JP2014177389A - Lithium battery electrode active material - Google Patents
Lithium battery electrode active material Download PDFInfo
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- JP2014177389A JP2014177389A JP2013054385A JP2013054385A JP2014177389A JP 2014177389 A JP2014177389 A JP 2014177389A JP 2013054385 A JP2013054385 A JP 2013054385A JP 2013054385 A JP2013054385 A JP 2013054385A JP 2014177389 A JP2014177389 A JP 2014177389A
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- 239000007772 electrode material Substances 0.000 title description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title 1
- 229910052744 lithium Inorganic materials 0.000 title 1
- 239000010419 fine particle Substances 0.000 claims abstract description 70
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 31
- 239000010432 diamond Substances 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 239000011149 active material Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 52
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052799 carbon Inorganic materials 0.000 abstract description 26
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 28
- 239000002134 carbon nanofiber Substances 0.000 description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 6
- 239000002482 conductive additive Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 108010083687 Ion Pumps Proteins 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、ナノ炭素材料複合体及びＬｉイオン電池用活物質、さらにはナノ炭素材料複合体を製造する方法に関する。さらに詳しくは、本発明は、マリモカーボンの空隙中にＳｉ微粒子が内包されたナノ炭素材料複合体と、これを利用したＬｉイオン電池用活物質、並びにナノ炭素材料複合体の製造方法に関する。 The present invention relates to a nanocarbon material composite and an active material for a Li-ion battery, and further to a method for producing a nanocarbon material composite. More specifically, the present invention relates to a nanocarbon material composite in which Si fine particles are encapsulated in a void of marimocarbon, an active material for a Li ion battery using the same, and a method for producing the nanocarbon material composite.
近年、リチウムイオン電池の電極材料が研究されている。現状のリチウムイオン電池の負極の材料は、一般にカーボンが使用されており、理論容量は３７０ｍＡｈ／ｇである。さらに大きな理論容量を得るためにリチウムイオン電池の負極の材料が検討されている。 In recent years, electrode materials for lithium ion batteries have been studied. Carbon is generally used as the material for the negative electrode of current lithium ion batteries, and the theoretical capacity is 370 mAh / g. In order to obtain a larger theoretical capacity, materials for negative electrodes of lithium ion batteries have been studied.
リチウムイオン電池の負極にＳｉ（シリコン）を用いた場合(非特許文献１参照)の理論容量は、負極にカーボンを用いた場合に比較して、大凡４倍以上、少なくとも１５００ｍＡｈ／ｇ以上が期待されている。Ｓｉからなる負極をＳｉ負極と呼ぶ。 The theoretical capacity when Si (silicon) is used for the negative electrode of a lithium ion battery (see Non-Patent Document 1) is expected to be at least four times that of when carbon is used for the negative electrode, at least 1500 mAh / g. Has been. A negative electrode made of Si is called a Si negative electrode.
しかしながら、従来のＳｉ負極を用いたリチウムイオン電池の充放電は、１００回程度が限界であり、実用化されていない。 However, charging and discharging of a conventional lithium ion battery using a Si negative electrode is limited to about 100 times and has not been put into practical use.
Ｓｉ負極を用いたリチウムイオン電池の充放電の回数が１００回程度であるのは、Ｓｉ負極が充放電する際に膨張と収縮により劣化することに起因している。このため、リチウムイオン電池の充放電特性を改善するためにＳｉ負極の研究が盛んに行われている。 The reason why the number of times of charge and discharge of the lithium ion battery using the Si negative electrode is about 100 is that the Si negative electrode deteriorates due to expansion and contraction when charging and discharging. For this reason, in order to improve the charge / discharge characteristics of a lithium ion battery, research on the Si negative electrode has been actively conducted.
さらに、リチウムイオン電池の電極材料には、伝導性の向上のために導電助剤が添加されている。導電助剤は、例えばカーボンブラックである。このため、リチウムイオン電池の電極を形成する際には、電極材料、カーボンブラック及びバインダーが均一に混合された状態にすることが重要となる。 Furthermore, a conductive additive is added to the electrode material of the lithium ion battery in order to improve conductivity. The conductive aid is, for example, carbon black. For this reason, when forming the electrode of a lithium ion battery, it is important to make the electrode material, carbon black, and a binder into a uniformly mixed state.
ナノサイズのカーボンブラックは凝集しやすく均一に分散させることは難しい。このような状態であるとカーボンブラックを添加しても伝導性が低いままである。 Nano-sized carbon black tends to aggregate and is difficult to disperse uniformly. In such a state, the conductivity remains low even when carbon black is added.
図６は、従来の電極材料１０１に添加されたナノサイズのカーボンブラック１０２の分散状態が良好でない場合を模式的に示す図である。図６に示すように、電極１００は、電極材料１０１に導電助剤としてカーボンブラック１０２等が添加されて形成されている。カーボンブラック１０２は凝集しているので、図に示すようにカーボンブラック１０２が存在しない不活性な領域１０３が生じる。このように、電極材料１０１に導電助剤としてカーボンブラック１０２を添加しても、カーボンブラック１０２が凝集するため不活性な領域１０３が生じることで、電極の伝導性は直ちには改善され難い。 FIG. 6 is a diagram schematically showing a case where the nano-sized carbon black 102 added to the conventional electrode material 101 is not well dispersed. As shown in FIG. 6, the electrode 100 is formed by adding carbon black 102 or the like as a conductive additive to an electrode material 101. Since the carbon black 102 is aggregated, an inactive region 103 in which the carbon black 102 does not exist is generated as shown in the figure. Thus, even if carbon black 102 is added as a conductive additive to electrode material 101, carbon black 102 agglomerates, so that inactive region 103 is generated, so that the conductivity of the electrode is not readily improved.
