JP5555978B2 - Negative electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the same - Google Patents
Negative electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the same Download PDFInfo
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Description
本発明は、負極活物質、特にリチウムイオン二次電池等の非水電解質二次電池用負極活物質、及びそれを用いた非水電解質二次電池に関する。 The present invention relates to a negative electrode active material, in particular, a negative electrode active material for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, and a non-aqueous electrolyte secondary battery using the same.
近年、携帯型の電子機器、通信機器等の著しい発展に伴い、経済性と機器の小型化、軽量化の観点から、高エネルギー密度の二次電池が強く要望されている。従来、この種の二次電池の高容量化策として、例えば、負極材料にＶ、Ｓｉ、Ｂ、Ｚｒ、Ｓｎ等の酸化物及びそれらの複合酸化物を用いる方法（特許文献１：特開平５−１７４８１８号公報、特許文献２：特開平６−６０８６７号公報）、溶湯急冷した金属酸化物を負極材として適用する方法（特許文献３：特開平１０−２９４１１２号公報）、負極材料に酸化珪素を用いる方法（特許文献４：特許第２９９７７４１号公報）、負極材料にＳｉ2Ｎ2Ｏ及びＧｅ2Ｎ2Ｏを用いる方法（特許文献５：特開平１１−１０２７０５号公報）等が知られている。 In recent years, with the remarkable development of portable electronic devices, communication devices, etc., secondary batteries with high energy density are strongly demanded from the viewpoints of economy and downsizing and weight reduction of devices. Conventionally, as a measure for increasing the capacity of this type of secondary battery, for example, a method of using an oxide such as V, Si, B, Zr, Sn, or a composite oxide thereof as a negative electrode material (Patent Document 1: Japanese Patent Laid-Open No. Hei 5). -174818, Patent Document 2: JP-A-6-60867), a method of applying a metal oxide quenched with molten metal as a negative electrode material (Patent Document 3: JP-A-10-294112), silicon oxide as a negative electrode material (Patent Document 4: Japanese Patent No. 2999741), a method using Si 2 N 2 O and Ge 2 N 2 O as negative electrode materials (Patent Document 5: Japanese Patent Laid-Open No. 11-102705), and the like are known. Yes.
しかしながら、上記従来の方法では、充放電容量が上がり、エネルギー密度が高くなるものの、サイクル性が不十分であったり、市場の要求特性には未だ不十分であったりし、必ずしも満足でき得るものではなく、更なるエネルギー密度の向上が望まれていた。 However, in the above conventional method, although the charge / discharge capacity is increased and the energy density is increased, the cycleability is insufficient, or the required characteristics of the market are still insufficient, and are not always satisfactory. However, further improvement in energy density has been desired.
その中でも、負極材料に酸化珪素を用いる方法（特許文献４：特許第２９９７７４１号公報）は、電池特性の良好なリチウムイオン二次電池は得られるものの、更なる容量の向上とサイクル特性の向上が求められていた。 Among them, the method using silicon oxide as the negative electrode material (Patent Document 4: Japanese Patent No. 2999741) can provide a lithium ion secondary battery with good battery characteristics, but can further improve the capacity and cycle characteristics. It was sought after.
本発明は、上記事情に鑑みなされたものであり、更なる容量の向上とサイクル特性の向上に適した負極活物質、及びそれを用いた非水電解質二次電池を提供することを目的とする。 This invention is made | formed in view of the said situation, and aims at providing the negative electrode active material suitable for the improvement of a further capacity | capacitance and a cycling characteristic, and a nonaqueous electrolyte secondary battery using the same. .
本発明者らは、上記目的を達成するため鋭意検討を行った結果、レーザー回折散乱式粒度分布測定法による粒度分布で、累積９０％径（以下、Ｄ90とする）が５０μｍ以下であり、かつ２μｍ未満の粒子（以下、微粉末Ｂとする）を１〜３０質量％含む粉末、特に該粉末中の２μｍ以上の粒子（以下、微粉末Ａとする）としてリチウムイオンを吸蔵・放出することが可能な珪素を含有し、更に上記２μｍ未満の粒子として導電性を付与されている粒子を用いたものを負極活物質とすると、この負極活物質が極めて優れた容量の向上とサイクル特性の向上をもたらすことを見出し、本発明を完成した。 The present inventors have made intensive studies for achieving the above object, the particle size distribution by a laser diffraction scattering particle size distribution measuring method, the 90% cumulative diameter (hereinafter referred to as D 90) is at 50μm or less, In addition, lithium ions are occluded / released as powder containing 1 to 30% by mass of particles (hereinafter referred to as fine powder B) of less than 2 μm, particularly as particles of 2 μm or more in the powder (hereinafter referred to as fine powder A). If the negative electrode active material is made of particles that contain silicon that can be used, and that have been given conductivity as particles smaller than 2 μm, the negative electrode active material has an extremely excellent capacity and cycle characteristics. The present invention has been completed.
