JP2009084099A - Method for producing carbon material, carbon material, and negative electrode material for lithium-ion secondary batteries using the same - Google Patents
Method for producing carbon material, carbon material, and negative electrode material for lithium-ion secondary batteries using the same Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 18
- 239000007833 carbon precursor Substances 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 20
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000007600 charging Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- 229910021469 graphitizable carbon Inorganic materials 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 21
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
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- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
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- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、炭素材の製造方法、炭素材及びこれを用いたリチウムイオン二次電池用負極材に関するものである。 The present invention relates to a carbon material production method, a carbon material, and a negative electrode material for a lithium ion secondary battery using the carbon material.
現在、リチウムイオン二次電池の負極に使用されている材料としては、主として天然グラファイト及び人造グラファイトが挙げられる。これらの材料の特徴は充放電効率が９０％以上と高いこと、真密度が難黒鉛化炭素材と比較して高いことなどから電極密度を高く高エネルギー化し易いなどの点がある。しかし、グラフファイト系炭素材料には理論充放電容量が存在し（３７２ｍＡｈ／ｇ）、二次電池のエネルギー密度を向上させるためには電極密度、充放電効率の更なる向上が必須とされている。
グラファイトに関しては、電極密度を向上させるために様々な検討がなされており、例えば、燐片状、ミルド状及び球状などのさまざまな形状による検討がなされている。さらに、充放電効率を高めるなどの検討もなされているが（例えば、特許文献１、非特許文献１参照。）、更なる検討が必要とされている。
また、難黒鉛化材などにも同様な検討がされているが、難黒鉛化材は黒鉛よりも、重量当りの放電容量は高いものの炭素材自身の真密度が低いこと、充放電効率が低いなどのことから体積当りの放電容量が低くなってしまうのが現状である（例えば、特許文献２参照。）。また、炭素質材料において低温で焼成された易黒鉛化材なども初期の放電容量は高いものの、初期充放電効率、サイクル性などに難を抱えており、難黒鉛化材も、易黒鉛化材も初期充放電効率、放電容量、サイクル性、負荷特性などのバランスを取ろうとすると、容量が黒鉛系材料と同等、もしくは小さくなってしまうのが欠点であった。
Currently, materials used for the negative electrode of lithium ion secondary batteries mainly include natural graphite and artificial graphite. The characteristics of these materials are that the charge / discharge efficiency is as high as 90% or more, and the true density is higher than that of the non-graphitizable carbon material. However, the graphite-based carbon material has a theoretical charge / discharge capacity (372 mAh / g), and in order to improve the energy density of the secondary battery, further improvements in electrode density and charge / discharge efficiency are essential. .
Regarding graphite, various studies have been made to improve the electrode density. For example, various shapes such as flakes, milleds, and spheres have been studied. Further studies have been made to increase the charge / discharge efficiency (see, for example, Patent Document 1 and Non-Patent Document 1), but further studies are required.
The same study has been made on non-graphitized materials, but non-graphitized materials have a higher discharge capacity per weight than graphite, but the carbon material itself has a lower true density and lower charge / discharge efficiency. The current situation is that the discharge capacity per volume becomes low (for example, see Patent Document 2). In addition, graphitized materials baked at low temperatures in carbonaceous materials have high initial discharge capacities, but have difficulties in initial charge and discharge efficiency, cycleability, etc. However, when trying to balance the initial charge / discharge efficiency, discharge capacity, cycle performance, load characteristics, etc., the capacity is equal to or smaller than that of the graphite-based material.
本発明は、電極とした場合、充放電特性、サイクル性及び負荷特性に優れた炭素材及びこれを用いたリチウムイオン二次電池用負極材を提供するものである。 The present invention provides a carbon material excellent in charge / discharge characteristics, cycle performance and load characteristics, and a negative electrode material for a lithium ion secondary battery using the same when used as an electrode.
