electrode density can be adjusted by pressure treatment. It The negative electrode for a lithium ion secondary battery of the present invention, it is preferable that the electrode density of 1.4g / cm 3 ~1.9g / cm 3 , a 1.5g / cm 3 ~1.85g / cm 3 it is more preferable, and further preferably from 1.6g / cm 3 ~1.8g / cm 3 . As for the electrode density, the higher the value, the more the volume capacity of the negative electrode tends to be improved, and the more the adhesion between the negative electrode materials and the adhesion between the negative electrode material and the current collector tend to be improved.
＜リチウムイオン二次電池＞
本発明のリチウムイオン二次電池は、正極と、本発明の負極と、電解質と、を備える。
本発明の負極は、例えば、セパレータを介して正極を対向して配置し、電解質を含む電解液を注入することにより、リチウムイオン二次電池とすることができる。
<Lithium ion secondary battery>
The lithium ion secondary battery of the present invention comprises a positive electrode, the negative electrode of the present invention, and an electrolyte.
The negative electrode of the present invention can be made, for example, a lithium ion secondary battery by arranging the positive electrode to face each other via a separator and injecting an electrolytic solution containing the electrolyte.
正極は、本発明の負極と同様にして、集電体表面上に正極層を形成することで得ることができる。正極における集電体には、本発明の負極で説明した集電体と同様のものを用いることができる。 The positive electrode can be obtained by forming a positive electrode layer on the surface of the current collector in the same manner as the negative electrode of the present invention. As the current collector in the positive electrode, one similar to the current collector described in the negative electrode of the present invention can be used.
本発明のリチウムイオン二次電池の正極に用いられる材料（正極材料ともいう）については、リチウムイオンをドーピング又はインターカレーション可能な化合物であればよく、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）等が挙げられる。 The material (also referred to as a positive electrode material) used for the positive electrode of the lithium ion secondary battery of the present invention may be a compound capable of doping or intercalating lithium ions, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), and the like.
正極は、正極材料と、ポリ弗化ビニリデン等の有機結着剤と、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン等の溶媒とを混合して正極塗布液を調製し、この正極塗布液をアルミニウム箔等の集電体の少なくとも一方の面に塗布し、次いで溶媒を乾燥除去し、必要に応じて加圧処理して作製することができる。
なお、正極塗布液には導電助剤を添加してもよい。導電助剤としては、カーボンブラック、アセチレンブラック、導電性を示す酸化物、導電性を示す窒化物等が挙げられる。これらの導電助剤は１種単独で又は２種類以上を組み合わせて使用してもよい。
The positive electrode is prepared by mixing a positive electrode material, an organic binder such as polyvinylidene fluoride, and a solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone to prepare a positive electrode coating solution, and It can be applied to at least one surface of a current collector such as an aluminum foil, dried by removing the solvent, and pressure-treated if necessary.
In addition, you may add a conductive support agent to positive electrode coating liquid. Examples of the conductive additive include carbon black, acetylene black, oxides exhibiting conductivity, nitrides exhibiting conductivity, and the like. You may use these conductive support agents individually by 1 type or in combination of 2 or more types.
本発明のリチウムイオン二次電池に用いられる電解液は、特に制限されず、公知のものを用いることができる。例えば、電解液として、有機溶剤に電解質を溶解させた溶液を用いることにより、非水系リチウムイオン二次電池を製造することができる。 The electrolyte used in the lithium ion secondary battery of the present invention is not particularly limited, and any known electrolyte can be used. For example, a non-aqueous lithium ion secondary battery can be manufactured by using, as the electrolytic solution, a solution in which an electrolyte is dissolved in an organic solvent.
電解質としては、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＣｌＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＡｌＯ４、ＬｉＡｌＣｌ４、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｌ、ＬｉＩ等が挙げられる。 As the electrolyte, LiPF 6, LiClO 4, LiBF 4, LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiC ( CF 3 SO 2 ) 3 , LiCl, LiI and the like.
有機溶剤としては、電解質を溶解できればよく、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、エチルメチルカーボネート、ビニルカーボネート、γ−ブチロラクトン、１，２−ジメトキシエタン及び２−メチルテトラヒドロフランが挙げられる。 The organic solvent only needs to be capable of dissolving the electrolyte, and examples thereof include propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, vinyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane and 2-methyltetrahydrofuran.
セパレータとしては、公知の各種セパレータを用いることができる。具体的には、紙製セパレータ、ポリプロピレン製セパレータ、ポリエチレン製セパレータ、ガラス繊維製セパレータ等が挙げられる。 Various known separators can be used as the separator. Specifically, paper separators, polypropylene separators, polyethylene separators, glass fiber separators and the like can be mentioned.