特許文献１には、ナノ炭素材料微粒子として、マリモ様の形状をしたカーボンが開示されている。マリモ様のカーボンは、酸化ダイヤモンド触媒微粒子を核として、ナノメートル（ｎｍ）サイズの径を有するカーボンナノ繊維が放射状に、恰もマリモのように成長した球状の形状を有している。 Patent Document 1 discloses carbon having a marimo-like shape as nano-carbon material fine particles. Marimo-like carbon has a spherical shape in which carbon nanofibers having a nanometer (nm) size diameter radiate and coconut-like growth, with oxidized diamond catalyst fine particles as nuclei.
図７は、特許文献１に開示されたマリモ様のカーボン(以下、マリモカーボンと称する。)の製造装置１１０の構成を示す。
図７に示すマリモカーボン製造装置１１０は、流動気相合成装置とも呼ばれており、酸化ダイヤモンド触媒微粒子１１２が投入される垂直に配設された反応槽１１３と、反応槽１１３の下部及び上部にそれぞれ設けられた炭化水素からなるガス１１４を導入する導入口１１５と、ガス１１４を排出する排出口１１６と、反応槽１１３を取り囲んで配設される加熱装置１１７と、酸化ダイヤモンド触媒微粒子１１２を通過させないがガス１１４を通過させるフィルター１１８、等とから構成されている。混合装置１２０は、炭化水素からなるガス１１４に、反応補助ガスや希釈ガス１１９を混合するために配設されている。
FIG. 7 shows a configuration of a marimo-like carbon (hereinafter referred to as marimo carbon) manufacturing apparatus 110 disclosed in Patent Document 1.
The marimocarbon production apparatus 110 shown in FIG. 7 is also referred to as a fluidized gas phase synthesis apparatus, and is arranged vertically in a reaction tank 113 into which diamond oxide catalyst fine particles 112 are charged, and below and above the reaction tank 113. Passing through the introduction port 115 for introducing the gas 114 made of hydrocarbon, the discharge port 116 for discharging the gas 114, the heating device 117 disposed so as to surround the reaction tank 113, and the diamond oxide catalyst fine particles 112. The filter 118 is configured to allow the gas 114 to pass therethrough. The mixing device 120 is arranged to mix the reaction auxiliary gas and the dilution gas 119 with the gas 114 made of hydrocarbon.
特許文献１によれば、酸化ダイヤモンド触媒微粒子が反応槽１１３中で浮遊し、かつ、撹拌されるので、炭化水素からなるガス１１４を導入し、反応槽１１３を電気炉で加熱すると、酸化ダイヤモンド触媒微粒子１１２の全表面に亘って触媒反応が均等に起こる。これにより、酸化ダイヤモンド触媒微粒子１１２の全表面に亘って長さの等しいナノ炭素材料が放射状に成長し、マリモ状の微粒子、つまり、マリモカーボンが得られる。 According to Patent Document 1, since the diamond oxide catalyst fine particles float in the reaction tank 113 and are stirred, when the gas 114 made of hydrocarbon is introduced and the reaction tank 113 is heated in an electric furnace, the diamond oxide catalyst Catalytic reaction occurs uniformly over the entire surface of the fine particles 112. As a result, nanocarbon materials having the same length grow radially over the entire surface of the oxidized diamond catalyst fine particles 112, and marimo-like fine particles, that is, marimocarbon, are obtained.
従来の負極材料中にナノサイズの固体のカーボンを均一に分散させることは、図６に示すようにカーボンが凝集してしまうため非常に難しいという課題があった。 Uniformly dispersing nano-sized solid carbon in a conventional negative electrode material has a problem that it is very difficult because carbon aggregates as shown in FIG.
本発明は上記課題に鑑み、ナノ炭素材料が凝集し難いナノ炭素材料複合体及びＬｉイオン電池用活物質並びにその製造方法を提供することを目的としている。 In view of the above problems, an object of the present invention is to provide a nanocarbon material composite in which a nanocarbon material hardly aggregates, an active material for a Li-ion battery, and a method for producing the same.
本発明者等は、鋭意検討し、マリモカーボンを構成するカーボンナノ繊維の間に形成される空隙にＳｉ微粒子を内包できることを見出し、本発明に想到した。 The present inventors diligently studied and found that Si fine particles can be encapsulated in voids formed between carbon nanofibers constituting marimocarbon, and arrived at the present invention.
