JP6045860B2 - Carbon material and non-aqueous secondary battery using the same - Google Patents
Carbon material and non-aqueous secondary battery using the same Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 72
- 239000002134 carbon nanofiber Substances 0.000 claims description 69
- 239000006229 carbon black Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 239000006258 conductive agent Substances 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 14
- 230000001186 cumulative effect Effects 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- -1 ethylene, propylene, butene Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
- 239000008096 xylene Substances 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
Description
本発明は非水系二次電池において、これら負極及び／又は正極に導電性を付与するための導電剤としての炭素材料と、それを用いて構成された非水系二次電池に関する。 The present invention relates to a carbon material as a conductive agent for imparting conductivity to the negative electrode and / or the positive electrode in a non-aqueous secondary battery, and a non-aqueous secondary battery configured using the carbon material.
リチウムイオン二次電池は、携帯電話、ノートパソコンなどの小型民生用機器の電源として幅広く用いられている。また、近年は中・大型用途として車載用や据置用の電源として開発が進められ、一部は実用化されている。そして使用機器の高性能化、大型化に伴い、特に昨今、バッテリーパックとして複数の電池を直列・並列につなげて使用したり、電極面積を大型化して使用することが一般的になってきており、電池の品質管理要求レベルはますます高まっている。 Lithium ion secondary batteries are widely used as power sources for small consumer devices such as mobile phones and laptop computers. In recent years, development has been promoted as a power source for in-vehicle use or stationary use for medium and large-sized applications, and a part of them has been put into practical use. As the equipment used increases in performance and size, it has become common to use multiple batteries connected in series or in parallel as a battery pack, or to increase the electrode area. The level of battery quality control requirements is increasing.
従来、リチウムイオン二次電池の正極としては、コバルト酸リチウム、マンガン酸リチウム等の複合酸化物からなる正極活物質と黒鉛やカーボンブラック等の導電剤とを含有してなる組成物を、アルミ箔等の金属箔からなる集電体に被着させてなるものが用いられている。一方、負極としては、黒鉛、ハードカーボン等の炭素質材料やスズ系アモルファス材料、チタン酸リチウム等の複合酸化物からなる負極活物質と黒鉛やカーボンブラック等の
導電剤とを含有してなる組成物を、銅箔等の金属箔からなる集電体に被着させてなるものが用いられている。
Conventionally, as a positive electrode of a lithium ion secondary battery, a composition containing a positive electrode active material composed of a composite oxide such as lithium cobaltate and lithium manganate and a conductive agent such as graphite and carbon black is used as an aluminum foil. What is made to adhere to the collector which consists of metal foils, such as, is used. On the other hand, as the negative electrode, a composition comprising a negative electrode active material composed of a carbonaceous material such as graphite or hard carbon, a tin-based amorphous material, or a composite oxide such as lithium titanate, and a conductive agent such as graphite or carbon black. The thing formed by making a thing adhere to the electrical power collector which consists of metal foils, such as copper foil, is used.
導電剤の役割は、導電性を有しない活物質に導電性を付与すること、充放電時に電極活物質が繰り返し膨張収縮して導電性が損なわれるのを防止することである。そのため、電極において、活物質と導電剤の分散が悪いと、電極内において局所的に導電性の劣る部分が現れ、活物質が有効に利用されずに放電容量が低下し、寿命が短くなる原因となる。 The role of the conductive agent is to impart conductivity to an active material having no conductivity, and to prevent the electrode active material from repeatedly expanding and contracting during charge / discharge, thereby impairing conductivity. Therefore, in the electrode, if the dispersion of the active material and the conductive agent is poor, a portion with poor conductivity appears locally in the electrode, the active material is not effectively used, the discharge capacity is reduced, and the life is shortened. It becomes.
そこで導電剤と活物質の均一混合を目的として、特許文献１には凝集しやすいカーボンブラックや黒鉛等の導電剤を有機溶媒中でボールミルを使用してより微細化する試みが行われている。また、特許文献２には分散剤を使用して高圧ジェットミルで有機溶媒に分散する試みが行われている。一方、特許文献３、４には、活物質と導電剤を乾式で均一混合する手法、活物質表面に導電剤を被覆する手法が試みられている。いずれも特殊な装置による前処理が必要で、前処理時の異物混入や、活物質、導電剤のダメージによる本来の性能の低下といった問題があった。 Therefore, for the purpose of uniform mixing of the conductive agent and the active material, Patent Document 1 attempts to further refine the conductive agent such as carbon black and graphite, which are easily aggregated, in an organic solvent using a ball mill. Patent Document 2 attempts to disperse an organic solvent using a high-pressure jet mill using a dispersant. On the other hand, Patent Documents 3 and 4 attempt a method of uniformly mixing an active material and a conductive agent in a dry manner and a method of coating a conductive agent on the surface of the active material. In any case, pretreatment by a special apparatus is required, and there are problems such as contamination of foreign matters during pretreatment and deterioration of the original performance due to damage to the active material and the conductive agent.