即ち、本発明は下記第（１）項〜第（９）項により達成される。
（１） 難黒鉛性炭素源を炭化して得られる炭素材の製造方法であって、
前記難黒鉛性炭素源を用いて、第１の加熱を行い、炭素前駆体を得る第１の熱処理工程、
及び前記炭素前駆体を用いて、第２の加熱を行い、炭素材を得る第２の熱処理工程、
を含むことを特徴とする炭素材の製造方法。
（２） 前記炭素前駆体は、炭素：水素の元素比が７：３〜９：１で構成されるものである第（１）項に記載の炭素材の製造方法。
（３） 前記炭素材は、炭素：水素の元素比が９５：５〜９９．７：０．３で構成されるものである第（１）項又は第（２）項に記載の炭素材の製造方法。
（４） 前記炭素前駆体と炭素材は、温度４０℃相対湿度９０％の雰囲気中で１４４時間放置した後に、前記炭素前駆体の重量増加と前記炭素材の重量増加との比が、５：５〜９：１となるものである第（１）項〜第（３）項のいずれか１項に記載の炭素材の製造方法。
（５） 前記炭素前駆体及び炭素材は、０．１〜７μｍの平均粒子径を有するものである第（１）項〜第（４）項のいずれか１項に記載の炭素材の製造方法。
（６） 前記炭素前駆体は、１０〜８５ｍ2／ｇのＢＥＴ比表面積を有するものである第（１）項〜第（５）項のいずれか１項に記載の炭素材の製造方法。
（７） 第（１）項〜第（６）項のいずれか１項に記載の炭素材の製造方法によって得られる炭素材。
（８） 前記炭素材は、１〜１０ｍ2／ｇのＢＥＴ比表面積を有するものである第（７）項に記載の炭素材。
（９） 第（７）項又は第（８）項に記載の炭素材を含むことを特徴とするリチウムイオン二次電池用負極材。
That is, the present invention is achieved by the following items (1) to (9).
(1) A method for producing a carbon material obtained by carbonizing a non-graphitizable carbon source,
A first heat treatment step of obtaining a carbon precursor by performing a first heating using the non-graphitizable carbon source;
And a second heat treatment step for obtaining a carbon material by performing a second heating using the carbon precursor,
The carbon material manufacturing method characterized by including.
(2) The said carbon precursor is a manufacturing method of the carbon material as described in the (1) term whose element ratio of carbon: hydrogen is comprised by 7: 3-9: 1.
(3) The carbon material according to (1) or (2), wherein the carbon: hydrogen element ratio is 95: 5 to 99.7: 0.3. Production method.
(4) After the carbon precursor and the carbon material are allowed to stand for 144 hours in an atmosphere of a temperature of 40 ° C. and a relative humidity of 90%, the ratio of the increase in the weight of the carbon precursor to the increase in the weight of the carbon material is 5: The method for producing a carbon material according to any one of (1) to (3), which is 5 to 9: 1.
(5) The method for producing a carbon material according to any one of (1) to (4), wherein the carbon precursor and the carbon material have an average particle diameter of 0.1 to 7 μm. .
(6) The method for producing a carbon material according to any one of (1) to (5), wherein the carbon precursor has a BET specific surface area of 10 to 85 m 2 / g.
(7) A carbon material obtained by the method for producing a carbon material according to any one of items (1) to (6).
(8) The carbon material according to item (7), wherein the carbon material has a BET specific surface area of 1 to 10 m 2 / g.
(9) A negative electrode material for a lithium ion secondary battery, comprising the carbon material according to (7) or (8).
本発明によれば、電極とした場合、充放電特性、サイクル性、負荷特性に優れた炭素材を得ることができる。本発明の炭素材を、特に、リチウムイオン二次電池負極材電極として用いた場合に、電極に活物質を高密度に充填することが可能であり、電極の薄膜化、低抵抗化、電極密度を優れたものにすることができ、単位体積当たり・単位重量当たりの二次電池の容量・出力を高めることができる。 According to this invention, when it is set as an electrode, the carbon material excellent in charging / discharging characteristics, cycling characteristics, and load characteristics can be obtained. In particular, when the carbon material of the present invention is used as a negative electrode material for a lithium ion secondary battery, it is possible to fill the electrode with an active material at a high density. And the capacity and output of the secondary battery per unit volume / unit weight can be increased.
本発明は、難黒鉛性炭素源を炭化して得られる炭素材の製造方法であって、前記難黒鉛性炭素源を用いて、第１の加熱を行い、炭素前駆体を得る第１の熱処理工程、及び前記炭素前駆体を用いて、第２の加熱を行い、炭素材を得る第２の熱処理工程、を含むことを特徴とする炭素材の製造方法である。これにより、電極とした場合、充放電特性、サイクル性及び負荷特性に優れた炭素材を得ることができ、上記で得た炭素材を、リチウムイオン二次電池用負極材に用いた場合、電極に活物質として高密度に充填することができ、また、これを用いることにより単位体積当たり・単位重量当たりの放電容量が高いリチウムイオン二次電池用負極材を得ることができる。 The present invention is a method for producing a carbon material obtained by carbonizing a non-graphitizable carbon source, wherein the first heat treatment is performed using the non-graphitic carbon source to obtain a carbon precursor. And a second heat treatment step of performing a second heating using the carbon precursor to obtain a carbon material. Thereby, when it is set as an electrode, a carbon material excellent in charge / discharge characteristics, cycle performance and load characteristics can be obtained. When the carbon material obtained above is used for a negative electrode material for a lithium ion secondary battery, the electrode In addition, it is possible to obtain a negative electrode material for a lithium ion secondary battery having a high discharge capacity per unit volume and unit weight.