上記目的を達成するために、本発明のナノ炭素材料複合体は、酸化ダイヤモンド触媒微粒子を核として繊維状のナノ炭素材料が放射状に形成されたマリモカーボンの空隙に、Ｓｉ微粒子が内包されてなる。 In order to achieve the above object, the nanocarbon material composite of the present invention is formed by encapsulating Si fine particles in the voids of marimocarbon in which fibrous nanocarbon materials are radially formed with oxidized diamond catalyst fine particles as nuclei. .
上記構成において、マリモカーボンの直径は、好ましくは、１μｍ〜１００μｍの範囲である。Ｓｉ微粒子は、好ましくは多結晶である。 In the above configuration, the diameter of marimocarbon is preferably in the range of 1 μm to 100 μm. The Si fine particles are preferably polycrystalline.
本発明のナノ炭素材料複合体の製造方法は、酸化ダイヤモンド触媒微粒子を核として繊維状のナノ炭素材料を放射状に形成するマリモカーボンの形成工程と、マリモカーボンを反応槽に収容し、反応槽を排気した後で、Ｓｉ微粒子をマリモカーボンの空隙に析出するＳｉ微粒子の析出工程と、を含む。 The method for producing a nanocarbon material composite according to the present invention includes a marimocarbon forming step in which a fibrous nanocarbon material is formed radially with diamond oxide catalyst fine particles as nuclei, and the marimocarbon is accommodated in a reaction vessel. And a step of depositing Si fine particles in which the Si fine particles are precipitated in the voids of the marimocarbon after being evacuated.
上記Ｓｉ微粒子の析出工程は、好ましくは化学蒸気堆積法による。 The Si fine particle deposition step is preferably performed by chemical vapor deposition.
本発明のリチウムイオン電池は、上記の何れかに記載のナノ炭素材料複合体を用いたことを特徴とする。 The lithium ion battery of the present invention is characterized by using any of the nanocarbon material composites described above.
本発明のＬｉイオン電池用活物質は、上記の何れかに記載のナノ炭素材料複合体を、活物質に用いたことを特徴とする。 The active material for a Li-ion battery according to the present invention is characterized in that the nanocarbon material composite described above is used as an active material.
本発明のナノ炭素材料複合体によれば、マリモカーボンを構成するカーボンナノ繊維の空隙にＳｉ微粒子を内包することにより、Ｓｉ微粒子をカーボンナノ繊維中に均一に分散させることができ、例えばリチウムイオン電池等の活物質、特に、負極や負極用活物質等に用いることが可能となる。 According to the nanocarbon material composite of the present invention, Si fine particles can be uniformly dispersed in carbon nanofibers by encapsulating Si fine particles in the voids of carbon nanofibers constituting marimocarbon. It becomes possible to use for active materials, such as a battery, especially a negative electrode, the active material for negative electrodes, etc.
本発明のナノ炭素材料複合体の製造方法によれば、マリモカーボンにＳｉ微粒子を化学上蒸気堆積（Chemical Vapor Deposition、ＣＶＤ）で堆積させることにより容易にナノ炭素材料複合体を製造することができる。 According to the method for producing a nanocarbon material composite of the present invention, a nanocarbon material composite can be easily produced by depositing Si fine particles on marimocarbon by chemical vapor deposition (CVD). .
以下、本発明の実施例について、図面を参照しながら説明する。
図１は、本発明のナノ炭素材料複合体１の構造を模式的に示す図であり、図２は、図１のナノ炭素材料複合体１を構成するマリモカーボン２の構造を模式的に示す図である。
図１に示すように、本発明のナノ炭素材料複合体１は、マリモカーボン２とＳｉ微粒子３とからなり、マリモカーボン２の空隙２ａにＳｉ微粒子３が内包された構造を有している。つまり、ナノ炭素材料複合体１は、酸化ダイヤモンド触媒微粒子４を核として繊維状のナノ炭素材料が放射状に形成されたマリモカーボン２の空隙２ａに、Ｓｉ微粒子３が内包されて構成される。図１では、外形を点線で示す空隙２ａに、Ｓｉ微粒子３が分散している。
Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a diagram schematically showing the structure of a nanocarbon material composite 1 of the present invention, and FIG. 2 schematically shows the structure of marimocarbon 2 constituting the nanocarbon material composite 1 of FIG. FIG.
As shown in FIG. 1, the nanocarbon material composite 1 of the present invention is composed of marimocarbon 2 and Si fine particles 3, and has a structure in which Si fine particles 3 are enclosed in voids 2 a of marimocarbon 2. That is, the nanocarbon material composite 1 is configured such that Si fine particles 3 are encapsulated in voids 2a of marimocarbon 2 in which fibrous nanocarbon materials are formed radially with diamond catalyst fine particles 4 as nuclei. In FIG. 1, Si fine particles 3 are dispersed in a gap 2 a whose outer shape is indicated by a dotted line.