リチウムイオン二次電池の製造方法は、特に制限されない。例えば、以下の工程により製造することができる。まず正極と負極の２つの電極を、セパレータを介して捲回する。得られたスパイラル状の捲回群を電池缶に挿入し、予め負極の集電体に溶接しておいたタブ端子を電池缶底に溶接する。得られた電池缶に電解液を注入し、更に予め正極の集電体に溶接しておいたタブ端子を電池の蓋に溶接し、蓋を絶縁性のガスケットを介して電池缶の上部に配置し、蓋と電池缶とが接した部分をかしめて密閉することによって電池を得る。 The method for producing the lithium ion secondary battery is not particularly limited. For example, it can manufacture by the following processes. First, two electrodes of positive and negative electrodes are wound via a separator. The obtained spiral wound group is inserted into the battery can, and the tab terminal previously welded to the current collector of the negative electrode is welded to the bottom of the battery can. An electrolytic solution is injected into the obtained battery can, and a tab terminal previously welded to the current collector of the positive electrode is welded to the lid of the battery, and the lid is disposed on the upper portion of the battery can via the insulating gasket. The battery is obtained by caulking and sealing a portion where the lid and the battery can are in contact with each other.
本発明のリチウムイオン二次電池の形態は、特に限定されず、ペーパー型電池、ボタン型電池、コイン型電池、積層型電池、円筒型電池、角型電池等のリチウムイオン二次電池が挙げられる。 The form of the lithium ion secondary battery of the present invention is not particularly limited, and may be a lithium ion secondary battery such as a paper type battery, a button type battery, a coin type battery, a laminated type battery, a cylindrical type battery, and a square type battery. .
本発明のリチウムイオン二次電池用負極材料は、リチウムイオン二次電池用に限られず、リチウムイオンを挿入脱離することを充放電機構とする電気化学装置全般に適用することが可能である。 The negative electrode material for a lithium ion secondary battery of the present invention is not limited to that for a lithium ion secondary battery, and can be applied to general electrochemical devices in which insertion and desorption of lithium ions is a charge / discharge mechanism.
以下、合成例、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に制限するものではない。なお、特に断りのない限り、「部」及び「％」は質量基準である。 Hereinafter, the present invention will be more specifically described by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, unless there is particular notice, "part" and "%" are mass references.
［実施例１］
（負極材料の作製）
塊状の酸化ケイ素（株式会社高純度化学研究所、規格１０ｍｍ〜３０ｍｍ角）を乳鉢により粗粉砕しケイ素酸化物粒子を得た。このケイ素酸化物粒子を振動ミル（小型振動ミルＮＢ−０、日陶科学株式会社）によって更に粉砕した後、３００Ｍ（３００メッシュ）の試験篩で整粒し、平均粒径Ｄ５０％が５μｍのケイ素酸化物粒子を得た。平均粒子径の測定は、以下の方法で行った。
Example 1
(Preparation of negative electrode material)
A massive silicon oxide (High Purity Chemical Laboratory Co., Ltd., standard 10 mm to 30 mm square) was roughly crushed by a mortar to obtain silicon oxide particles. The silicon oxide particles are further ground by a vibration mill (small vibration mill NB-0, Nippon Ceramic Science Co., Ltd.) and then sized by a test sieve of 300 M (300 mesh), and silicon with an average particle diameter D 50% of 5 μm Oxide particles were obtained. The measurement of the average particle size was performed by the following method.
＜平均粒子径の測定＞
測定試料（５ｍｇ）を界面活性剤（エソミンＴ／１５、ライオン株式会社）０．０１質量％水溶液中に入れ、振動攪拌機で分散した。得られた分散液をレーザー回折式粒度分布測定装置（ＳＡＬＤ３０００Ｊ、株式会社島津製作所）の試料水槽に入れ、超音波をかけながらポンプで循環させ、レーザー回折式で測定した。測定条件は下記の通りとした。得られた粒度分布の体積累積５０％粒径（Ｄ５０％）を平均粒子径とした。以下、実施例において、平均粒子径の測定は同様にして行った。
・光源：赤色半導体レーザー（６９０ｎｍ）
・吸光度：０．１０〜０．１５
・屈折率：２．００−０．２０
<Measurement of average particle size>
A measurement sample (5 mg) was placed in a 0.01% by mass aqueous solution of surfactant (Esomin T / 15, Lion Corporation) and dispersed with a vibrating stirrer. The obtained dispersion was placed in a sample water tank of a laser diffraction type particle size distribution measuring apparatus (SALD 3000J, Shimadzu Corporation), circulated by a pump while applying ultrasonic waves, and measured by a laser diffraction type. The measurement conditions were as follows. The volume cumulative 50% particle size (D 50%) of the obtained particle size distribution was taken as the average particle size. Hereinafter, in the examples, measurement of the average particle size was performed in the same manner.