本発明に用いる難黒鉛性炭素源としては、フェノール樹脂、メラミン樹脂、ケトン樹脂、アミノ樹脂及びアミド樹脂などのアルデヒド樹脂、エポキシ樹脂、ウレタン樹脂、ユリア樹脂、ジアリルフタレート樹脂、ポリエステル樹脂、ポリカーボーネート樹脂、シリコン樹脂、ポリアセタール樹脂及びナイロン樹脂等の熱硬化性樹脂、などが挙げられ、これらの難黒鉛性炭素源は１種又は２種以上が用いられる。また難黒鉛性炭素源として、さらに、上記難黒鉛性炭素源には、添加剤を含んでいてもよい。前記添加剤としては、前記樹脂に対する硬化剤及び硬化触媒などが挙げられ、例えば、フェノール樹脂として、ノボラック型フェノール樹脂を用いる場合は、前記硬化剤として、ヘキサメチレンテトラミン、トリオキサン及びパラホルムアルデヒド等のアルデヒド源、アミン系硬化剤、イミダゾール系硬化剤などが挙げられる。前記熱硬化性樹脂は硬化剤などを加えることにより、第１の熱処理の前に予め硬化させて用いても良い。 Examples of the non-graphitizable carbon source used in the present invention include phenol resins, melamine resins, ketone resins, amino resins and amide resins, aldehyde resins, epoxy resins, urethane resins, urea resins, diallyl phthalate resins, polyester resins, and polycarbonates. Examples thereof include thermosetting resins such as resins, silicon resins, polyacetal resins, and nylon resins, and one or more of these non-graphitizable carbon sources are used. Further, as the non-graphitic carbon source, the non-graphitic carbon source may further contain an additive. Examples of the additive include a curing agent and a curing catalyst for the resin. For example, when a novolac type phenol resin is used as a phenol resin, an aldehyde such as hexamethylenetetramine, trioxane, and paraformaldehyde is used as the curing agent. Source, amine curing agent, imidazole curing agent and the like. The thermosetting resin may be used by being cured in advance before the first heat treatment by adding a curing agent or the like.
次に、本発明の炭素材の製造方法について、具体的に説明するが、本発明はこれらに限定されない。
本発明の炭素材の製造方法は、前記難黒鉛性炭素源を用いて、炭素前駆体を得る第１の熱処理工程、及び前記炭素前駆体を用いて、炭素材を得る第２の熱処理工程、を含むものである。
Next, although the manufacturing method of the carbon material of this invention is demonstrated concretely, this invention is not limited to these.
The method for producing a carbon material of the present invention includes a first heat treatment step for obtaining a carbon precursor using the non-graphitizable carbon source, and a second heat treatment step for obtaining a carbon material using the carbon precursor, Is included.
本発明における炭素前駆体とは、第一の熱処理により得られる炭素を指し、炭素中間体を意味する。前記炭素前駆体としては炭素：水素の元素比が７：３〜９：１の元素組成を有することが好ましい。 The carbon precursor in the present invention refers to carbon obtained by the first heat treatment, and means a carbon intermediate. The carbon precursor preferably has an elemental composition with a carbon: hydrogen element ratio of 7: 3 to 9: 1.
まず、第１の熱処理工程について説明する。
前記第１の熱処理工程においては、前記難黒鉛性炭素源を、第１の熱処理を行うことにより、炭素前駆体を得るが、第１の熱処理条件としては、例えば、熱処理温度として、４００〜８００℃の温度範囲が好ましく、さらに好ましくは４００〜６００℃の温度範囲である。これらの温度は、第１の熱処理における最終到達温度（保持温度）である。また、前記熱処理時間として、通常、最終熱処理温度まで１〜５０時間で行うことができる。
また、第１の熱処理における雰囲気としては、大気中、水素ガス、窒素ガス、ヘリウムガス及びアルゴンガスなどの不活性ガス雰囲気中、並びに、真空中など、いずれであっても良く、また、これらの２種以上の雰囲気中で熱処理を行うことができる。これらの中でも、良好な充放電特性を発現する炭素材を効率よく製造する上で、不活性ガス雰囲気中で行うことが好ましい。
First, the first heat treatment step will be described.