これらの問題に対し、導電剤としてカーボンナノファイバーを用いることが提案されている。しかしカーボンナノファイバーは、カーボンブラックよりも結晶性が高く粉体の抵抗値は低いものの、そのファイバーが絡み合った凝集体として存在するため、活物質と混合する際の分散性が悪く、導電性付与能力が十分に発揮できていない。そのため、酸処理や機械的な撹拌処理による凝集体の分散も検討されているが、カーボンナノファイバーが短く切断され、本来の特長が失われてしまうことがある。そこで、カーボンブラックとカーボンナノファイバーの複合体が検討されている。例えば特許文献５では、アセチレンブラックの反応場でカーボンナノファイバーを生成するという提案がされているが、アセチレンブラックとカーボンナノチューブの生成条件が異なるため、一つの生成場での同時生成を行うと品質が安定しないといった課題がある。また、特許文献６では、カーボンブラック生成場にカーボンナノファイバーを導入し複合体を得るという提案がされているが、原料のカーボンナノファイバーが凝集しているため、複合体の凝集サイズも大きくなり、活物質との均一混合が困難であるといった課題があり、十分な解決策が見いだされていないのが現状である。 For these problems, it has been proposed to use carbon nanofibers as a conductive agent. However, although carbon nanofibers have higher crystallinity and lower powder resistance than carbon black, they exist as aggregates in which the fibers are intertwined. The ability is not fully demonstrated. Therefore, although dispersion of aggregates by acid treatment or mechanical stirring treatment has been studied, carbon nanofibers may be cut short and the original characteristics may be lost. Therefore, a composite of carbon black and carbon nanofiber has been studied. For example, Patent Document 5 proposes that carbon nanofibers are generated in a reaction field of acetylene black. However, since the generation conditions of acetylene black and carbon nanotubes are different, the quality can be improved by simultaneous generation in one generation field. There is a problem that is not stable. Patent Document 6 proposes that carbon nanofibers are introduced into a carbon black production field to obtain a composite, but the aggregate size of the composite also increases because the raw carbon nanofibers are aggregated. However, there is a problem that uniform mixing with an active material is difficult, and a sufficient solution has not been found.
本発明の目的は、分散性及び導電性付与能力に優れた炭素材料及びそれを用いた非水系二次電池を提供することである。 The objective of this invention is providing the carbon material excellent in the dispersibility and electroconductivity provision capability, and a non-aqueous secondary battery using the same.
本発明者らは上記の課題を解決するために、以下の手法を採用した。
（１）比表面積が３０〜７０ｍ２／ｇ、ＤＢＰ吸収量と比表面積の比が３．０（ｍｌ／１００ｇ）／（ｍ２／ｇ）以上であるカーボンブラックと、平均繊維径が５〜４０ｎｍであるカーボンナノファイバーからなる、粒子径分布における累積５０％粒子径ｄ５０が２．０〜１０．０μｍ、累積９０％粒子径ｄ９０が２０．０μｍ以下である非水系二次電池の正極の導電剤用の炭素材料。
（２）カーボンナノファイバーの含有比率が５〜３５質量％である前記（１）に記載の非水系二次電池の正極の導電剤用の炭素材料。
（３）カーボンブラックにカーボンナノファイバー生成用触媒を担持し、これと炭素含有化合物を接触させる前記（１）又は前記（２）に記載の非水系二次電池の正極の導電剤用の炭素材料の製造方法。
（４）カーボンナノファイバー生成用触媒を湿式分散させた後、カーボンブラックへ担持させる前記（３）に記載の非水系二次電池の正極の導電剤用の炭素材料の製造方法。
（５）前記（１）〜（２）に記載の炭素材料を正極に含有する非水系二次電池。
In order to solve the above problems, the present inventors have adopted the following method.
(1) Carbon black having a specific surface area of 30 to 70 m 2 / g, a ratio of DBP absorption to specific surface area of 3.0 (ml / 100 g) / (m 2 / g) or more, and an average fiber diameter of 5 to 5 Conductivity of the positive electrode of a non-aqueous secondary battery comprising carbon nanofibers of 40 nm and having a cumulative 50% particle size d50 in the particle size distribution of 2.0 to 10.0 μm and a cumulative 90% particle size d90 of 20.0 μm or less. Carbon material for chemicals .
(2) The carbon material for the conductive agent of the positive electrode of the nonaqueous secondary battery according to (1), wherein the content ratio of the carbon nanofibers is 5 to 35% by mass.
(3) The carbon material for the conductive agent of the positive electrode of the non-aqueous secondary battery according to (1) or (2), wherein a carbon nanofiber generating catalyst is supported on carbon black and brought into contact with a carbon-containing compound. Manufacturing method.
(4) The method for producing a carbon material for the conductive agent of the positive electrode of the nonaqueous secondary battery according to (3), wherein the catalyst for producing carbon nanofibers is wet-dispersed and then supported on carbon black.
(5) A nonaqueous secondary battery containing the carbon material according to (1) to (2) in a positive electrode .
本発明によれば、分散性及び導電性付与能力に優れた炭素材料及びそれを用いた非水系二次電池を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the carbon material excellent in the dispersibility and electroconductivity provision ability, and a non-aqueous secondary battery using the same can be obtained.