即ち、本発明は、下記の負極活物質、非水電解質二次電池用負極材料、電極ペースト、電極及び非水電解質二次電池を提供する。
請求項１：
レーザー回折散乱式粒度分布測定法による粒度分布で、累積９０％径（Ｄ90）が５０μｍ以下であり、かつ粒子径２μｍ以上の微粉末Ａと、粒子径２μｍ未満の微粉末Ｂを１〜３０質量％含む粉末であって、上記微粉末Ａが酸化珪素であり、上記微粉末Ｂが導電性炭素である負極活物質。
請求項２：
微粉末Ａが、導電性を付与した粉末であることを特徴とする請求項１記載の負極活物質。
請求項３：
上記微粉末Ａが、ＣＶＤにより表面に導電性炭素の被覆層を有するものである請求項１記載の負極活物質。
請求項４：
請求項１乃至３のいずれか１項記載の負極活物質を用いたことを特徴とする非水電解質二次電池用負極材料。
請求項５：
請求項４記載の非水電解質二次電池用負極材料とバインダーを含むことを特徴とする電極ペースト。
請求項６：
請求項５記載の電極ペーストの成型体であることを特徴とする電極。
請求項７：
請求項６記載の電極を構成要素とする非水電解質二次電池。
That is, this invention provides the following negative electrode active material, the negative electrode material for nonaqueous electrolyte secondary batteries, an electrode paste, an electrode, and a nonaqueous electrolyte secondary battery.
Claim 1:
1 to 30 fine powders A having a cumulative 90% diameter (D 90 ) of 50 μm or less and a fine powder B having a particle diameter of 2 μm or more and a fine powder B having a particle diameter of less than 2 μm in a particle size distribution by a laser diffraction scattering type particle size distribution measurement method. a powder containing by weight%, the fine powder a is an acid Ka珪oxygen, a negative electrode active material in which the fine powder B is a conductive carbon.
Claim 2:
Negative electrode active material of claim 1 Symbol mounting, characterized in that fine powder A is a powder having conductivity.
Claim 3:
The fine powder A is negative active material of Der Ru請 Motomeko 1, wherein those having a coating layer of conductive carbon on the surface by CVD.
Claim 4:
A negative electrode material for a nonaqueous electrolyte secondary battery, wherein the negative electrode active material according to any one of claims 1 to 3 is used.
Claim 5:
An electrode paste comprising the negative electrode material for a nonaqueous electrolyte secondary battery according to claim 4 and a binder.
Claim 6:
An electrode, which is a molded body of the electrode paste according to
Claim 7:
A nonaqueous electrolyte secondary battery comprising the electrode according to claim 6 as a constituent element.
本発明の負極活物質を用いることにより、非水電解質二次電池の容量の向上とサイクル特性の向上が可能になる。 By using the negative electrode active material of the present invention, it is possible to improve the capacity and cycle characteristics of the nonaqueous electrolyte secondary battery.
本発明に係る負極活物質は、レーザー回折散乱式粒度分布測定法による粒度分布で、累積９０％径（Ｄ90）が５０μｍ以下であり、かつ２μｍ未満の粒子（微粉末Ｂ）を１〜３０質量％含む粉末である。 The negative electrode active material according to the present invention has a particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method, and particles (fine powder B) having a cumulative 90% diameter (D 90 ) of 50 μm or less and less than 2 μm (1 to 30). It is a powder containing mass%.
Ｄ90は５０μｍ以下であるが、好ましくは３０μｍ以下である。５０μｍより大きいと粒子径が大きすぎて負極としての性能が不十分である。負極活物質中の２μｍ未満の微粉末Ｂは全体の１〜３０質量％であるが、好ましくは５〜２０質量％である。１質量％より少なくても３０質量％より多くても本発明の効果を達成し得ない。 D90 is 50 μm or less, preferably 30 μm or less. When it is larger than 50 μm, the particle diameter is too large and the performance as the negative electrode is insufficient. The fine powder B of less than 2 μm in the negative electrode active material is 1 to 30% by mass, preferably 5 to 20% by mass. Even if it is less than 1 mass% or more than 30 mass%, the effect of the present invention cannot be achieved.
本発明の負極活物質を構成するＤ90が５０μｍ以下の粉末は、２μｍ以上の粉末（微粉末Ａ）を含むが、この微粉末Ａは、リチウムイオンを吸蔵・放出することが可能な珪素を含有することが好ましい。 The powder having a D 90 of 50 μm or less that constitutes the negative electrode active material of the present invention includes a powder (fine powder A) of 2 μm or more. The fine powder A contains silicon capable of inserting and extracting lithium ions. It is preferable to contain.