In the first heat treatment step, a carbon precursor is obtained by performing the first heat treatment on the non-graphitizable carbon source. As the first heat treatment condition, for example, a heat treatment temperature is 400 to 800. A temperature range of ° C. is preferred, and a temperature range of 400 to 600 ° C. is more preferred. These temperatures are final reached temperatures (holding temperatures) in the first heat treatment. Moreover, as said heat processing time, it can carry out normally in 1 to 50 hours to the final heat processing temperature.
In addition, the atmosphere in the first heat treatment may be any of air, an inert gas atmosphere such as hydrogen gas, nitrogen gas, helium gas, and argon gas, and a vacuum. Heat treatment can be performed in two or more atmospheres. Among these, it is preferable to carry out in an inert gas atmosphere in order to efficiently produce a carbon material that exhibits good charge / discharge characteristics.
前記難黒鉛性炭素源が、揮発分を含む場合は、前記第１の熱処理の前に、前記炭素源が炭素化せず、前記揮発分が揮散する温度で揮発分を除去する工程を行うことが好ましい。 When the non-graphitizable carbon source contains a volatile component, a step of removing the volatile component at a temperature at which the carbon source is not carbonized and the volatile component is volatilized is performed before the first heat treatment. Is preferred.
このようにして得られる炭素前駆体は、炭素：水素の元素比が７：３〜９：１で構成されるものであることが好ましい。
このような元素比となることにより、炭素前駆体及び炭素材の吸湿率、比表面積、細孔構造の制御がし易くなり、充放電特性、サイクル性及び負荷特性に優れた炭素材を得ることができる。
The carbon precursor thus obtained is preferably one having a carbon: hydrogen element ratio of 7: 3 to 9: 1.
By becoming such an element ratio, it becomes easy to control the moisture absorption rate, specific surface area, and pore structure of the carbon precursor and the carbon material, and obtain a carbon material excellent in charge / discharge characteristics, cycle performance and load characteristics. Can do.
また、前記炭素前駆体の吸湿率としては、０．１〜１０％が好ましく、０．１〜５％がより好ましい。該吸湿率は低いほど好ましいが、前記範囲とすることにより、前記炭素前駆体における炭素の割合が多くなり、良好な充放電特性をもつ炭素材を得ることができる。 Moreover, as a moisture absorption rate of the said carbon precursor, 0.1 to 10% is preferable and 0.1 to 5% is more preferable. The lower the moisture absorption rate, the better. However, by setting the moisture absorption rate within the above range, the carbon ratio in the carbon precursor increases and a carbon material having good charge / discharge characteristics can be obtained.
さらに、炭素材を得る第２の熱処理工程に用いる炭素前駆体としては、１０〜８５ｍ2／ｇのＢＥＴ比表面積を有することが好ましく、２０〜６０ｍ2／ｇであることがより好ましい。このようなＢＥＴ比表面積とすることにより、上記吸湿率を制御し易くなると共に、第２の熱処理を行い得られた炭素材のＢＥＴ比表面積を制御することができ、炭素材の品質を安定化することができる。炭素材の品質を安定化することは二次電池の品質・設計を簡略化することに繋がり、また、二次電池の製品品質を安定化することができ、非常に有用である。 Further, as the carbon precursor used in the second heat treatment step of obtaining a carbon material preferably has a BET specific surface area of 10~85m 2 / g, more preferably 20~60m 2 / g. By adopting such a BET specific surface area, the moisture absorption rate can be easily controlled, and the BET specific surface area of the carbon material obtained by performing the second heat treatment can be controlled to stabilize the quality of the carbon material. can do. Stabilizing the quality of the carbon material leads to simplification of the quality and design of the secondary battery, and can stabilize the product quality of the secondary battery, which is very useful.