Light source: red semiconductor laser (690 nm)
Absorbance: 0.10 to 0.15
-Refractive index: 2.00-0.20
得られたケイ素酸化物粒子９００ｇと、石炭系ピッチ（固定炭素５０質量％）１００ｇを混合装置（ロッキングミキサーＲＭ−１０Ｇ、愛知電機株式会社）に投入し、５分間混合した後、アルミナ製の熱処理容器に充填した。熱処理容器に充填した後、これを雰囲気焼成炉において、窒素雰囲気下で、１０００℃、５時間熱処理し、熱処理物を得た。 After 900 g of the obtained silicon oxide particles and 100 g of coal-based pitch (50% by mass of fixed carbon) are introduced into a mixing apparatus (rocking mixer RM-10G, Aichi Electric Co., Ltd.) and mixed for 5 minutes, alumina heat treatment is performed. The container was filled. After filling the heat treatment container, it was heat treated in an atmosphere firing furnace under a nitrogen atmosphere at 1000 ° C. for 5 hours to obtain a heat treated product.
得られた熱処理物を乳鉢により解砕し、３００Ｍ（３００メッシュ）の試験篩により篩い分けして、ケイ素酸化物粒子の表面が炭素の単体で被覆され、平均粒径Ｄ５０％が５μｍのＳｉＯ−Ｃ粒子を得た。 The heat-treated product obtained is crushed with a mortar and sieved with a 300 M (300 mesh) test sieve, the surface of silicon oxide particles is coated with a single substance of carbon, and SiO 50 with an average particle diameter D 50% of 5 μm C particles were obtained.
＜炭素の単体の含有率の測定方法＞
ＳｉＯ−Ｃ粒子の炭素の単体の含有率を高周波焼成−赤外分析法にて測定した。高周波焼成−赤外分析法は、高周波炉にて酸素気流で試料を加熱燃焼させ、試料中の炭素及び硫黄をそれぞれＣＯ２及びＳＯ２に変換し、赤外線吸収法によって定量する分析方法である。測定装置及び測定条件等は下記の通りである。
・装置：炭素硫黄同時分析装置（ＣＳＬＳ６００、ＬＥＣＯジャパン合同会社）
・周波数：１８ＭＨｚ
・高周波出力：１６００Ｗ
・試料質量：約０．０５ｇ
・分析時間：装置の設定モードで自動モードを使用
・助燃材：Ｆｅ＋Ｗ／Ｓｎ
・標準試料：Ｌｅｃｏ５０１−０２４（Ｃ：３．０３％±０．０４ Ｓ：０．０５５％±０．００２）
９７
・測定回数：２回（表１〜表３中の炭素単体含有率の値は２回の測定値の平均値である）
<Method of measuring single carbon content>
The content of single carbon in the SiO-C particles was measured by high-frequency firing-infrared analysis. The high-frequency firing-infrared analysis method is an analysis method in which a sample is heated and burned in an oxygen stream in a high-frequency furnace to convert carbon and sulfur in the sample to CO 2 and SO 2 , respectively, and quantified by an infrared absorption method. The measuring device and the measuring conditions are as follows.
・ Device: Simultaneous analysis of carbon and sulfur (CSLS600, LECO Japan Limited)
・ Frequency: 18 MHz
・ High frequency output: 1600W
Sample weight: about 0.05 g
・ Analysis time: Use the automatic mode in the setting mode of the device ・ Supporting material: Fe + W / Sn
Standard sample: Leco 501-024 (C: 3.03% ± 0.04 S: 0.055% ± 0.002)
97
-Number of measurements: 2 times (The value of the elemental carbon content in Tables 1 to 3 is the average value of 2 measurements)
＜ケイ素の結晶子の大きさの測定＞ <Measurement of Size of Crystallite of Silicon>
粉末Ｘ線回折測定装置（ＭｕｌｔｉＦｌｅｘ（２ｋＷ）、株式会社リガク）を用いて負極材料の分析を行った。ケイ素の結晶子の大きさは、２θ＝２８．４°付近に存在するＳｉ（１１１）の結晶面に帰属されるピークの半値幅から、Ｓｃｈｅｒｒｅｒの式を用いて算出した。
測定条件は下記の通りとした。
The negative electrode material was analyzed using a powder X-ray diffraction measurement apparatus (MultiFlex (2 kW), Rigaku Corporation). The size of the crystallite of silicon was calculated using the Scherrer's equation from the half width of the peak attributed to the crystal plane of Si (111) present near 2θ = 28.4 °.