本発明の炭素材料は、カーボンブラックとカーボンナノファイバーからなるものである。ここでカーボンナノファイバーとは、繊維径が数百ｎｍ以下である繊維状炭素のことであり、一般にカーボンナノチューブと称される中空構造を有する繊維状炭素も含まれる。
本発明者は、炭素材料の分散性及び導電性付与能力を向上させるために鋭意検討を行った結果、炭素材料の構造がこれらの特性に大きく影響することを見出した。
すなわち、比表面積が３０〜７０ｍ２／ｇであり、ＤＢＰ吸収量と比表面積の比が３．０（ｍｌ／１００ｇ）／（ｍ２／ｇ）以上であるカーボンブラックと、平均繊維径が５〜４０ｎｍであるカーボンナノファイバーからなる炭素材料の体積基準粒子径分布における累積５０％粒子径ｄ５０を２．０〜１０．０μｍ、累積９０％粒子径ｄ９０を２０．０μｍ以下とすることにより、活物質との接触点を効果的に増やすことができ、これを用いた非水系二次電池の特性を大幅に向上させることができた。ここで体積基準粒子径分布は、レーザー回折・散乱法などに従い粒度分布測定装置で測定ができ、微粉側からの累積５０％の粒子径を累積５０％粒子径ｄ５０、微粉側からの累積９０％の粒子径を累積９０％粒子径ｄ９０として求めることができる。
累積５０％粒子径ｄ５０が２．０μｍ未満であるとカーボンブラックとカーボンナノファイバーから形成される導電パスが短くなるため、導電性が低くなり、１０．０μｍを超えると活物質との接触点、すなわち導電パス数が少なくなり、局所的に導電性の劣る部分が生じてしまう。また、累積９０％粒子径ｄ９０が２０．０μｍを超えると、カーボンブラックとカーボンナノファイバーが強く凝集しているため、電極作製時の混合処理によっても凝集を解砕することができない。
The carbon material of the present invention is composed of carbon black and carbon nanofibers. Here, the carbon nanofiber is fibrous carbon having a fiber diameter of several hundred nm or less, and includes fibrous carbon having a hollow structure generally called a carbon nanotube.
As a result of intensive studies in order to improve the dispersibility and conductivity imparting ability of the carbon material, the present inventor has found that the structure of the carbon material greatly affects these characteristics.
That is, the specific surface area is 30 to 70 m 2 / g, the ratio of the DBP absorption amount to the specific surface area is 3.0 (ml / 100 g) / (m 2 / g) or more, and the average fiber diameter is 5 By setting the cumulative 50% particle diameter d50 in the volume-based particle diameter distribution of the carbon material composed of carbon nanofibers of ˜40 nm to 2.0 to 10.0 μm and the cumulative 90% particle diameter d90 to 20.0 μm or less. The number of contact points with the substance can be effectively increased, and the characteristics of the non-aqueous secondary battery using this can be greatly improved. Here, the volume-based particle size distribution can be measured with a particle size distribution measuring device according to a laser diffraction / scattering method, the particle size of 50% cumulative from the fine powder side is 50% cumulative particle size d50, and the cumulative 90% from the fine powder side. Can be obtained as a cumulative 90% particle diameter d90.
If the cumulative 50% particle diameter d50 is less than 2.0 μm, the conductive path formed from carbon black and carbon nanofibers is shortened, so that the conductivity is low, and if it exceeds 10.0 μm, the contact point with the active material, That is, the number of conductive paths is reduced, and a locally inferior portion is generated. If the cumulative 90% particle diameter d90 exceeds 20.0 μm, the carbon black and the carbon nanofibers are strongly aggregated, so that the aggregation cannot be crushed even by the mixing process during electrode production.
本発明では、カーボンブラックの比表面積が３０〜７０ｍ２／ｇである。ここで比表面積は、ＪＩＳ Ｋ６２１７−２に従って測定することができる。比表面積が３０ｍ２／ｇ未満であると、活物質やカーボンナノチューブとの接触面積が小さくなり、十分な導電性が発揮できなくなる。また、比表面積が７０ｍ２／ｇを超えると電極作製時のスラリー粘度が上昇してしまう原因となる。
また、本発明では、カーボンブラックのＤＢＰ吸収量と比表面積の比が３．０（ｍｌ／１００ｇ）／（ｍ２／ｇ）以上である。ここでＤＢＰ吸収量は、ＪＩＳ Ｋ６２１７−４に従って測定することができる。ＤＢＰ吸収量はカーボンブラックのストラクチャー（一次粒子が複数融着した構造）を評価する物性値である。しかし一般的に、比表面積値が高いとＤＢＰ吸収量が多くなるため、ＤＢＰ吸収量と比表面積の比をとり、比表面積の影響を考慮したうえでのストラクチャー評価を行った。ＤＢＰ吸収量と比表面積の比が３．０（ｍｌ／１００ｇ）／（ｍ２／ｇ）未満であると、ストラクチャーが十分に発達していないため、二次電池の充放電に伴う活物質の体積変化を緩衝することができず、サイクル特性が低下してしまう。
In the present invention, the specific surface area of carbon black is 30 to 70 m 2 / g. Here, the specific surface area can be measured according to JIS K6217-2. When the specific surface area is less than 30 m 2 / g, the contact area with the active material and the carbon nanotubes becomes small, and sufficient conductivity cannot be exhibited. Moreover, when a specific surface area exceeds 70 m < 2 > / g, it will cause the slurry viscosity at the time of electrode preparation to raise.
In the present invention, the ratio between the DBP absorption amount and the specific surface area of the carbon black is 3.0 (ml / 100 g) / (m 2 / g) or more. Here, the DBP absorption can be measured according to JIS K6217-4. The DBP absorption amount is a physical property value for evaluating the structure of carbon black (a structure in which a plurality of primary particles are fused). However, in general, when the specific surface area value is high, the DBP absorption amount increases. Therefore, the ratio between the DBP absorption amount and the specific surface area was taken, and the structure evaluation was performed in consideration of the influence of the specific surface area. When the ratio of the DBP absorption amount to the specific surface area is less than 3.0 (ml / 100 g) / (m 2 / g), the structure is not sufficiently developed. The volume change cannot be buffered, and the cycle characteristics deteriorate.