前記炭素前駆体におけるＢＥＴ比表面積の調整方法としては、粉砕による方法が挙げられる。粉砕方法の具体例としては、ボールミル、ジェットミル、乾式ビーズミルなど粉砕装置を用いた方法が挙げられるが、粒子形状や均一な粒度分布が得られることから、ボールミルによる粉砕が好ましい。
また、上記粉砕により得られる炭素前駆体の平均粒子径は０．１〜７μｍであることが好ましく、更に好ましくは３〜５μｍである。前記平均粒子径は、炭素材の平均粒子径に相当するものとなる。このような粒子径とすることにより、第２の熱処理を行った場合に炭素材の炭化度を均一化することができ、負極材として用いた場合、電極密度を大きく向上させることができると共に、電極の薄膜化及び抵抗値を低下させることができる。
Examples of the method for adjusting the BET specific surface area in the carbon precursor include a method by pulverization. Specific examples of the pulverization method include a method using a pulverizer such as a ball mill, a jet mill, and a dry bead mill. However, pulverization by a ball mill is preferable because a particle shape and a uniform particle size distribution can be obtained.
Moreover, it is preferable that the average particle diameter of the carbon precursor obtained by the said grinding | pulverization is 0.1-7 micrometers, More preferably, it is 3-5 micrometers. The average particle diameter corresponds to the average particle diameter of the carbon material. By using such a particle size, the carbonization degree of the carbon material can be made uniform when the second heat treatment is performed, and when used as a negative electrode material, the electrode density can be greatly improved, It is possible to reduce the thickness of the electrode and the resistance value.
本発明におけるＢＥＴ法による比表面積は、本発明で得られる炭素前駆体及び炭素材を、ＢＥＴ３点法（０．０５＜Ｐ／Ｐｏ＜０．３５）により測定することにより得ることができる。
具体的な算出法としては、下記（１）式より単分子吸着量Ｗｍを算出し、下記（２）式より総表面積Ｓｔｏｔａｌを算出し、下記（３）式より比表面積Ｓを求めた。
１／［Ｗ（Ｐｏ／Ｐ−１）＝（Ｃ−１）／ＷｍＣ（Ｐ／Ｐｏ）／ＷｍＣ・・（１）
式（１）中、Ｐ：吸着平衡にある吸着質の気体の圧力、Ｐｏ：吸着温度における吸着質の飽和蒸気圧、Ｗ：吸着平衡圧Ｐにおける吸着量、Ｗｍ：単分子層吸着量、Ｃ：固体表面と吸着質との相互作用の大きさに関する定数（Ｃ＝ｅｘｐ｛（Ｅ１−Ｅ２）ＲＴ｝）［Ｅ１：第一層の吸着熱（ｋＪ／ｍｏｌ）、Ｅ２：吸着質の測定温度における液化熱（ｋＪ／ｍｏｌ）］
Ｓｔｏｔａｌ＝（ＷｍＮＡｃｓ）Ｍ・・・・・・・・・（２）
式（２）中、Ｎ：アボガドロ数、Ｍ：分子量、Ａｃｓ：吸着断面積
Ｓ＝Ｓｔｏｔａｌ／ｗ・・・・・・（３）
式（３）中、ｗ：サンプル重量（ｇ）
The specific surface area by the BET method in the present invention can be obtained by measuring the carbon precursor and carbon material obtained in the present invention by the BET three-point method (0.05 <P / Po <0.35).
As a specific calculation method, the monomolecular adsorption amount Wm was calculated from the following formula (1), the total surface area Total was calculated from the following formula (2), and the specific surface area S was calculated from the following formula (3).
1 / [W (Po / P-1) = (C-1) / WmC (P / Po) / WmC (1)
In the formula (1), P: pressure of the adsorbate gas in the adsorption equilibrium, Po: saturated vapor pressure of the adsorbate at the adsorption temperature, W: adsorption amount at the adsorption equilibrium pressure P, Wm: monomolecular layer adsorption amount, C : Constant on the magnitude of the interaction between the solid surface and the adsorbate (C = exp {(E1-E2) RT}) [E1: heat of adsorption of the first layer (kJ / mol), E2: measurement temperature of the adsorbate Liquefaction heat (kJ / mol)]
Total = (WmNAcs) M (2)
In the formula (2), N: Avogadro number, M: molecular weight, Acs: adsorption cross section S = Total / w (3)
In formula (3), w: sample weight (g)
本発明における平均粒子径は、上記工程（ｂ）を経た炭素材前駆体、後述の工程（ｃ）を経た炭素材について、レーザー回折散乱方式により測定することができ、例えば、堀場製作所社製レーザー回折ＬＡ−９２０を用いて測定することができる。 The average particle diameter in the present invention can be measured by the laser diffraction scattering method for the carbon material precursor that has undergone the above step (b) and the carbon material that has undergone the following step (c). For example, a laser manufactured by Horiba, Ltd. It can be measured using diffraction LA-920.