図２に示すように、マリモカーボン２は、酸化ダイヤモンド（ｓｐ3炭素）に担持された触媒、つまり酸化ダイヤモンド触媒微粒子４を介して形成されたｓｐ2炭素からなる繊維状のカーボンナノ繊維２ｂ（Ｃarbon Nano Filament、ＣＮＦとも呼ばれている。）が、放射状に０．１μｍから１０μｍの長さに伸びており、恰もマリモのように全体として球形状を呈している。即ち、マリモカーボン２は、球状のカーボンナノ繊維２ｂで構成されている。 As shown in FIG. 2, marimocarbon 2 is a fibrous carbon nanofiber 2 b (sp 2 carbon formed of catalyst supported on oxidized diamond (sp 3 carbon), that is, sp 2 carbon formed through oxidized diamond catalyst fine particles 4. Carbon Nano Filament (also called CNF)) extends radially from 0.1 μm to 10 μm, and the coral also has a spherical shape as a whole like Marimo. That is, the marimo carbon 2 is composed of spherical carbon nanofibers 2b.
本発明のナノ炭素材料複合体１においては、図１に示すように、マリモカーボン２の空隙２ａの外側には、マリモカーボン２を構成するカーボンナノ繊維２ｂの一部２ｃが露出している。 In the nanocarbon material composite 1 of the present invention, as shown in FIG. 1, a part 2 c of the carbon nanofibers 2 b constituting the marimocarbon 2 is exposed outside the void 2 a of the marimocarbon 2.
マリモカーボン２の球の直径は、１〜５０μｍ、さらには、１μｍ〜１００μｍとすることができる。マリモカーボン２は、多くのカーボンナノ繊維２ｂを有している。マリモカーボン２を構成する各カーボンナノ繊維２ｂは互いに絡まり合っており、全体として球状の構造を有している。そして、マリモカーボン２のカーボンナノ繊維２ｂ間には多くの空隙２ａが形成されている。 The diameter of the sphere of the marimocarbon 2 can be 1 to 50 μm, and further 1 μm to 100 μm. The marimo carbon 2 has many carbon nanofibers 2b. The carbon nanofibers 2b constituting the marimo carbon 2 are entangled with each other and have a spherical structure as a whole. Many voids 2 a are formed between the carbon nanofibers 2 b of the marimo carbon 2.
図２に示す酸化ダイヤモンド触媒微粒子４に用いる酸化ダイヤモンドは、工業的に研磨用として市販されている５００ｎｍ以下の粒径のダイヤモンド粉末を酸化することにより調製できる（特許文献２参照）。ダイヤモンド粉末は、１０ｍ2／ｇ以上の高い比表面積を有するものを用いることが好ましい。酸化ダイヤモンド触媒微粒子４に用いる酸化ダイヤモンドは、ダイヤモンド粉末を３５０〜４５０℃の温度で、酸素雰囲気下又は空気中で表面を酸化させた後に触媒の担体として用いる。 The diamond oxide used for the diamond oxide catalyst fine particles 4 shown in FIG. 2 can be prepared by oxidizing diamond powder having a particle size of 500 nm or less that is commercially available for polishing (see Patent Document 2). It is preferable to use a diamond powder having a high specific surface area of 10 m 2 / g or more. The diamond oxide used for the diamond oxide catalyst fine particles 4 is used as a catalyst carrier after the surface of a diamond powder is oxidized at 350 to 450 ° C. in an oxygen atmosphere or in air.
酸化ダイヤモンド触媒微粒子４の触媒としては、Ｎｉ、Ｃｏ、Ｐｄ等が使用できる。酸化ダイヤモンドに触媒を担持するには、触媒となる金属を含む金属塩の水溶液に酸化ダイヤモンドを浸漬し、所定時間、例えば１２時間放置した後で、過剰の水を蒸発させ、乾燥後４００〜５００℃の空気中で焼成し、金属塩の分解と酸化を起こさせ、金属塩を酸化物に転換する。
次に、空気焼成後、Ｎｉ等からなる金属の酸化物を、水素等の還元雰囲気で金属へ還元して触媒とすることにより酸化ダイヤモンド触媒微粒子４を得ることができる（特許文献２参照）。
Ni, Co, Pd or the like can be used as a catalyst for the oxidized diamond catalyst fine particles 4. In order to support the catalyst on the diamond oxide, the diamond oxide is immersed in an aqueous solution of a metal salt containing a metal serving as a catalyst, left for a predetermined time, for example, 12 hours, excess water is evaporated, and 400 to 500 after drying. Baking in air at 0 ° C. causes decomposition and oxidation of the metal salt, converting the metal salt into an oxide.
Next, after air firing, diamond oxide catalyst particles 4 can be obtained by reducing a metal oxide composed of Ni or the like to a metal in a reducing atmosphere such as hydrogen to form a catalyst (see Patent Document 2).