本発明では、カーボンナノチューブの平均繊維径が５〜４０ｎｍである。ここでカーボンナノチューブの平均繊維径は、透過型電子顕微鏡にて微細構造を観察し、確認できる。平均繊維径が４０ｎｍより大きくなると、炭素材料単位重量当たりに含まれる繊維本数が少なくなり、活物質及びカーボンブラックとの接触点が少なくなるため、導電性が低下してしまう。特に炭素材料の添加量が少ない場合にその影響が顕著となる。平均繊維径を５ｎｍ未満にするためには、カーボンナノファイバーの合成条件を厳しく管理しなければならず、生産が難しくなる。 In the present invention, the average fiber diameter of the carbon nanotube is 5 to 40 nm. Here, the average fiber diameter of the carbon nanotubes can be confirmed by observing the fine structure with a transmission electron microscope. When the average fiber diameter is larger than 40 nm, the number of fibers contained per unit weight of the carbon material is decreased, and the number of contact points between the active material and carbon black is decreased. In particular, when the amount of carbon material added is small, the effect becomes significant. In order to make the average fiber diameter less than 5 nm, the synthesis conditions of the carbon nanofibers must be strictly controlled, and the production becomes difficult.
本発明の炭素材料中のカーボンナノファイバーの含有比率は５〜３５質量％であることが好ましく、１０〜２０質量％であることがより好ましい。
カーボンナノファイバーの含有比率が５質量％未満であると十分な導電性が得られない場合があり、３５質量％を超えるとカーボンナノファイバーが凝集しやすくなるため分散性が低下する場合がある。カーボンナノファイバーの含有比率は、カーボンブラックに担持させるカーボンナノファイバー生成用触媒の量や、合成温度や合成時間により調整することができる。
The content ratio of the carbon nanofibers in the carbon material of the present invention is preferably 5 to 35% by mass, and more preferably 10 to 20% by mass.
When the content ratio of the carbon nanofibers is less than 5% by mass, sufficient conductivity may not be obtained, and when it exceeds 35% by mass, the carbon nanofibers are likely to aggregate and the dispersibility may be lowered. The content ratio of carbon nanofibers can be adjusted by the amount of carbon nanofiber production catalyst supported on carbon black, the synthesis temperature, and the synthesis time.
本発明の炭素材料を構成するカーボンブラックの種類は特に限定されないが、例えば、サーマルブラック、ファーネスブラック、ランプブラック、チャンネルブラック、アセチレンブラックなどが用いられるが、中でもアセチレンブラックがより好ましい。アセチレンブラックは高純度、高結晶性の一次粒子が連鎖した構造を有しているため、導電性に優れているためである。 The type of carbon black constituting the carbon material of the present invention is not particularly limited. For example, thermal black, furnace black, lamp black, channel black, acetylene black and the like are used, and among them, acetylene black is more preferable. This is because acetylene black has a structure in which primary particles of high purity and high crystallinity are chained, and thus is excellent in conductivity.
カーボンナノファイバーは、カーボンナノファイバー生成用触媒粒子を核として生成・成長する。一般的な化学的気相成長法ではカーボンナノファイバー生成用触媒を静置した状態で炭素含有化合物と接触させるため、空間に占めるカーボンナノファイバー生成用触媒の密度が高く、生成するカーボンナノファイバーも密集した状態となり、お互いが絡み合って１００μｍオーダーの凝集体を形成してしまう。そこで本発明では、導電剤として広く使用されているカーボンブラックの表面にカーボンナノファイバー生成用触媒を適量担持させ、カーボンナノファイバーを生成・成長させることにより、得られる炭素材料の凝集サイズを例えば２０μｍ以下といったように従来のカーボンナノファイバー単体の凝集サイズよりも小さくし、分散性及び導電性付与能力の向上を達成するに至った。したがって本発明の炭素材料においては、カーボンブラックとカーボンナノファイバーが結合していない場合でも十分な導電性付与能力を発揮する。ここで結合とは、単なる接触状態ではなく、炭素質で物理的に融着していることを意味する。従来、カーボンナノファイバー生成用触媒を担持させる場合、合成後のカーボンナノファイバーを分離・回収するためにアルミナやシリカなどの異材料を担体として用いるのが一般的であるが、本発明は、炭素質であるカーボンブラックを担体とし、さらに、担体に対するカーボンナノファイバー生成用触媒の配合量を例えば２０質量％以下といったように少なくすることを特徴とした製造方法である。 Carbon nanofibers are generated and grown using catalyst particles for carbon nanofiber generation as nuclei. In a general chemical vapor deposition method, the carbon nanofiber generation catalyst is left in contact with the carbon-containing compound in a stationary state, so the density of the carbon nanofiber generation catalyst in the space is high, and the generated carbon nanofibers are also It will be in a dense state and entangled with each other to form an aggregate of the order of 100 μm. Therefore, in the present invention, an appropriate amount of a catalyst for generating carbon nanofibers is supported on the surface of carbon black widely used as a conductive agent, and carbon nanofibers are generated and grown, whereby the obtained carbon material has an aggregate size of, for example, 20 μm. As described below, it has been made smaller than the aggregate size of the conventional carbon nanofibers alone, thereby achieving improvement in dispersibility and conductivity imparting ability. Therefore, the carbon material of the present invention exhibits sufficient conductivity imparting ability even when carbon black and carbon nanofibers are not bonded. The term “bond” here means not a simple contact state but physically bonded with carbonaceous material. Conventionally, when a catalyst for producing carbon nanofibers is supported, it is common to use a different material such as alumina or silica as a carrier in order to separate and recover the synthesized carbon nanofibers. The production method is characterized in that carbon black, which is a quality, is used as a carrier, and the amount of the carbon nanofiber production catalyst to the carrier is reduced to, for example, 20% by mass or less.