この場合、本発明のリチウムイオンを吸蔵・放出することが可能な珪素を含有する微粉末Ａの具体的な材料としては、金属不純物濃度が各々１ｐｐｍ以下の高純度シリコン粉末、塩酸で洗浄した後、フッ化水素酸、又はフッ化水素酸と硝酸との混合物で処理することで金属不純物を取り除いたケミカルグレードのシリコン粉末、冶金的に精製された金属珪素を粉末状に加工したもの、更にそれらの合金や珪素の低級酸化物や部分酸化物、珪素の窒化物や部分窒化物を含む。特に珪素、酸化珪素、又はそれらの混合物が好ましい。珪素の低級酸化物である酸化珪素は、充放電を繰り返した際に生じる体積膨張と収縮が珪素そのものを用いた場合に比べて非常に小さくなり、サイクル特性も良好であり、好ましい。 In this case, the specific material of fine powder A containing silicon capable of occluding and releasing lithium ions of the present invention is a high-purity silicon powder having a metal impurity concentration of 1 ppm or less, after washing with hydrochloric acid. , Hydrofluoric acid, or chemical grade silicon powder from which metal impurities have been removed by treatment with a mixture of hydrofluoric acid and nitric acid, metallurgically refined metal silicon, and those further processed Alloy, lower oxide or partial oxide of silicon, silicon nitride or partial nitride. In particular, silicon, silicon oxide, or a mixture thereof is preferable. Silicon oxide, which is a lower oxide of silicon, is preferable because the volume expansion and contraction that occur when charging and discharging are repeated are much smaller than when silicon itself is used, and the cycle characteristics are good.
また、リチウムイオンを吸蔵・放出することが可能な珪素を含有する微粉末Ａは、結晶の大きさが１〜５００ｎｍの珪素の微結晶が二酸化珪素に分散した構造を有する粒子であることが好ましい。このような粒子は、例えば、特開２００４−４７４０４号公報に記載されたものが挙げられる。 The fine powder A containing silicon capable of inserting and extracting lithium ions is preferably a particle having a structure in which fine crystals of silicon having a crystal size of 1 to 500 nm are dispersed in silicon dioxide. . Examples of such particles include those described in JP-A-2004-47404.
この場合、上記微粉末Ａは、導電性を付与した粉末であることが好ましい。導電性の付与の方法としては特に制限されないが、例えば化学蒸着（ＣＶＤ）法等の手法によって表面に導電性炭素の被覆層を設けるなどの方法を使用でき、好ましくは上記特開２００４−４７４０４号公報記載の導電性珪素複合体を使用することができる。 In this case, the fine powder A is preferably a powder imparted with conductivity. The method for imparting electrical conductivity is not particularly limited, but for example, a method of providing a conductive carbon coating layer on the surface by a chemical vapor deposition (CVD) method or the like can be used, and preferably the above-mentioned JP-A-2004-47404. The conductive silicon composite described in the publication can be used.
一方、Ｄ90が５０μｍ以下の粉末において、粒子径２μｍ未満の粒子（微粉末Ｂ）は、珪素、酸化珪素、導電性炭素、又はそれらの混合物であることが好ましく、またこの場合、上記特開２００４−４７４０４号公報に開示されたような結晶の大きさが１〜５００ｎｍの、珪素の微結晶が二酸化珪素に分散した構造を有する粒子を用いることができる。 On the other hand, in the powder having a D 90 of 50 μm or less, the particles (fine powder B) having a particle diameter of less than 2 μm are preferably silicon, silicon oxide, conductive carbon, or a mixture thereof. As disclosed in Japanese Patent Application Publication No. 2004-47404, particles having a structure in which silicon microcrystals are dispersed in silicon dioxide having a crystal size of 1 to 500 nm can be used.
微粉末Ｂも導電性を付与したものが好ましく、具体的には上記特開２００４−４７４０４号公報に記載の導電性珪素複合体や黒鉛、アセチレンブラック等の導電性炭素を用いることができる。 The fine powder B preferably has conductivity, and specifically, conductive silicon composites described in JP-A-2004-47404, conductive carbon such as graphite and acetylene black can be used.
なお、本発明の負極活物質を構成するＤ90が５０μｍ以下の粉末中に含まれるリチウムイオンを吸蔵・放出することが可能な珪素、その他の材料は、５０〜９９．７質量％、特に７０〜９９．５質量％であることが好ましい。この場合、残部は、導電性炭素等のリチウムイオンを吸蔵・放出することのない導電性粉体、導電性炭素等からなる被覆層等であることが好ましい。 Note that silicon capable of occluding and releasing lithium ions contained in a powder having a D 90 of 50 μm or less constituting the negative electrode active material of the present invention, and other materials are 50 to 99.7% by mass, particularly 70%. It is preferably ˜99.5% by mass. In this case, the balance is preferably a conductive powder that does not occlude / release lithium ions such as conductive carbon, a coating layer made of conductive carbon, or the like.