The measurement conditions were as follows.
・線源：ＣｕＫα線（波長：０．１５４０５６ｎｍ）
・測定範囲：２θ＝１０°〜４０°
・サンプリングステップ幅：０．０２°
・スキャンスピード：１°／分
・管電流：４０ｍＡ
・管電圧：４０ｋＶ
・発散スリット：１°
・散乱スリット：１°
・受光スリット：０．３ｍｍ
· Radiation source: CuKα ray (wavelength: 0.154056 nm)
・ Measurement range: 2θ = 10 ° -40 °
• Sampling step width: 0.02 °
・ Scan speed: 1 ° / min ・ Tube current: 40 mA
・ Tube voltage: 40kV
・ Divergence slit: 1 °
Scattering slit: 1 °
· Light receiving slit: 0.3 mm
なお、得られたプロファイルは、上記装置に付属の構造解析ソフト（ＪＡＤＥ６、株式会社リガク）を用いて下記の設定で、バックグラウンド（ＢＧ）除去及びピーク分離した。 The obtained profile was subjected to background (BG) removal and peak separation according to the following settings using structural analysis software (JADE 6, Rigaku Corporation) attached to the above-mentioned apparatus.
［Ｋα２ピーク除去及びバックグラウンド除去］
・Ｋα１／Ｋα２強度比：２．０
・ＢＧ点からのＢＧカーブ上下（σ）：０．０
[Kα2 peak removal and background removal]
・ Kα1 / Kα2 intensity ratio: 2.0
・ Up and down of BG curve from BG point (σ): 0.0
［ピークの指定］
・Ｓｉ（１１１）に帰属するピーク：２８．４°±０．３°
・ＳｉＯ２に帰属するピーク：２１°±０．３°
[Specify Peak]
・ The peak attributable to Si (111): 28.4 ° ± 0.3 °
· Peak attributable to SiO 2 : 21 ° ± 0.3 °
［ピーク分離］
・プロファイル形状関数：Ｐｓｅｕｄｏ−Ｖｏｉｇｔ
・バックグラウンド固定
[Peak separation]
Profile shape function: Pseudo-Voigt
・ Fixed background
上記設定により構造解析ソフトから導き出されたＳｉ（１１１）に帰属するピークの半値幅を読み取り、下記Ｓｃｈｅｒｒｅｒの式よりケイ素の結晶子の大きさを算出した。
Ｄ＝Ｋλ／Ｂ ｃｏｓθ
Ｂ＝（Ｂｏｂｓ ２−ｂ２）１／２
Ｄ：結晶子の大きさ（ｎｍ）
Ｋ：Ｓｃｈｅｒｒｅｒ定数（０．９４）
λ：線源波長（０．１５４０５６ｎｍ）
θ：測定半値幅ピーク角度
Ｂｏｂｓ：半値幅（構造解析ソフトから得られた測定値）
ｂ：標準ケイ素（Ｓｉ）の測定半値幅
The half value width of the peak belonging to Si (111) derived from the structural analysis software by the above setting was read, and the size of the silicon crystallite was calculated from the following Scherrer equation.
D = Kλ / B cos θ
B = (B obs 2- b 2 ) 1/2
D: Size of crystallite (nm)
K: Scherrer constant (0.94)
λ: source wavelength (0.154056 nm)
θ: measured half width width peak angle B obs : half width (measured value obtained from structural analysis software)
b: Measured half width of standard silicon (Si)
＜導電性粒子の複合＞
次に、導電性粒子として、平均粒子径Ｄ５０％が３μｍの鱗片状黒鉛(ＫＳ-６、Ｔｉｍｃａｌ)及びアセチレンブラック（ＨＳ１００、電気化学工業株式会社）を準備した。
<Composition of conductive particles>
Next, flake-like graphite (KS-6, Timcal) and acetylene black (HS100, Denki Kagaku Kogyo Co., Ltd.) having an average particle diameter D 50% of 3 μm were prepared as conductive particles.