カーボンナノファイバー生成用触媒としては、鉄族元素（鉄、コバルト又はニッケル）の単体又は鉄族元素を含む化合物、例えば鉄族元素の酸化物、硝酸化物又は水酸化物などを用いることができるが、特に酸化物が好ましい。鉄族元素含有合金又は鉄族元素含有合金を含む化合物、例えば鉄族元素含有合金の酸化物、硝酸化物又は水酸化物を用いても良い。これらの物質は単独で用いて良いが、二種以上の物質を同時に用いることも可能である。また、生成させるカーボンナノチューブの平均繊維径を５〜４０ｎｍとするためには、カーボンナノファイバー生成用触媒の一次粒子径が２０ｎｍ以下であることが好ましい。 As the catalyst for producing carbon nanofibers, a simple substance of an iron group element (iron, cobalt or nickel) or a compound containing an iron group element, for example, an oxide, nitrate or hydroxide of an iron group element can be used. In particular, an oxide is preferable. You may use the iron group element containing alloy or the compound containing an iron group element containing alloy, for example, the oxide, nitrate, or hydroxide of an iron group element containing alloy. These substances may be used alone, but two or more kinds of substances may be used simultaneously. Moreover, in order to make the average fiber diameter of the carbon nanotube to produce | generate to 5-40 nm, it is preferable that the primary particle diameter of the catalyst for carbon nanofiber production | generation is 20 nm or less.
カーボンナノファイバー生成用触媒は、カーボンブラックに担持されていることが必要である。担持させる方法は、例えば、アルコールなどの液体に鉄族元素の単体又は鉄族元素を含む化合物などのカーボンナノファイバー生成用触媒を懸濁させ、あるいは溶解させ、この液中にカーボンブラックを投入し、撹拌、混合、乾燥することにより担持させることができる。また、担持前のカーボンナノファイバー生成用触媒に分散処理を施すことが好ましい。分散処理の方法は特に限定されないが、分散能力が高く、分散後のカーボンブラックとの混合に適している湿式分散が好ましい。例えば、湿式ビーズミルや湿式ジェットミルなどの装置が使用できる。これにより、１００μｍオーダーに凝集しているカーボンナノファイバー生成用触媒を１００ｎｍオーダーにまで分散し、生成するカーボンナノファイバーの繊維径を細くすることができる。また、カーボンナノファイバー生成用触媒を湿式分散させた液中にカーボンブラックを入れ、混合、濾過、乾燥させることでカーボンナノファイバー生成用触媒の再凝集を抑制することができる。
本発明は、カーボンブラックの比表面積とストラクチャーを制御した特定のカーボンブラックに、カーボンナノファイバー生成用触媒を担持させた原料粉を用いることにより、凝集が少なく、分散性の優れた炭素材料が製造できるものである。
The catalyst for producing carbon nanofibers needs to be supported on carbon black. The supporting method is, for example, suspending or dissolving a carbon nanofiber producing catalyst such as a simple substance of an iron group element or a compound containing an iron group element in a liquid such as alcohol, and charging carbon black into this liquid. It can be supported by stirring, mixing and drying. Moreover, it is preferable to perform a dispersion treatment on the carbon nanofiber generating catalyst before supporting. The method for the dispersion treatment is not particularly limited, but wet dispersion is preferable because it has high dispersion ability and is suitable for mixing with carbon black after dispersion. For example, an apparatus such as a wet bead mill or a wet jet mill can be used. Thereby, the catalyst for carbon nanofiber production | generation which has aggregated to the order of 100 micrometers can be disperse | distributed to the order of 100 nm, and the fiber diameter of the carbon nanofiber to produce | generate can be made thin. Further, carbon black is put into a liquid in which a carbon nanofiber production catalyst is wet dispersed, and mixing, filtration, and drying can suppress reaggregation of the carbon nanofiber production catalyst.
The present invention produces a carbon material with less agglomeration and excellent dispersibility by using a raw material powder carrying a carbon nanofiber production catalyst on a specific carbon black with a controlled specific surface area and structure of carbon black. It can be done.