次に、本発明の負極活物質を所定の粒子径とするためには、よく知られた粉砕機とよく知られた分級機が用いられる。粉砕機は、例えば、ボール、ビーズ等の粉砕媒体を運動させ、その運動エネルギーによる衝撃力や摩擦力、圧縮力を利用して被砕物を粉砕するボールミル、媒体撹拌ミルや、ローラによる圧縮力を利用して粉砕を行うローラミルや、被砕物を高速で内張材に衝突もしくは粒子相互に衝突させ、その衝撃による衝撃力によって粉砕を行うジェットミルや、ハンマー、ブレード、ピン等を固設したローターの回転による衝撃力を利用して被砕物を粉砕するハンマーミル、ピンミル、ディスクミルや、剪断力を利用するコロイドミルや高圧湿式対向衝突式分散機「アルティマイザー」等が用いられる。粉砕は、湿式、乾式共に用いられる。また、粉砕後に粒度分布を整えるため、乾式分級や湿式分級もしくはふるい分け分級が用いられる。乾式分級は、主として気流を用い、分散、分離（細粒子と粗粒子の分離）、捕集（固体と気体の分離）、排出のプロセスが逐次若しくは同時に行われ、粒子相互間の干渉、粒子の形状、気流の流れの乱れ、速度分布、静電気の影響等で分級効率が低下させないよう、分級をする前に前処理（水分、分散性、湿度等の調整）を行ったり、使用される気流の水分や酸素濃度を調整して用いられる。また、乾式で分級機が一体となっているタイプでは、一度に粉砕、分級が行われ、所望の粒度分布とすることが可能となる。 Next, in order to make the negative electrode active material of the present invention have a predetermined particle size, a well-known pulverizer and a well-known classifier are used. The pulverizer, for example, moves the grinding media such as balls and beads, and uses the impact force, friction force, and compression force due to the kinetic energy to pulverize the material to be crushed, the media agitation mill, and the compression force by the roller. A roller mill that uses pulverization, a jet mill that makes crushed objects collide with the lining material or collide with each other at high speed, and pulverizes by the impact force of the impact, and a rotor with a fixed hammer, blade, pin, etc. A hammer mill, a pin mill, a disk mill, a colloid mill using a shearing force, a high-pressure wet opposed collision disperser “Ultimizer”, or the like is used. For pulverization, both wet and dry processes are used. In order to adjust the particle size distribution after pulverization, dry classification, wet classification or sieving classification is used. In the dry classification, airflow is mainly used, and dispersion, separation (separation of fine particles and coarse particles), collection (separation of solid and gas), and discharge are performed sequentially or simultaneously. Pre-classification (adjustment of moisture, dispersibility, humidity, etc.) before classification is performed to prevent the classification efficiency from being lowered due to the shape, air flow disturbance, velocity distribution, static electricity, etc. Used by adjusting moisture and oxygen concentration. Further, in a dry type in which a classifier is integrated, pulverization and classification are performed at a time, and a desired particle size distribution can be obtained.
上記負極活物質は、非水電解質二次電池、特にリチウムイオン二次電池の負極材料として好適に用いられる。 The negative electrode active material is suitably used as a negative electrode material for non-aqueous electrolyte secondary batteries, particularly lithium ion secondary batteries.