水８００ｇに対して、鱗片状黒鉛(ＫＳ-６、Ｔｉｍｃａｌ)を１５６ｇ、アセチレンブラック（ＨＳ-１００、電気化学工業株式会社）を４０ｇ、カルボキシメチルセルロースを４ｇ入れ、ビースミルで分散及び混合し、導電性粒子の分散液（固形分２５質量％）を得た。 Into 800 g of water, 156 g of scaly graphite (KS-6, Timcal), 40 g of acetylene black (HS-100, Denki Kagaku Kogyo Co., Ltd.) and 4 g of carboxymethylcellulose are added and dispersed and mixed in a bead mill, and conductive A dispersion of particles (solid content 25% by mass) was obtained.
次に、水４５０ｇに得られた導電性粒子の分散液１００ｇを入れ攪拌機で良く攪拌した後、ＳｉＯ−Ｃ粒子５００ｇを添加し、更に撹拌してＳｉＯ−Ｃ粒子及び導電性粒子が分散した分散液を得た。 Next, 100 g of the obtained dispersion liquid of conductive particles is added to 450 g of water and stirred well with a stirrer, and then 500 g of SiO-C particles are added and further stirred to disperse SiO-C particles and conductive particles dispersed. I got a liquid.
得られたＳｉＯ−Ｃ粒子及び導電性粒子が分散した液を乾燥機に入れ、１５０℃で１２時間乾燥処理をし、水を除去した。これにより導電性粒子が表面に付着したＣＰ／ＳｉＯ−Ｃ粒子を得た。その後、乳鉢により解砕し、次いで３００メッシュの試験篩により篩分けし、平均粒子径Ｄ５０％が５．５μｍの負極材料を得た。 The liquid in which the obtained SiO-C particles and the conductive particles were dispersed was placed in a drier and dried at 150 ° C. for 12 hours to remove water. As a result, CP / SiO-C particles having conductive particles attached to the surface were obtained. Thereafter, the mixture was crushed with a mortar and then sieved with a 300-mesh test sieve to obtain a negative electrode material having an average particle diameter D of 50% of 5.5 μm.
＜導電性粒子の含有率の測定＞
導電性粒子の含有率は、高周波焼成−赤外分析法にて測定した。本測定ではＳｉＯ-Ｃ粒子の炭素の単体の含有率も含まれるため、予め炭素の単体の含有率を、高周波焼成−赤外分析法にて測定した。測定は、上記炭素の単体の含有率の測定方法と同様にした。
<Measurement of content of conductive particles>
The content of the conductive particles was measured by high-frequency firing-infrared analysis. In this measurement, since the content rate of the simple substance of carbon of the SiO-C particles is also included, the content rate of the simple substance of carbon is measured in advance by the high frequency baking-infrared analysis method. The measurement was performed in the same manner as the method of measuring the content of carbon alone.
＜有機物の複合＞
純水１リットルに対して有機物としてプルランを０．７ｇ溶解後、１００ｇのＣＰ／ＳｉＯ−Ｃ粒子を投入し、ホモナイザーで１０分間撹拌し、分散処理を行った。その後、トレハロース０．１ｇを投入し、１５０℃の恒温槽中で１２時間乾燥させて、負極材料である有機物が付着したＣＰ／ＳｉＯ−Ｃ粒子を得た。得られた負極材料の平均粒子径Ｄ５０％は、５．５μｍであった。
<Composition of organic matter>
After 0.7 g of pullulan as an organic substance was dissolved in 1 liter of pure water, 100 g of CP / SiO-C particles were added, and the mixture was stirred for 10 minutes with a homogenizer to carry out dispersion treatment. Thereafter, 0.1 g of trehalose was added and dried in a thermostat at 150 ° C. for 12 hours to obtain CP / SiO-C particles to which an organic substance as a negative electrode material is attached. The average particle diameter D50% of the obtained negative electrode material was 5.5 μm.
＜有機物の含有率の測定方法＞
得られた負極材料を大気下の電気炉で、３００℃で２時間加熱し、加熱前後の質量を測定した。加熱前の質量（Ａ）は１．００００ｇであり、加熱後の質量（Ｂ）は０．９９２８ｇであり、質量の変化率は０．７２％であった。
<Method of measuring the content of organic matter>
The obtained negative electrode material was heated at 300 ° C. for 2 hours in an electric furnace under the atmosphere, and the mass before and after heating was measured. The mass (A) before heating was 1.0000 g, the mass (B) after heating was 0.9928 g, and the rate of change in mass was 0.72%.