本発明に係る炭素含有化合物は、例えば、メタン、エタン、プロパン、ブタンなどの飽和炭化水素、エチレン、プロピレン、ブテン、ブタジエンなどの２重結合を有する不飽和炭化水素、アセチレン、プロピン、ブチンなどの３重結合を有する不飽和炭化水素、ベンゼン、トルエン、キシレンなどの芳香族炭化水素などを用いることができる。また、一酸化炭素や、一酸化炭素を含むカーバイド炉やコークス炉などの副生ガスも用いることができる。炭素含有物だけ存在すればカーボンナノファイバーが生成しそうであるが、実際はＨ２などの還元性ガスを共存させなければ反応率が著しく低下する。還元ガスの還元作用によって触媒の失活が抑制されるためであると考えられる。炭素含有化合物はさらに、窒素、アルゴンなどの不活性ガスによって希釈しても良い。合成炉の温度は３００〜１０００℃、圧力は０．０１ＭＰａ〜１ＭＰａが好ましい。温度３００℃未満若しくは１０００℃超又は圧力０．０１ＭＰａ未満では反応が殆ど生じないため好ましくない。また圧力１ＭＰａ超は装置の耐圧対策が煩雑になる割には収率や物性の改善効果が顕著に認められないため好ましくない。 Examples of the carbon-containing compound according to the present invention include saturated hydrocarbons such as methane, ethane, propane, and butane, unsaturated hydrocarbons having a double bond such as ethylene, propylene, butene, and butadiene, acetylene, propyne, and butyne. An unsaturated hydrocarbon having a triple bond, an aromatic hydrocarbon such as benzene, toluene, and xylene can be used. In addition, by-products such as carbon monoxide and a carbide furnace or a coke furnace containing carbon monoxide can also be used. If only carbon-containing materials are present, carbon nanofibers are likely to be produced. However, in reality, the reaction rate is significantly reduced unless a reducing gas such as H 2 coexists. This is considered to be because the deactivation of the catalyst is suppressed by the reducing action of the reducing gas. The carbon-containing compound may be further diluted with an inert gas such as nitrogen or argon. The temperature of the synthesis furnace is preferably 300 to 1000 ° C., and the pressure is preferably 0.01 MPa to 1 MPa. If the temperature is less than 300 ° C., more than 1000 ° C. or less than 0.01 MPa, the reaction hardly occurs, which is not preferable. A pressure of over 1 MPa is not preferable because the effect of improving the yield and physical properties is not remarkably recognized although the pressure resistance of the apparatus becomes complicated.
カーボンナノファイバーを生成する際、炭素含有化合物を導入する前に、予めカーボンナノファイバー生成用触媒の活性化を行うことが好ましい。具体的には、カーボンナノファイバー生成装置内にカーボンナノファイバー生成用触媒を担持したカーボンブラックを配置し、炉内をカーボンナノファイバーが生成する温度・圧力に調整した後に、Ｈ２などの還元性ガスを数分〜１時間程度装置内に導入して触媒表面から酸素又は水分を除去することによって、触媒を活性化する。その後炭素含有化合物を導入することにより、カーボンナノファイバーの生成が促進される。 When producing carbon nanofibers, it is preferable to activate the carbon nanofiber production catalyst in advance before introducing the carbon-containing compound. Specifically, carbon black carrying a catalyst for producing carbon nanofibers is placed in the carbon nanofiber production device, the temperature inside the furnace is adjusted to the temperature and pressure at which the carbon nanofibers are produced, and then reducing properties such as H 2 are reduced. The catalyst is activated by introducing gas into the apparatus for about several minutes to 1 hour to remove oxygen or moisture from the catalyst surface. Thereafter, by introducing a carbon-containing compound, the production of carbon nanofibers is promoted.
本発明の炭素材料を用いることで、従来のカーボンブラックやカーボンナノファイバーのみを用いた場合よりもレート特性、サイクル特性に優れた非水系二次電池を得ることができる。なお、一つの生成場でカーボンブラックとカーボンナノファイバーを同時に生成する方法、カーボンブラック生成場にカーボンナノファイバーを投入する方法では、本発明の構造を有する炭素材料を得ることは困難である。 By using the carbon material of the present invention, a non-aqueous secondary battery having excellent rate characteristics and cycle characteristics can be obtained as compared with the case of using only conventional carbon black or carbon nanofibers. Note that it is difficult to obtain a carbon material having the structure of the present invention by the method of simultaneously producing carbon black and carbon nanofibers in one production field and the method of introducing carbon nanofibers to the carbon black production field.
以下、実施例及び比較例により、本発明に係る炭素材料の製造方法を詳細に説明する。しかし、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 Hereinafter, the manufacturing method of the carbon material which concerns on this invention is demonstrated in detail by an Example and a comparative example. However, the present invention is not limited to the following examples unless it exceeds the gist.