酸化ダイヤモンド触媒微粒子４にカーボンナノ繊維２ｂを成長させるには、図７に示す流動気相合成装置（特許文献１参照）を使用し、原料ガス１６として炭化水素を用いて、酸化ダイヤモンド触媒微粒子４にカーボンナノ繊維２ｂを成長させて製造することができる。酸化ダイヤモンド触媒微粒子４の粒径は、５００ｎｍ以下であれば良く、大きすぎると流動気相合成装置１１０の反応槽１１３において浮遊し難くなるので好ましくない。原料ガス１６としてメタンを用い、触媒としてＮｉ、Ｃｏ又はＰｄを用いた場合には、成長温度は、４００℃〜６００℃の範囲が好ましい。また、酸化ダイヤモンド触媒微粒子４を所定の温度で浮遊させかつ撹拌させてカーボンナノ繊維２ｂを成長させる際に、生成するマリモカーボン２の粒径は攪拌時間、つまり反応時間に比例して大きくなるので、使用目的に応じて反応時間を設定すればよい。 In order to grow the carbon nanofibers 2b on the oxidized diamond catalyst fine particles 4, a fluidized gas phase synthesizer (see Patent Document 1) shown in FIG. The carbon nanofibers 2b can be grown and manufactured. The particle diameter of the diamond oxide catalyst fine particles 4 may be 500 nm or less, and if it is too large, it is difficult to float in the reaction vessel 113 of the fluidized gas phase synthesis apparatus 110, which is not preferable. When methane is used as the source gas 16 and Ni, Co or Pd is used as the catalyst, the growth temperature is preferably in the range of 400 ° C to 600 ° C. Further, when the carbon nanofibers 2b are grown by suspending and stirring the diamond oxide catalyst fine particles 4 at a predetermined temperature, the particle diameter of the produced marimocarbon 2 increases in proportion to the stirring time, that is, the reaction time. The reaction time may be set according to the purpose of use.
触媒としてＮｉ、Ｃｏを用いた場合に形成されるマリモカーボン２のカーボンナノ繊維２ｂは、例えば直径が１８ｎｍ程度の単層カーボンナノチューブからなる。 The carbon nanofibers 2b of marimocarbon 2 formed when Ni or Co is used as the catalyst are composed of single-walled carbon nanotubes having a diameter of about 18 nm, for example.
触媒としてＰｄを用いた場合に形成されるマリモカーボン２のカーボンナノ繊維２ｂは、例えば直径が２７ｎｍ程度のコイン積層型カーボンナノグラファイト繊維からなる（特許文献３参照）。コイン積層型グラファイト繊維は、直径が数〜数百ｎｍのコイン型の単層グラファイトが積層された炭素繊維であり、コイン型単層グラファイトの間隔は０．３〜１ｎｍである。 The carbon nanofibers 2b of marimocarbon 2 formed when Pd is used as the catalyst are made of, for example, coin-laminated carbon nanographite fibers having a diameter of about 27 nm (see Patent Document 3). Coin-stacked graphite fibers are carbon fibers in which coin-type single-layer graphite having a diameter of several to several hundred nm is stacked, and the interval between coin-type single-layer graphite is 0.3 to 1 nm.
Ｓｉ微粒子３は、例えば多結晶である。Ｓｉ微粒子３の大きさは、０．１μｍ（１００ｎｍ）〜１０μｍである。 The Si fine particles 3 are, for example, polycrystalline. The size of the Si fine particles 3 is 0.1 μm (100 nm) to 10 μm.
図３は、本発明の複数のナノ炭素材料複合体１からなる構造を模式的に示す図である。図３に示すように、本発明の複数のナノ炭素材料複合体１からなる構造は、図１に示すマリモカーボン２の最外側のカーボンナノ繊維２ｃと隣接するマリモカーボン２の最外側のカーボンナノ繊維２ｃとが互いに絡み合って配設されている。このため、本発明の複数のナノ炭素材料複合体１からなる構造では、非常に多くのカーボンナノ繊維２ｂが四方に分散し、その間の空隙２ａにＳｉ微粒子３が内包され、かつマリモカーボン２同士がマリモカーボン２から伸び出したカーボンナノ繊維２ｃで互いに絡み合った構造が形成される。このため、ナノ炭素材料複合体１では、Ｓｉ微粒子３がマリモカーボン２の空隙２ａ中に均一に分散され、かつ、マリモカーボン２により導電性が向上する。 FIG. 3 is a diagram schematically showing a structure composed of a plurality of nanocarbon material composites 1 of the present invention. As shown in FIG. 3, the structure composed of the plurality of nanocarbon material composites 1 of the present invention has the outermost carbon nanofibers of the marimocarbon 2 adjacent to the outermost carbon nanofibers 2c of the marimocarbon 2 shown in FIG. The fibers 2c are entangled with each other. For this reason, in the structure composed of a plurality of nanocarbon material composites 1 of the present invention, a very large number of carbon nanofibers 2b are dispersed in all directions, Si fine particles 3 are encapsulated in voids 2a therebetween, and marimocarbon 2 Are entangled with each other by the carbon nanofibers 2 c extending from the marimocarbon 2. Therefore, in the nanocarbon material composite 1, the Si fine particles 3 are uniformly dispersed in the voids 2 a of the marimocarbon 2, and the marimocarbon 2 improves the conductivity.
マリモカーボン２とＳｉ微粒子３とからなるナノ炭素材料複合体１は、リチウムイオン二次電池の負極に使用することができる。Ｓｉ微粒子３を内包したマリモカーボン２は、本明細書では、Ｓｉ微粒子／マリモカーボン複合体１とも表記する。具体的には、Ｓｉ微粒子／マリモカーボン複合体１は、負極又は負極用活物質や、導電助剤として用いることができる。さらに、Ｓｉ微粒子／マリモカーボン複合体１は、負極や負極用活物質或いは導電助剤の添加剤として用いることができる。 The nanocarbon material composite 1 composed of marimocarbon 2 and Si fine particles 3 can be used for a negative electrode of a lithium ion secondary battery. The marimocarbon 2 containing the Si fine particles 3 is also referred to as Si fine particles / marimocarbon composite 1 in this specification. Specifically, the Si fine particles / marimocarbon composite 1 can be used as a negative electrode or a negative electrode active material or a conductive aid. Further, the Si fine particles / marimocarbon composite 1 can be used as an additive for a negative electrode, a negative electrode active material, or a conductive additive.