＜負極材料のＢＥＴ比表面積の測定＞
高速比表面積／細孔分布測定装置（ＡＳＡＰ２０２０、マイクロメリティックスジャパン合同会社）を用い、液体窒素温度（７７Ｋ）での窒素吸着を５点法で測定しＢＥＴ法（相対圧範囲：０．０５〜０．２）より算出した。
<Measurement of BET specific surface area of negative electrode material>
Using a high-speed specific surface area / pore distribution analyzer (ASAP 2020, Micromeritics Japan Ltd.), the nitrogen adsorption at liquid nitrogen temperature (77 K) is measured by the five-point method, and the BET method (relative pressure range: 0.05) Calculated from 0.20.2).
（負極の作製方法）
上記手法で作製した負極材料の粉末（９７．６質量部）、カルボキシメチルセルロース（ＣＭＣ）（１．２質量部）、スチレン−ブタジエンゴム（ＳＢＲ、１．２質量部）を混練し、均一なスラリーを作製した。このスラリーを、電解銅箔の光沢面に塗布量が１０ｍｇ／ｃｍ２となるように塗布し、９０℃、２時間で予備乾燥させた後、ロールプレスで密度１．６５ｇ／ｃｍ３になるように調整した。その後、真空雰囲気下で、１２０℃で４時間乾燥させることによって硬化処理を行い、負極を得た。
(Production method of negative electrode)
Powder of negative electrode material prepared by the above method (97.6 parts by mass), carboxymethyl cellulose (CMC) (1.2 parts by mass), styrene-butadiene rubber (SBR, 1.2 parts by mass) are kneaded and uniform slurry Was produced. This slurry is applied to the shiny side of the electrodeposited copper foil so that the coating amount is 10 mg / cm 2, and after being predried for 2 hours at 90 ° C., the density is 1.65 g / cm 3 with a roll press. Adjusted to Thereafter, curing was performed by drying at 120 ° C. for 4 hours in a vacuum atmosphere to obtain a negative electrode.
（リチウムイオン二次電池の作製）
上記で得られた電極を負極とし、対極として金属リチウム、電解液として１ＭのＬｉＰＦ６を含むエチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）及びエチルメチルメチルカーボネート（ＥＭＣ）（体積比１：１：１）とビニレンカーボネート（ＶＣ）（１．０質量％）の混合液、セパレータとして厚さ２５μｍのポリエチレン製微孔膜、スペーサーとして厚さ２５０μｍの銅板を用いて２０１６型コインセルを作製した。
(Preparation of lithium ion secondary battery)
The electrode obtained above is used as a negative electrode, metal lithium as a counter electrode, ethylene carbonate (EC) containing 1 M LiPF 6 as an electrolyte, diethyl carbonate (DEC) and ethyl methyl methyl carbonate (EMC) (volume ratio 1: 1: 1) A mixed solution of vinylene carbonate (VC) (1.0% by mass), a polyethylene microporous membrane with a thickness of 25 μm as a separator, and a copper plate with a thickness of 250 μm as a spacer were used to fabricate 2016 type coin cell.
（電池評価）
＜初回充電容量、初回放電容量、充放電効率＞
上記で得られた電池を、２５℃に保持した恒温槽に入れ、０．４５ｍＡ/ｃｍ２で０Ｖになるまで定電流充電を行った後、０Ｖの定電圧で電流が０．０９ｍＡ/ｃｍ２に相当する値に減衰するまで更に充電し、初回充電容量を測定した。充電後、３０分間の休止を入れたのちに放電を行った。放電は０．４５ｍＡ/ｃｍ２で１．５Ｖになるまで行い、初回放電容量を測定した。このとき、容量は用いた負極材料の質量あたりに換算した。初回放電容量を初回充電容量で割った値を初期の充放電効率（％）として算出した。結果を表１に示す。
(Battery evaluation)
<Initial charge capacity, initial discharge capacity, charge / discharge efficiency>
The resultant battery above, placed in a constant temperature bath maintained at 25 ℃, 0.45mA / cm 2 after the constant current charging until 0V, the current at a constant voltage of 0V is 0.09 mA / cm 2 The battery was further charged until it had decayed to a value corresponding to, and the initial charge capacity was measured. After charging, after 30 minutes of rest, discharging was performed. The discharge was performed at 1.5 mA at 0.45 mA / cm 2 , and the initial discharge capacity was measured. At this time, the capacity was converted to the weight of the used negative electrode material. The value obtained by dividing the initial discharge capacity by the initial charge capacity was calculated as the initial charge / discharge efficiency (%). The results are shown in Table 1.