［実施例１］
カーボンナノファイバー生成用触媒として酸化コバルト（Ｃｏ３Ｏ４）粉末（シグマアルドリッチ社製「６３７０２５」純度９９．８％、一次粒子径２０〜３０ｎｍ）２ｇをエタノール２００ｇ中に投入し、湿式ビーズミル（浅田鉄工社製「ＰＣＭ−ＬＲ」）にて１時間分散処理した。メディアビーズには直径０．３ｍｍのジルコニアビーズ１３０ｇを用いた。処理後のスラリーにカーボンブラック（比表面積３９ｍ２／ｇ、ＤＢＰ吸収量１４０ｍｌ／１００ｇ）３８ｇとエタノール７００ｇを投入し、撹拌羽根式の撹拌器にて混合し、その後、濾過・乾燥を行い、原料粉を得た。次に、得られた原料粉を石英ガラス製の反応容器内に充填し、カーボンナノファイバー生成装置内に装填した。装置内を真空雰囲気にした後、窒素ガスを充填して圧力を０．１ＭＰａとし、６００℃まで昇温した。次に、水素ガスで置換して３０分間保持した。次に、一酸化炭素ガスを５５体積％、水素ガスを２０体積％、窒素ガスを２５体積％の割合で混合した原料ガスを装置内に導入し、１時間保持した。その後、装置内を窒素ガスで置換して室温まで冷却し、装置を開放して反応容器から生成物を回収した。これらの生成条件を表１に示す。また、得られた炭素材料を透過型電子顕微鏡で観察した結果を図１に示す。
[Example 1]
As a catalyst for producing carbon nanofibers, 2 g of cobalt oxide (Co 3 O 4 ) powder (“637025” purity 99.8%, primary particle diameter 20-30 nm, manufactured by Sigma-Aldrich) was charged into 200 g of ethanol, and a wet bead mill (Asada Dispersion treatment was performed for 1 hour using “PCM-LR” manufactured by Iron Works. As media beads, 130 g of zirconia beads having a diameter of 0.3 mm were used. Carbon black (specific surface area 39 m 2 / g, DBP absorption 140 ml / 100 g) 38 g and ethanol 700 g are added to the treated slurry, mixed with a stirring blade type stirrer, then filtered and dried, I got a powder. Next, the obtained raw material powder was filled into a reaction vessel made of quartz glass and loaded into a carbon nanofiber generating apparatus. After the inside of the apparatus was evacuated, nitrogen gas was charged to a pressure of 0.1 MPa, and the temperature was raised to 600 ° C. Next, it was replaced with hydrogen gas and held for 30 minutes. Next, a raw material gas in which carbon monoxide gas was mixed at 55% by volume, hydrogen gas at 20% by volume, and nitrogen gas at 25% by volume was introduced into the apparatus and held for 1 hour. Thereafter, the inside of the apparatus was replaced with nitrogen gas and cooled to room temperature, the apparatus was opened, and the product was recovered from the reaction vessel. These generation conditions are shown in Table 1. Moreover, the result of having observed the obtained carbon material with the transmission electron microscope is shown in FIG.
生成物の評価方法を示す。
（１）カーボンブラックとカーボンナノファイバーからなる炭素材料の粒子径分布については、粒度分布測定装置（日機装社製「マイクロトラック粒度分布計ＭＴ３３００ＥＸII」「自動循環器ＳＤＣ」）を用い、以下の条件で測定した。
測定条件： 測定範囲／０．０２〜２０００μｍ、粒子透過性／吸収、粒子形状／非球形、溶媒／エタノール。
サンプル投入量： サンプル投入時に表示される最適濃度範囲になるように調整した。
分散条件： 測定前に「自動循環器ＳＤＣ」の超音波分散機能（出力４０Ｗ）で５分間処理した。
（２）カーボンナノファイバーの平均繊維径については、透過型電子顕微鏡（観察倍率１０万倍）から微細構造を観察し、繊維径を１００本測定し、その平均から算出した。
（３）カーボンナノファイバーの含有比率については、回収した生成物の質量から原料粉の質量を差し引き、生成したカーボンナノファイバーの質量を求め、算出した。
The evaluation method of a product is shown.
(1) About the particle size distribution of the carbon material consisting of carbon black and carbon nanofiber, using a particle size distribution measuring device ("Microtrack particle size distribution meter MT3300EXII""Automatic Circulator SDC" manufactured by Nikkiso Co., Ltd.) under the following conditions It was measured.
Measurement conditions: Measurement range / 0.02 to 2000 μm, particle permeability / absorption, particle shape / non-spherical, solvent / ethanol.
Sample input amount: The sample was adjusted so as to be in the optimum concentration range displayed at the time of sample input.
Dispersion condition: Before the measurement, the ultrasonic dispersion function (output 40 W) of the “automatic circulator SDC” was used for 5 minutes.
(2) About the average fiber diameter of carbon nanofiber, the fine structure was observed from the transmission electron microscope (observation magnification 100,000 times), 100 fiber diameters were measured, and it computed from the average.
(3) The content ratio of the carbon nanofibers was calculated by subtracting the mass of the raw material powder from the mass of the recovered product to determine the mass of the generated carbon nanofibers.
正極活物質のＬｉＦｅＰＯ４（Ｐｈｏｓｔｅｃｈ社製、一次粒子径５００ｎｍ）８０質量
％と、炭素材料１０質量％、結着剤のＰＶＤＦ（クレハ社製、ＫＦポリマー）１０質量％とを混合し混合物（合剤）とした。溶媒としてＮＭＰを添加し、プラネタリーミキサーを用いて、２０００ｒｐｍで１５分間混合し、合剤スラリーとした。この合剤スラリーを、厚さ２０μｍのアルミニウム箔（集電体）に塗布・乾燥し、その後、プレス・裁断して正極を作製した。対極として金属リチウムを用い、エチレンカーボネート／ジメチルカーボネートを１／１の容積比で混合した溶液に、過塩素酸リチウム１モル濃度を溶解させたものを電解液としてコイン形電池（ＣＲ２０３２）を作製した。
80% by mass of LiFePO 4 (manufactured by Phostech, primary particle size: 500 nm), 10% by mass of carbon material, and 10% by mass of PVDF (manufactured by Kureha Co., Ltd., KF polymer) as a binder were mixed to form a mixture (combination). Agent). NMP was added as a solvent and mixed for 15 minutes at 2000 rpm using a planetary mixer to obtain a mixture slurry. This mixture slurry was applied and dried on an aluminum foil (current collector) having a thickness of 20 μm, and then pressed and cut to produce a positive electrode. Using lithium metal as a counter electrode, a coin-type battery (CR2032) was prepared using a solution in which 1 mol of lithium perchlorate was dissolved in a mixed solution of ethylene carbonate / dimethyl carbonate at a volume ratio of 1/1. .