この場合、かかる二次電池の正極活物質としては、リチウムイオンを吸蔵・放出することが可能な酸化物あるいは硫化物等が挙げられ、これらのいずれか１種又は２種以上が用いられる。具体的には、例えばＴｉＳ2、ＭｏＳ2、ＮｂＳ2、ＺｒＳ2、ＶＳ2あるいはＶ2Ｏ5、ＭｏＯ3及びＭｇ（Ｖ3Ｏ8）2等のリチウムを含有しない金属硫化物もしくは酸化物、又はリチウムを含有するリチウム複合酸化物が挙げられ、また、ＮｂＳｅ2等の複合金属も挙げられる。中でも、エネルギー密度を高くするためには、ＬｉＭｅｔＯ2を主体とするリチウム複合酸化物が好ましい。なお、Ｍｅｔは具体的には、コバルト、ニッケル、鉄、及びマンガンのうち少なくとも１種が好ましく、ｘは、通常、０．０５≦ｘ≦１．１０の範囲内の値である。このようなリチウム複合酸化物の具体例としては、層構造をもつＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＦｅＯ2、ＬｉxＮｉyＣｏ1-yＯ2、スピネル構造のＬｉＭｎ2Ｏ4及び斜方晶のＬｉＭｎＯ2が挙げられる。更に高電圧対応型として置換スピネルマンガン化合物ＬｉＭｅｔxＭｎ1-xＯ4も使用されており、この場合のＭｅｔはチタン、クロム、鉄、コバルト、銅及び亜鉛等が挙げられる。 In this case, examples of the positive electrode active material of the secondary battery include oxides or sulfides that can occlude and release lithium ions, and any one or more of these are used. Specifically, for example, a metal sulfide or oxide containing no lithium such as TiS 2 , MoS 2 , NbS 2 , ZrS 2 , VS 2 or V 2 O 5 , MoO 3 and Mg (V 3 O 8 ) 2 , or lithium composite oxide is exemplified containing lithium and a composite metal such as NbSe 2 may be mentioned. Among these, in order to increase the energy density, a lithium composite oxide mainly composed of LiMetO 2 is preferable. Specifically, Met is preferably at least one of cobalt, nickel, iron, and manganese, and x is usually a value in the range of 0.05 ≦ x ≦ 1.10. Specific examples of such a lithium composite oxide include LiCoO 2 having a layer structure, LiNiO 2 , LiFeO 2 , Li x Ni y Co 1-y O 2 , spinel-structured LiMn 2 O 4, and orthorhombic LiMnO. 2 is mentioned. Further, a substituted spinel manganese compound LiMet x Mn 1-x O 4 is also used as a high voltage compatible type, and examples of Met in this case include titanium, chromium, iron, cobalt, copper, and zinc.
なお、上記のリチウム複合酸化物は、例えば、リチウムの炭酸塩、硝酸塩、塩化物あるいは水酸化物と、遷移金属の炭酸塩、硝酸塩、酸化物あるいは水酸化物とを所望の組成に応じて粉砕混合し、酸素雰囲気中において６００〜１０００℃の範囲内の温度で焼成することにより調製される。 The lithium composite oxide is obtained by, for example, grinding lithium carbonate, nitrate, chloride or hydroxide and transition metal carbonate, nitrate, oxide or hydroxide according to a desired composition. It is prepared by mixing and baking at a temperature in the range of 600 to 1000 ° C. in an oxygen atmosphere.
更に、正極活物質としては有機物も使用することができる。例示すると、ポリアセチレン、ポリピロール、ポリパラフェニレン、ポリアニリン、ポリチオフェン、ポリアセン、ポリスルフィド化合物等である。 Furthermore, an organic substance can also be used as the positive electrode active material. Illustrative examples include polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyacene, polysulfide compounds and the like.
正極、負極の作製方法については特に制限はない。一般的には、溶媒に活物質、結着剤（バインダー）、導電剤等を加えてスラリー状とし、集電体シートに塗布し、乾燥、圧着して作製する。 There is no restriction | limiting in particular about the preparation methods of a positive electrode and a negative electrode. In general, an active material, a binder (binder), a conductive agent and the like are added to a solvent to form a slurry, which is applied to a current collector sheet, dried and pressed.
結着剤としては、一般的にポリフッ化ビニリデン、ポリテトラフルオロエチレン、スチレン・ブタジエンゴム、イソプレンゴム、各種ポリイミド樹脂等が挙げられる。 Examples of the binder generally include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, various polyimide resins, and the like.
導電剤としては、一般的に黒鉛、カーボンブラック等の炭素系材料や、銅、ニッケル等の金属材料が挙げられる。 Examples of the conductive agent generally include carbon-based materials such as graphite and carbon black, and metal materials such as copper and nickel.
集電体としては、正極用にはアルミニウム、又はその合金、負極用には銅、ステンレス、ニッケル等の金属又はそれらの合金等が挙げられる。 Examples of the current collector include aluminum or an alloy thereof for the positive electrode, and a metal such as copper, stainless steel, nickel, or an alloy thereof for the negative electrode.
正極と負極の間に用いられるセパレータは電解液に対して安定であり、保液性に優れていれば特に制限はないが、一般的にはポリエチレン、ポリプロピレン等のポリオレフィンの多孔質シート又は不織布が挙げられる。 The separator used between the positive electrode and the negative electrode is not particularly limited as long as it is stable with respect to the electrolytic solution and has excellent liquid retention, but generally a porous sheet or non-woven fabric of polyolefin such as polyethylene or polypropylene is used. Can be mentioned.
電池の形状は任意であり、特に制限はない。一般的にはコイン形状に打ち抜いた電極とセパレータを積層したコインタイプ、電極シートとセパレータをスパイラル状にしたシリンダータイプ等が挙げられる。 The shape of the battery is arbitrary and is not particularly limited. In general, a coin type in which an electrode punched into a coin shape and a separator are stacked, a cylinder type in which an electrode sheet and a separator are spiraled, and the like can be given.