本発明のナノ炭素材料複合体１に用いるマリモカーボン２は、カーボンブラックやカーボンナノチューブと比べて取り扱いが容易であり、カーボンナノ繊維２ｂ間に大きな空隙２ａを有している。そして、本発明のナノ炭素材料複合体１は、この空隙２ａにＳｉ微粒子３が担持されているので、カーボンブラックやカーボンナノチューブを活物質等に混合する際に生じる凝集が、生起しないという利点を有している。このため、本発明のナノ炭素材料複合体１を負極、負極用活物質、導電助剤、或いはこれらの添加剤に用いた場合、伝導性の向上、つまり低抵抗化が図れる。 The marimocarbon 2 used in the nanocarbon material composite 1 of the present invention is easier to handle than carbon black and carbon nanotubes, and has large voids 2a between the carbon nanofibers 2b. In the nanocarbon material composite 1 of the present invention, since the Si fine particles 3 are supported in the voids 2a, the agglomeration that occurs when carbon black or carbon nanotubes are mixed with an active material or the like does not occur. Have. For this reason, when the nanocarbon material composite 1 of the present invention is used for the negative electrode, the negative electrode active material, the conductive additive, or these additives, the conductivity can be improved, that is, the resistance can be reduced.
これにより、本発明のナノ炭素材料複合体１を用いた二次電池の充放電特性の性能を向上させることができる。さらに、マリモカーボン２の空隙２ａに内包されているＳｉ微粒子３は、Ｓｉ微粒子３自体にクラックが入っても、Ｓｉ微粒子３がナノ炭素材料複合体１にカーボンナノ繊維を含有して構成されているので、Ｓｉ微粒子３が崩れてバラバラにならない。これにより、本発明のナノ炭素材料複合体１を用いた二次電池やリチウムイオン電池用の充放電に伴うＳｉ微粒子３の膨張と収縮の繰り返しによる劣化が緩和される。このため、本発明のナノ炭素材料複合体１を負極としたリチウムイオン電池の充放電の繰り返し回数を向上させることができる。 Thereby, the performance of the charge / discharge characteristic of the secondary battery using the nanocarbon material composite 1 of the present invention can be improved. Further, the Si fine particles 3 encapsulated in the voids 2a of the marimocarbon 2 are configured such that the Si fine particles 3 contain carbon nanofibers in the nanocarbon material composite 1 even if the Si fine particles 3 themselves crack. As a result, the Si fine particles 3 do not collapse and fall apart. Thereby, the deterioration by the repetition of expansion | swelling and shrinkage | contraction of Si fine particle 3 accompanying the charging / discharging for the secondary battery using the nano carbon material composite_body | complex 1 of this invention or a lithium ion battery is relieved. For this reason, the repetition frequency of charging / discharging of the lithium ion battery which used the nanocarbon material composite 1 of this invention as the negative electrode can be improved.
本発明のマリモカーボン２とＳｉ微粒子３とからなるナノ炭素材料複合体１によれば、二次電池の負極、負極用活物質、導電助剤だけではなく、触媒としても利用できる。 According to the nanocarbon material composite 1 composed of marimocarbon 2 and Si fine particles 3 of the present invention, it can be used not only as a negative electrode for a secondary battery, an active material for a negative electrode, and a conductive assistant, but also as a catalyst.
（ナノ炭素材料複合体の製造方法）
本発明のナノ炭素材料複合体１の製造方法について説明する。
図４は、本発明のナノ炭素材料複合体１の製造に用いるＣＶＤ装置１０を模式的に示す図である。図４に示すように、ＣＶＤ装置１０は、反応槽１１と、反応槽１１を加熱する電気炉１２と、電気炉１２の温度を制御する温度制御部１３と、反応槽１１に希釈ガス１５と原料ガス１６からなる反応ガス１７を供給する反応ガス供給部１８と、排気部１９等を含んで構成されている。
(Method for producing nanocarbon material composite)
A method for producing the nanocarbon material composite 1 of the present invention will be described.
FIG. 4 is a diagram schematically showing a CVD apparatus 10 used for manufacturing the nanocarbon material composite 1 of the present invention. As shown in FIG. 4, the CVD apparatus 10 includes a reaction tank 11, an electric furnace 12 that heats the reaction tank 11, a temperature control unit 13 that controls the temperature of the electric furnace 12, and a dilution gas 15 in the reaction tank 11. A reaction gas supply unit 18 for supplying a reaction gas 17 made of a source gas 16 and an exhaust unit 19 are included.