＜サイクル特性＞
上記で得られた各電池を、２５℃に保持した恒温槽に入れ、０．４５ｍＡ/ｃｍ２で０Ｖになるまで定電流充電を行った後、０Ｖの定電圧で電流が０．０９ｍＡ/ｃｍ２に相当する値に減衰するまで更に充電した。充電後、３０分間の休止を入れた後放電を行った。放電は０．４５ｍＡ/ｃｍ２で１．５Ｖになるまで行った。この充電―放電を１サイクルとし、１０回サイクル試験を行うことで、下記式により算出されるサイクル特性の評価を行った
式：サイクル特性＝１０サイクル目の放電容量／１サイクル目の放電容量
<Cycle characteristics>
Each battery obtained above is placed in a thermostatic bath maintained at 25 ° C., and after performing constant current charge to 0 V at 0.45 mA / cm 2 , the current is 0.09 mA / cm at a constant voltage of 0 V It was further charged until it decayed to a value corresponding to 2 . After charging, it was discharged for 30 minutes after rest. The discharge was performed at 1.5 mA at 0.45 mA / cm 2 . The cycle characteristics were calculated by the following equation by performing this cycle of charge-discharge as one cycle, and the cycle characteristics were evaluated: Equation: Cycle characteristics = 10th cycle discharge capacity / 1st cycle discharge capacity
＜貯蔵特性（寿命：維持率及び回復率）＞
上記で得られた各電池を２５℃に保持した恒温槽に入れ、０．４５ｍＡ/ｃｍ２で０Ｖになるまで定電流充電を行った後、０Ｖの定電圧で電流が０．０９ｍＡ/ｃｍ２に相当する値に減衰するまで更に充電した。充電後、３０分間の休止を入れた後、放電を行った。放電は０．４５ｍＡ/ｃｍ２で１．５Ｖになるまで行った。
次に、上記と同条件で２サイクル目の充電をした後、充電状態のまま電池を７０℃に保持した恒温槽に入れ、７２時間に保管した。その後、再度２５℃に保持した恒温槽に入れ、０．４５ｍＡ/ｃｍ２で１．５Ｖになるまで放電を行った。初回の放電容量に対して、７０℃保管直後の放電容量の比率を、貯蔵特性の維持率とした。
次いで、２５℃の恒温槽で、上記と同条件で３サイクル目の充放電試験を行った。初回の放電容量に対して、この３サイクル目の放電容量の比率を、貯蔵特性の回復率とした。
<Storage characteristics (life: maintenance rate and recovery rate)>
Each of the batteries obtained in the above was placed in a constant temperature bath maintained at 25 ° C., after constant current charging until 0V at 0.45 mA / cm 2, current at a constant voltage of 0V is 0.09 mA / cm 2 The battery was further charged until it decreased to a value corresponding to. After charging, after 30 minutes of rest, discharging was performed. The discharge was performed at 1.5 mA at 0.45 mA / cm 2 .
Next, after charging for the second cycle under the same conditions as described above, the battery was put in a thermostat kept at 70 ° C. in a charged state, and stored for 72 hours. Then, it was put into a thermostat kept at 25 ° C. again, and discharge was performed at 0.45 mA / cm 2 to 1.5 V. The ratio of the discharge capacity immediately after storage at 70 ° C. to the initial discharge capacity was taken as the retention rate of the storage characteristics.
Then, a charge / discharge test of the third cycle was performed in a constant temperature bath at 25 ° C. under the same conditions as described above. The ratio of the discharge capacity at the third cycle to the initial discharge capacity was taken as the recovery rate of the storage characteristics.