以下、実施例、参考例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において組成の％は質量％、部は質量部を示す。 EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% of composition indicates mass%, and part indicates mass part.
［参考例１］
［負極活物質（導電性珪素複合体）の作製］
負極活物質である導電性珪素複合体は、特開２００４−４７４０４号公報の記載に基づき作製した。以下にその作製方法を示す。
（１）酸化珪素粉末Ａの製造
二酸化珪素粉末（ＢＥＴ比表面積＝２００ｍ2／ｇ）とケミカルグレード金属珪素粉末（ＢＥＴ比表面積＝４ｍ2／ｇ）を等モルの割合で混合した混合粉末を、１３５０℃、０．１Ｔｏｒｒの高温減圧雰囲気で熱処理し、発生したＳｉＯガスをＳＵＳ製基体に析出させた。次に、この析出物を回収した後、ジョークラッシャーで粗砕した。この粗砕物をジェットミル（ホソカワミクロン社製ＡＦＧ−１００）を用いて分級機の回転数９０００ｒｐｍにて粉砕し、Ｄ50＝７．６μｍ、Ｄ90＝１１．９μｍの酸化珪素粉末Ａ（ＳｉＯx：ｘ＝１．０２）をサイクロンにて回収した。その粒度分布を図１に示す。ここで得られた粉末をＣｕ−Ｋα線によるＸ線回折を行い、得られた粉末は無定形の酸化珪素（ＳｉＯx）粉末であることを確認した。
（２）酸化珪素微粉末Ｂの製造
酸化珪素粉末Ａと同様の方法で得られた酸化珪素を用い、ビーズミルで４時間粉砕し、Ｄ50＝０．８μｍの酸化珪素微粉末Ｂを得た。その粒度分布を図２に示す。
（３）酸化珪素粉末Ａと酸化珪素粉末Ｂの混合
得られた酸化珪素粉末Ａ１００部と酸化珪素微粉末Ｂ１０部を混合機を用いて充分混合した。
（４）混合粉体の導電性付与
混合粉体をロータリーキルン型の反応器を用いて、メタン−アルゴン混合ガス通気下で１１５０℃、平均滞留時間約２時間の条件で酸化珪素の不均化と同時に熱ＣＶＤを行った。運転終了後、降温し、黒色粉末を回収した。得られた黒色粉末の蒸着炭素量は５．１％であった。この導電性付与後の粉体はＸ線回折パターンの分析より、酸化珪素粉末とは異なり、２θ＝２８．４°付近のＳｉ（１１１）に帰属される回折線が存在し、この回折線の半価幅よりシェーラー法で結晶の大きさを求め、二酸化珪素中に分散した珪素の結晶の大きさは１１ｎｍであり、このことから微細な珪素（Ｓｉ）の結晶が、二酸化珪素（ＳｉＯ2）の中に分散している導電性珪素複合体粉末であることを確認した。なお、この導電性珪素複合体粉末における２μｍ未満の粒子の割合を表１に示す。
[ Reference Example 1]
[Preparation of negative electrode active material (conductive silicon composite)]
A conductive silicon composite as a negative electrode active material was prepared based on the description in JP-A-2004-47404. The manufacturing method is shown below.
(1) Production of silicon oxide powder A A mixed powder obtained by mixing silicon dioxide powder (BET specific surface area = 200 m 2 / g) and chemical grade metal silicon powder (BET specific surface area = 4 m 2 / g) at an equimolar ratio, Heat treatment was performed in a high-temperature and reduced-pressure atmosphere at 1350 ° C. and 0.1 Torr, and the generated SiO gas was deposited on a SUS substrate. Next, the precipitate was collected and then roughly crushed with a jaw crusher. This coarsely pulverized product was pulverized using a jet mill (AFG-100 manufactured by Hosokawa Micron Corporation) at a rotation speed of 9000 rpm of a classifier, and silicon oxide powder A (SiO x : D 50 = 7.6 μm, D 90 = 11.9 μm). x = 1.02) was recovered with a cyclone. The particle size distribution is shown in FIG. The powder obtained here was subjected to X-ray diffraction using Cu-Kα rays, and it was confirmed that the obtained powder was amorphous silicon oxide (SiO x ) powder.
(2) Production of silicon oxide fine powder B Using silicon oxide obtained by the same method as silicon oxide powder A, it was pulverized with a bead mill for 4 hours to obtain silicon oxide fine powder B with D 50 = 0.8 μm. The particle size distribution is shown in FIG.