反応ガス供給部１８は、希釈ガス１５の図示しないガスボンベ及び圧力調整器に接続されるストップバルブ２１、マスフローコントローラ等の流量調整器２２と、原料ガス１６の図示しないガスボンベ及び圧力調整器に接続されるストップバルブ２１、マスフローコントローラ等の流量調整器２２と、流量調整器２２と反応槽１１とを接続するフランジ２４と、これらを接続するステンレス等からなる配管２５等から構成されている。 The reaction gas supply unit 18 is connected to a stop valve 21 connected to a gas cylinder and a pressure regulator (not shown) of the dilution gas 15, a flow regulator 22 such as a mass flow controller, and a gas cylinder and a pressure regulator (not shown) of the source gas 16. A stop valve 21, a flow rate regulator 22 such as a mass flow controller, a flange 24 connecting the flow rate regulator 22 and the reaction tank 11, a pipe 25 made of stainless steel or the like for connecting them, and the like.
排気部１９は、真空ポンプと反応槽１１とを接続するフランジ、真空ポンプと反応槽１１との間に挿入されるゲートバルブ、真空計等の図示しない部品から構成されている。真空ポンプとしては、荒引き用ポンプ、油拡散ポンプ、ターボ分子ポンプ、イオンポンプ等を用いる。これらの真空ポンプは、反応槽１１が所定の圧力となるように適宜に組み合わせて使用することができる。 The exhaust part 19 is composed of a flange (not shown) such as a flange connecting the vacuum pump and the reaction tank 11, a gate valve inserted between the vacuum pump and the reaction tank 11, and a vacuum gauge. As the vacuum pump, a roughing pump, an oil diffusion pump, a turbo molecular pump, an ion pump, or the like is used. These vacuum pumps can be used in appropriate combination so that the reaction tank 11 has a predetermined pressure.
電気炉１２、温度制御部１３、反応ガス供給部１８、排気部１９等は、さらに図示しないマイクロコンピュータ等によりシーケンス制御されてもよい。 The electric furnace 12, the temperature control unit 13, the reaction gas supply unit 18, the exhaust unit 19 and the like may be further sequence-controlled by a microcomputer or the like (not shown).
図５は、本発明のナノ炭素材料複合体１の製造方法を説明するフロー図である。
（ａ）最初に、マリモカーボン２を合成する。
（ｂ）合成したマリモカーボン２をＣＶＤ装置１０の反応槽１１に収容する。
（ｃ）マリモカーボン２を収容したＣＶＤ装置１０の反応槽１１を十分に排気し、マリモカーボン２の繊維内に残留しているガスを排気する。排気は、反応槽１１に接続した排気部１９により行うことができる。
（ｄ）反応槽１１に希釈ガス１５を導入し、反応槽１１内に収容したＳｉ微粒子３を成長温度に加熱する。加熱には、電気炉１２、ランプ、レーザーを使用できる。Ｓｉ微粒子３をカーボン容器等に収容し、カーボン容器を加熱コイルにより誘導加熱してもよい。
（ｅ）反応槽１１にＳｉ微粒子３を成長させるための原料ガス１６を導入する。原料ガス１６としては、ＳｉとＨ（水素）、ＳｉとＣｌ（塩素）、ＳｉとＣｌとＨ（水素）との化合物ガスを使用することができる。原料ガス１６は例えば、ＳｉＨ4である。これらの原料ガス１６は、不活性ガスや水素ガスで希釈してもよい。不活性ガスは、Ａｒ（アルゴン）やＨｅ（ヘリウム）を用いればよい。原料ガス１６を、成長温度で所定時間流すことにより、マリモカーボン２のカーボンナノ繊維２ｂの隙間２ａにＳｉ微粒子３を成長させ、ナノ炭素材料複合体１を形成することができる。多結晶のＳｉ微粒子３は、例えば、原料ガス１６をＡｒで希釈してＳｉＨ4とし、成長温度を６００〜８００℃として、マリモカーボン２の空隙２ａ内に析出することができる。
（ｆ）所定時間成長した後、原料ガス１６であるＳｉＨ4の反応槽１１への供給を停止し、電気炉１２による加熱を停止して、室温程度まで降温する。
（ｇ）反応槽１１から合成したＳｉ微粒子／マリモカーボン複合体１を回収する。
FIG. 5 is a flow diagram illustrating a method for producing the nanocarbon material composite 1 of the present invention.
(A) First, marimocarbon 2 is synthesized.
(B) The synthesized marimocarbon 2 is accommodated in the reaction tank 11 of the CVD apparatus 10.
(C) The reaction tank 11 of the CVD apparatus 10 containing the marimocarbon 2 is sufficiently exhausted, and the gas remaining in the fibers of the marimocarbon 2 is exhausted. Exhaust can be performed by the exhaust unit 19 connected to the reaction tank 11.
(D) The dilution gas 15 is introduced into the reaction vessel 11 and the Si fine particles 3 accommodated in the reaction vessel 11 are heated to the growth temperature. An electric furnace 12, a lamp, or a laser can be used for heating. The Si fine particles 3 may be accommodated in a carbon container or the like, and the carbon container may be induction heated by a heating coil.