［比較例１］
ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表１に示す。
Comparative Example 1
A negative electrode material was obtained in the same manner as Example 1, except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
［実施例２］
導電性粒子を鱗片状黒鉛(ＫＳ-６、Ｔｉｍｃａｌ)のみとした以外は、実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表１に示す。
Example 2
A negative electrode material was obtained in the same manner as Example 1, except that the conductive particles were only scaly graphite (KS-6, Timcal). Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
［比較例２］
実施例２において、ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例２と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表１に示す。
Comparative Example 2
A negative electrode material was obtained in the same manner as in Example 2 except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed in Example 2. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
［実施例３］
導電性粒子をアセチレンブラック（ＨＳ１００、電気化学工業株式会社）のみとした以外は、実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表２に示す。
[Example 3]
A negative electrode material was obtained in the same manner as Example 1, except that the conductive particles were only acetylene black (HS100, Denki Kagaku Kogyo Co., Ltd.). Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
［比較例３］
実施例３において、ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例３と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表２に示す。
Comparative Example 3
A negative electrode material was obtained in the same manner as in Example 3 except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed in Example 3. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
［実施例４］
導電性粒子の分散液を２００ｇとした以外は、実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表２に示す。
Example 4
A negative electrode material was obtained in the same manner as Example 1, except that the dispersion liquid of the conductive particles was changed to 200 g. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
［比較例４］
実施例４において、ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例４と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表２に示す。
Comparative Example 4
A negative electrode material was obtained in the same manner as in Example 4 except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed in Example 4. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
［実施例５］
炭素の単体の被覆工程において、ケイ素酸化物粒子８００ｇと、石炭系ピッチ（固定炭素５０質量％）２００ｇとした以外は、実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表３に示す。
[Example 5]
A negative electrode material was obtained in the same manner as Example 1, except that in the single carbon coating step, 800 g of silicon oxide particles and 200 g of coal-based pitch (50% by mass of fixed carbon) were used. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
［比較例５］
実施例５において、ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例５と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表３に示す。
Comparative Example 5
A negative electrode material was obtained in the same manner as in Example 5 except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed in Example 5. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
［実施例６］
炭素の単体の被覆工程において、熱処理温度を１０５０℃とした以外は、実施例１と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表３に示す。
[Example 6]
A negative electrode material was obtained in the same manner as in Example 1 except that the heat treatment temperature was changed to 1050 ° C. in the single carbon coating step. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
［比較例６］
実施例６おいて、ＣＰ／ＳｉＯ−Ｃ粒子の表面に有機物を付着させる工程を行わなかったこと以外は実施例６と同様にして、負極材料を得た。そして、得られた負極材料を用いて、実施例１と同様にして、２０１６型コインセルを作製し、実施例１と同様に評価を行った。結果を表３に示す。
Comparative Example 6
A negative electrode material was obtained in the same manner as in Example 6 except that the step of attaching the organic matter to the surface of the CP / SiO-C particles was not performed in Example 6. Then, using the obtained negative electrode material, in the same manner as in Example 1, a 2016-type coin cell was produced, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
表１〜表３の結果から、実施例１〜６で示したリチウムイオン二次電池用負極材料は、有機物をＣＰ／ＳｉＯ−Ｃ粒子の表面に付着させていない比較例１〜６に比べて、リチウムイオン二次電池の維持率、回復率が高まっており、寿命に優れた材料であることがわかる。 From the results of Tables 1 to 3, the negative electrode materials for lithium ion secondary batteries shown in Examples 1 to 6 are compared with Comparative Examples 1 to 6 in which the organic matter is not attached to the surface of the CP / SiO-C particles. The maintenance rate and recovery rate of the lithium ion secondary battery are increased, and it can be seen that the material has an excellent life.
１０ 炭素の単体
１２ 炭素の単体の粒子
１４ 導電性粒子
１６ 有機物
２０ ケイ素酸化物粒子
10 carbon single particle 12 carbon single particle 14 conductive particle 16 organic substance 20 silicon oxide particle
Claims (8)
前記炭素の単体の含有率が、前記ケイ素酸化物粒子と前記炭素の単体の合計量の０．５質量％〜１０．０質量％であり、
前記導電性粒子による突起構造を有するリチウムイオン二次電池用負極材料。 Silicon oxide particles, simple substance of carbon present in part or all of the surface of the silicon oxide particles, and particulate graphite and carbon black attached to the surface of silicon oxide particles in which the single substance of carbon is present on the surface And a kind of conductive particles selected from the group consisting of: and an organic substance covering a part or all of the surface of the silicon oxide particles having the conductive particles attached to the surface ,
The content rate of the single carbon is 0.5 mass% to 10.0 mass% of the total amount of the silicon oxide particles and the single carbon,
The negative electrode material for lithium ion secondary batteries which has the protrusion structure by the said electroconductive particle.
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| JP5318921B2 (en) * | 2011-07-22 | 2013-10-16 | 日本カーボン株式会社 | Graphite particles for lithium ion secondary batteries |
| JP5696008B2 (en) * | 2011-09-07 | 2015-04-08 | 株式会社日立製作所 | Coated active material and lithium secondary battery using the same |
| JP2013197069A (en) * | 2012-03-22 | 2013-09-30 | National Institute Of Advanced Industrial & Technology | Negative electrode material for lithium secondary battery and manufacturing method thereof, negative electrode for lithium secondary battery and manufacturing method thereof, lithium secondary battery, and electric device with lithium secondary battery |
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- 2014-04-25 JP JP2014092065A patent/JP6511726B2/en active Active
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