(3) Mixing of silicon oxide powder A and silicon
(4) Adding conductivity to mixed powder Using a rotary kiln type reactor, the mixed powder was disproportionated with silicon oxide under conditions of 1150 ° C. and an average residence time of about 2 hours under a methane-argon mixed gas flow. Simultaneously, thermal CVD was performed. After the operation was completed, the temperature was lowered and black powder was recovered. The amount of deposited carbon of the obtained black powder was 5.1%. From the analysis of the X-ray diffraction pattern, the powder after imparting conductivity has a diffraction line attributed to Si (111) near 2θ = 28.4 °, unlike the silicon oxide powder. The size of the crystal is obtained from the half width by the Scherrer method, and the size of the silicon crystal dispersed in the silicon dioxide is 11 nm. From this, the crystal of fine silicon (Si) is silicon dioxide (SiO 2 ). It was confirmed that the conductive silicon composite powder was dispersed in the powder. In addition, Table 1 shows the ratio of particles of less than 2 μm in the conductive silicon composite powder.
［負極の作製］
負極の作製は、以下の手順で行った。
前記で得られた導電性珪素複合体粉末にポリイミドを１０％加え、更にＮ−メチルピロリドンを加え、スラリーとし、このスラリーを厚さ１５μｍの銅箔に塗布し、８０℃で１時間真空乾燥後、ローラープレスにより電極を加圧成形し、３５０℃で１時間真空乾燥し、２ｃｍ2に打ち抜き負極とした。
[Production of negative electrode]
The negative electrode was produced according to the following procedure.
10% of polyimide is added to the conductive silicon composite powder obtained above, and N-methylpyrrolidone is further added to form a slurry. This slurry is applied to a copper foil having a thickness of 15 μm and dried in a vacuum at 80 ° C. for 1 hour. The electrode was press-molded with a roller press, vacuum-dried at 350 ° C. for 1 hour, punched out to 2 cm 2 and used as a negative electrode.
［電池の作製］
ここで、得られた負極の充放電特性を評価するために、対極にリチウム箔を使用し、非水電解質として六フッ化リンリチウムをエチレンカーボネートとジエチルカーボネートの１／１（体積比）混合液に１モル／Ｌの濃度で溶解させた非水電解質溶液を用い、セパレーターに厚さ２５μｍのポリエチレン製微多孔質フィルムを用いた評価用リチウムイオン二次電池を作製した。
作製したリチウムイオン二次電池は、一晩室温で放置した後、二次電池充放電試験装置（（株）ナガノ製）を用い、テストセルの電圧が０Ｖに達するまで０．５ｍＡ／ｃｍ2の定電流で充電を行い、０Ｖに達した後は、セル電圧を０Ｖに保つように電流を減少させて充電を行った。そして、電流値が０．１ｍＡ／ｃｍ2を下回った時点で充電を終了した。放電は０．５ｍＡ／ｃｍ2の定電流で行い、セル電圧が２．０Ｖを上回った時点で放電を終了し、放電容量を求めた。以上の充放電試験を１００回繰り返し、１００サイクル後のサイクル保持率を求めた。結果を表２に示す。
[Production of battery]
Here, in order to evaluate the charge / discharge characteristics of the obtained negative electrode, a lithium foil was used as a counter electrode, and lithium hexafluoride was mixed with 1/1 (volume ratio) of ethylene carbonate and diethyl carbonate as a non-aqueous electrolyte. A lithium ion secondary battery for evaluation using a non-aqueous electrolyte solution dissolved at a concentration of 1 mol / L and a polyethylene microporous film having a thickness of 25 μm as a separator was prepared.
The prepared lithium ion secondary battery was allowed to stand at room temperature overnight, and then charged with a secondary battery charge / discharge tester (manufactured by Nagano Co., Ltd.) until the test cell voltage reached 0 V at 0.5 mA / cm 2 . Charging was performed at a constant current, and after reaching 0V, charging was performed by decreasing the current so as to keep the cell voltage at 0V. The charging was terminated when the current value fell below 0.1 mA / cm 2 . Discharging was performed at a constant current of 0.5 mA / cm 2 , and discharging was terminated when the cell voltage exceeded 2.0 V, and the discharge capacity was determined. The above charge / discharge test was repeated 100 times, and the cycle retention after 100 cycles was determined. The results are shown in Table 2.