(E) The raw material gas 16 for growing the Si fine particles 3 is introduced into the reaction vessel 11. As the source gas 16, a compound gas of Si and H (hydrogen), Si and Cl (chlorine), Si, Cl and H (hydrogen) can be used. The source gas 16 is, for example, SiH 4 . These source gases 16 may be diluted with an inert gas or hydrogen gas. As the inert gas, Ar (argon) or He (helium) may be used. By flowing the raw material gas 16 at a growth temperature for a predetermined time, the Si fine particles 3 are grown in the gaps 2a between the carbon nanofibers 2b of the marimocarbon 2, and the nanocarbon material composite 1 can be formed. The polycrystalline Si fine particles 3 can be deposited in the voids 2a of the marimocarbon 2 at a growth temperature of 600 to 800 ° C., for example, by diluting the source gas 16 with Ar to make SiH 4 .
(F) After growing for a predetermined time, the supply of SiH 4 as the raw material gas 16 to the reaction vessel 11 is stopped, the heating by the electric furnace 12 is stopped, and the temperature is lowered to about room temperature.
(G) The synthesized Si fine particles / marimocarbon composite 1 is recovered from the reaction vessel 11.
次に、本発明の製造方法の一例について説明する。
最初に、マリモカーボン２を、Ｎｉを酸化ダイヤモンド触媒微粒子４上にメタンガスの分解によって合成した（非特許文献１４参照）。
Ｎｉを触媒として合成したマリモカーボン２を、図４に示すＣＶＤ装置１０を用いて、Ｓｉ微粒子３を堆積する。
先ず、反応槽１１内の石英容器に載置し、反応槽１１内のマリモカーボン２中の残留ガスを排気部１９より真空排気した後、反応槽１１内に希釈ガス１５を流す。
次に、反応槽１１を電気炉１２により６００℃まで昇温し、続いて、原料ガス１６としてＳｉＨ4を、希釈ガス１５としてＡｒを用いて、ＳｉＨ4の流量が１０％で流量が１００ｓｃｃｍ（ｓｃｃｍはｃｍ3／分である。）の反応ガス１７を反応槽１１に供給する。反応時間は６０分とし、６０分経過後に、電気炉１２の通電を停止し、反応槽１１を自然冷却することにより、Ｓｉ微粒子／マリモカーボン複合体１を製造することができる。
Next, an example of the manufacturing method of the present invention will be described.
First, marimocarbon 2 was synthesized by decomposing Ni on oxidized diamond catalyst fine particles 4 by decomposition of methane gas (see Non-Patent Document 14).
Si fine particles 3 are deposited on the marimocarbon 2 synthesized using Ni as a catalyst, using the CVD apparatus 10 shown in FIG.
First, after placing in a quartz container in the reaction vessel 11 and evacuating the residual gas in the marimocarbon 2 in the reaction vessel 11 from the exhaust unit 19, a dilution gas 15 is caused to flow into the reaction vessel 11.
Next, the reaction vessel 11 by an electric furnace 12 was raised to 600 ° C., followed by the SiH 4 as a raw material gas 16, using Ar as a dilution gas 15, the flow rate of SiH 4 is the flow rate at 10% 100 sccm ( sccm is cm 3 / min)). The reaction time is 60 minutes, and after 60 minutes, the energization of the electric furnace 12 is stopped, and the reaction vessel 11 is naturally cooled, whereby the Si fine particles / marimocarbon composite 1 can be produced.
本発明は、上記実施の形態に限定されるものではなく、特許請求の範囲に記載した発明の範囲内で種々の変形が可能であり、それらも本発明の範囲内に含まれることはいうまでもない。 The present invention is not limited to the above embodiment, and various modifications are possible within the scope of the invention described in the claims, and it goes without saying that these are also included in the scope of the present invention. Nor.
１：ナノ炭素材料複合体
２：マリモカーボン
２ａ：空隙
２ｂ：カーボンナノ繊維
２ｃ：最外側のカーボンナノ繊維
３：Ｓｉ微粒子
４：酸化ダイヤモンド触媒微粒子
１０：ＣＶＤ装置
１１：反応槽
１２：電気炉
１３：温度制御部
１５：希釈ガス
１６：原料ガス
１７：反応ガス
１８：反応ガス供給部
１９：排気部
２１：ストップバルブ
２２：流量調整器
２４：フランジ
２５：配管
1: nanocarbon material composite 2: marimocarbon 2a: void 2b: carbon nanofiber 2c: outermost carbon nanofiber 3: Si fine particles 4: oxidized diamond catalyst fine particles 10: CVD apparatus 11: reaction vessel 12: electric furnace 13 : Temperature control unit 15: Dilution gas 16: Raw material gas 17: Reaction gas 18: Reaction gas supply unit 19: Exhaust unit 21: Stop valve 22: Flow rate regulator 24: Flange 25: Piping
Claims (7)
上記マリモカーボンを反応槽に収容し、該反応槽を排気した後で、Ｓｉ微粒子を上記マリモカーボンの空隙に析出する工程と、
を、含むナノ炭素材料複合体の製造方法。 Marimocarbon formation process that forms fibrous nanocarbon material radially with oxide diamond catalyst fine particles as nuclei,
Depositing the marimocarbon in a reaction vessel, evacuating the reaction vessel, and then depositing Si fine particles in the voids of the marimocarbon;
The manufacturing method of the nanocarbon material composite containing this.
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