電池の放電試験として、電池を初充電後、充放電効率が１００％近傍になるのを確認後、０．７ｍＡ／ｃｍ２の電流密度にて定電流放電を２．１Ｖまで行った際の放電容量を測定し、正極活物質で除した容量密度（ｍＡｈ／ｇ）を算出した。この容量（ｍＡｈ／ｇ）を１時間で充放電可能な電流値を「１Ｃ」とした。レート特性は、４．１Ｖ（０．２Ｃ定電流）で充電し、０．２Ｃ、３Ｃで放電した際の放電容量を求め、０．２Ｃの放電容量に対する３Ｃの放電容量の比（％）をレート特性（容量維持率）とした。サイクル特性は、３Ｃで充放電を繰り返し、１サイクル目における放電容量に対する１５０サイクル目の放電容量の比（％）をサイクル特性（容量維持率）とした。評価結果を表１に示す。 As a battery discharge test, after confirming that the charge / discharge efficiency is close to 100% after the initial charge of the battery, the discharge is performed when constant current discharge is performed up to 2.1 V at a current density of 0.7 mA / cm 2. The capacity was measured, and the capacity density (mAh / g) divided by the positive electrode active material was calculated. The current value that can charge and discharge the capacity (mAh / g) in 1 hour was defined as “1C”. The rate characteristics are obtained by charging at 4.1 V (0.2 C constant current), discharging at 0.2 C and 3 C, and calculating the ratio (%) of 3 C discharge capacity to 0.2 C discharge capacity. Rate characteristics (capacity maintenance rate) were used. For the cycle characteristics, charge / discharge was repeated at 3C, and the ratio (%) of the discharge capacity at the 150th cycle to the discharge capacity at the first cycle was defined as the cycle characteristic (capacity maintenance ratio). The evaluation results are shown in Table 1.
［実施例２〜４、８、９］
カーボンナノファイバー生成用触媒の配合比率、分散方法、カーボンナノファイバーの合成条件を表１に示すように変えたこと以外は実施例１と同様にして炭素材料を得た。評価結果を表１に示す。
[Examples 2 to 4, 8, and 9]
A carbon material was obtained in the same manner as in Example 1 except that the compounding ratio of the carbon nanofiber production catalyst, the dispersion method, and the synthesis conditions of the carbon nanofiber were changed as shown in Table 1. The evaluation results are shown in Table 1.
［実施例５〜７］
用いる原料のカーボンブラックを表１に示すように変えたこと以外は実施例１と同様にして炭素材料を得た。評価結果を表２に示す。
[Examples 5 to 7]
A carbon material was obtained in the same manner as in Example 1 except that the raw material carbon black used was changed as shown in Table 1. The evaluation results are shown in Table 2.
［比較例１］
カーボンナノファイバー生成用触媒を用いないこと以外は実施例１と同様にして炭素材料を得た。評価結果を表１に示す。
[Comparative Example 1]
A carbon material was obtained in the same manner as in Example 1 except that the carbon nanofiber production catalyst was not used. The evaluation results are shown in Table 1.
［比較例２］
カーボンブラックを用いないこと以外は実施例１と同様にして炭素材料を得た。評価結果を表１に示す。また、得られた炭素材料を透過型電子顕微鏡で観察した結果を図２に示す。
[Comparative Example 2]
A carbon material was obtained in the same manner as in Example 1 except that carbon black was not used. The evaluation results are shown in Table 1. Moreover, the result of having observed the obtained carbon material with the transmission electron microscope is shown in FIG.
［比較例３〜９］
用いる原料のカーボンブラック、カーボンナノファイバー生成用触媒の配合比率、分散方法、カーボンナノファイバーの合成条件を表１に示すように変えたこと以外は実施例１と同様にして炭素材料を得た。評価結果を表１に示す。
[Comparative Examples 3 to 9]
A carbon material was obtained in the same manner as in Example 1, except that the raw material carbon black used, the blending ratio of the carbon nanofiber production catalyst, the dispersion method, and the carbon nanofiber synthesis conditions were changed as shown in Table 1. The evaluation results are shown in Table 1.
実施例と比較例から、本発明の炭素材料を用いたコイン形電池は、電池のレート特性とサイクル特性が優れている。また、炭素材料を透過型電子顕微鏡で撮影した、実施例１の図１と比較例２の図２から、本発明の炭素材料は凝集粒子が小さいことが示されている。 From the examples and comparative examples, the coin-type battery using the carbon material of the present invention is excellent in the rate characteristics and cycle characteristics of the battery. Further, FIG. 1 of Example 1 and FIG. 2 of Comparative Example 2 obtained by photographing the carbon material with a transmission electron microscope show that the carbon material of the present invention has small aggregated particles.
本発明の炭素材料は一次電池、二次電池、燃料電池、キャパシタなどの電池用導電材として利用することができる。
The carbon material of the present invention can be used as a conductive material for a battery such as a primary battery, a secondary battery, a fuel cell, and a capacitor.
Claims (5)
A nonaqueous secondary battery containing the carbon material according to claim 1 in a positive electrode .
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