［実施例１］
参考例１の酸化珪素粉末Ａ（Ｄ50＝７．６μｍ）を用い、同様に導電性の付与を行った（蒸着炭素量４．９％）。また、粉末Ｂには、電気化学工業社製デンカブラック（一次粒子径０．０３５μｍ、凝集粒子径５．０μｍ）を用い、分散剤に日本触媒社製ポリビニルピロリドンＫ９０とＮ−メチルピロリドンを加え、アイメックス社製バッチ式ビーズミルＲＭＢを用いて解砕した。このアセチレンブラック分散品の粒度分布は、Ｄ50＝０．４μｍであった。図３にその粒度分布図を示す。これらを混合して導電性珪素複合体粉末を作製した。この導電性珪素複合体粉末における２μｍ未満の粒子の割合を表１に示す。また、参考例１と同様にして電池試験を行い、サイクル保持率を求めた。結果を表２に示す。
[Example 1 ]
Using silicon oxide powder A (D 50 = 7.6 μm) of Reference Example 1, conductivity was imparted in the same manner (vapor deposition carbon amount 4.9%). In addition, Denka Black (primary particle size 0.035 μm, aggregated particle size 5.0 μm) manufactured by Denki Kagaku Kogyo Co., Ltd. was used for powder B, and polyvinyl pyrrolidone K90 and N-methylpyrrolidone manufactured by Nippon Shokubai Co., Ltd. were added to the dispersant. Crushing was performed using a batch type bead mill RMB manufactured by IMEX. The particle size distribution of the acetylene black dispersion was D 50 = 0.4 μm. FIG. 3 shows the particle size distribution diagram. These were mixed to produce a conductive silicon composite powder. Table 1 shows the ratio of particles of less than 2 μm in the conductive silicon composite powder. In addition, a battery test was conducted in the same manner as in Reference Example 1 to determine the cycle retention rate. The results are shown in Table 2.
［参考例２］
参考例１と同様の方法で得られた酸化珪素を用い、ビーズミルで２時間粉砕し、Ｄ50＝８．１μｍの酸化珪素微粉末を得た。この粉末をレーザー回折散乱式粒度分布測定法による粒度分布測定を行ったところ、粒子径１．９５１μｍにおける累積値が１４．９６３％であった。図４にその粒度分布図を示す。この粉末に導電性の付与を行い、導電性珪素複合体粉末（蒸着炭素量５．３％）を作製した。この導電性珪素複合体粉末における２μｍ未満の粒子の割合を表１に示す。また、参考例１と同様にして電池試験を行い、サイクル保持率を求めた。結果を表２に示す。
[ Reference Example 2 ]
Silicon oxide obtained by the same method as in Reference Example 1 was used and pulverized with a bead mill for 2 hours to obtain fine silicon oxide powder having D 50 = 8.1 μm. When this powder was subjected to particle size distribution measurement by a laser diffraction / scattering particle size distribution measurement method, the cumulative value at a particle size of 1.951 μm was 14.9633%. FIG. 4 shows the particle size distribution diagram. Conductivity was imparted to this powder to produce a conductive silicon composite powder (vapor deposition carbon amount 5.3%). Table 1 shows the ratio of particles of less than 2 μm in the conductive silicon composite powder. In addition, a battery test was conducted in the same manner as in Reference Example 1 to determine the cycle retention rate. The results are shown in Table 2.
［比較例１］
実施例１で作製した酸化珪素粉末Ａ（Ｄ50＝７．６μｍ）に導電性を付与した導電性珪素複合体粉末（蒸着炭素量５．３％）を用い、単一で使用した他は参考例１と同様にして電池試験を行い、サイクル保持率を求めた。この導電性珪素複合体粉末における２μｍ未満の粒子の割合を表１に示し、電池試験の結果を表２に示す。
[Comparative Example 1]
Using silicon oxide powder A produced in Example 1 (D 50 = 7.6 [mu] m) conductive silicon composite powder to impart conductivity to (deposited carbon content 5.3%), except that was used in a single in Reference A battery test was conducted in the same manner as in Example 1 to determine the cycle retention. The ratio of particles less than 2 μm in this conductive silicon composite powder is shown in Table 1, and the results of the battery test are shown in Table 2.
［比較例２］
実施例１で作製した酸化珪素粉末Ａ（Ｄ50＝７．６μｍ）に導電性を付与した導電性珪素複合体粉末（蒸着炭素量５．３％）を用い、図５に示す粒度分布を有する電気化学工業社製デンカブラック（一次粒子径０．０３５μｍ、凝集粒子径５．０μｍ）を解砕せずに使用した他は参考例１と同様にしてリチウムイオン二次電池を作製し、サイクル特性を求めた。この導電性珪素複合体粉末における２μｍ未満の粒子の割合を表１に示し、電池試験の結果を表２に示す。
[Comparative Example 2]
The conductive silicon composite powder (deposited carbon amount 5.3%) imparted with conductivity to the silicon oxide powder A (D 50 = 7.6 μm) produced in Example 1 has the particle size distribution shown in FIG. A lithium ion secondary battery was produced in the same manner as in Reference Example 1 except that Denka Black (primary particle size 0.035 μm, aggregated particle size 5.0 μm) manufactured by Denki Kagaku Kogyo Co., Ltd. was used without crushing, and cycle characteristics were obtained. Asked. The ratio of particles less than 2 μm in this conductive silicon composite powder is shown in Table 1, and the results of the battery test are shown in Table 2.
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