本発明における吸湿率は、本発明で得られる炭素前駆体及び炭素材を、それぞれ５ｇ秤量した後、温度４０℃、湿度９０％の雰囲気中に、１４４ｈ放置した。その後、重量を測定し、下記の式により重量増加率を算出することができる。
重量増加率（％）＝１４４ｈ後重量（ｇ）／初期重量（ｇ）×１００
The moisture absorption in the present invention was determined by weighing 5 g of the carbon precursor and carbon material obtained in the present invention, respectively, and then leaving them for 144 hours in an atmosphere at a temperature of 40 ° C. and a humidity of 90%. Thereafter, the weight is measured, and the weight increase rate can be calculated by the following formula.
Weight increase rate (%) = weight after 144 h (g) / initial weight (g) × 100
次に、第２の熱処理工程について説明する。
前記第２の熱処理工程においては、前記炭素前駆体を用いて、第２の熱処理を行うことにより、炭素材を得るが、第２の熱処理条件としては、例えば、熱処理温度として、８００℃〜１４００℃の温度範囲が好ましく、さらに好ましくは１０００〜１３００℃の温度範囲である。これらの温度は、第２の熱処理における最終到達温度（保持温度）である。
また、上記第２の熱処理温度にする上で、通常、５０〜２００℃／時の昇温速度により加熱して行うことができる。第２の熱処理後の冷却においては、冷却速度について、特に限定されないが、通常、５０〜４００℃／時で冷却を行うことができる。
また、前記熱処理時間として、通常、前記保持温度において、１〜１５時間で行うことができる。
また、第２の熱処理における雰囲気としては、一酸化炭素ガス、窒素ガス、ヘリウムガス、微量の水素と酸素の混合ガスなどの不活性ガス雰囲気中が好ましく、また、これらの２種以上の雰囲気中で熱処理を行うことができる。
なお、第２の熱処理後に、不活性雰囲気を開放する際は、第２の熱処理工程において製造された炭素材が空気中の酸素と反応しない温度、すなわち室温〜１００℃の温度範囲で開放することが好ましい。
Next, the second heat treatment step will be described.
In the second heat treatment step, a carbon material is obtained by performing the second heat treatment using the carbon precursor. The second heat treatment condition is, for example, a heat treatment temperature of 800 ° C. to 1400 ° C. A temperature range of ° C. is preferable, and a temperature range of 1000 to 1300 ° C. is more preferable. These temperatures are final reached temperatures (holding temperatures) in the second heat treatment.
Moreover, when setting it as the said 2nd heat processing temperature, it can carry out by heating with the temperature increase rate of 50-200 degreeC / hour normally. In the cooling after the second heat treatment, the cooling rate is not particularly limited, but the cooling can usually be performed at 50 to 400 ° C./hour.
Moreover, as said heat processing time, it can carry out normally in the said holding temperature in 1 to 15 hours.
Further, the atmosphere in the second heat treatment is preferably an inert gas atmosphere such as carbon monoxide gas, nitrogen gas, helium gas, and a mixed gas of a trace amount of hydrogen and oxygen, and in these two or more atmospheres. Heat treatment can be performed.
When the inert atmosphere is released after the second heat treatment, the carbon material produced in the second heat treatment step is opened at a temperature at which it does not react with oxygen in the air, that is, in a temperature range of room temperature to 100 ° C. Is preferred.
このようにして得られる炭素材は、炭素：水素の元素比が９５：５〜９９．７：０．３で構成されるものであることが好ましい。
このような元素比となることにより、炭素材の比表面積をより小さくすることができ、また、均一な細孔構造となり、前記炭素材を電極に用いた場合、充放電特性、サイクル性及び負荷特性に優れた炭素材を得ることができる。
It is preferable that the carbon material obtained in this way is composed of a carbon: hydrogen element ratio of 95: 5 to 99.7: 0.3.
By using such an element ratio, the specific surface area of the carbon material can be further reduced, and a uniform pore structure is obtained. When the carbon material is used for an electrode, charge / discharge characteristics, cycle performance and load A carbon material having excellent characteristics can be obtained.
また、上記で得られた前記炭素前駆体と炭素材は、温度４０℃相対湿度９０％の雰囲気中で１４４時間放置した後に、前記炭素前駆体の重量増加と前記炭素材の重量増加との比が、５：５〜９：１となることが好ましい。 The carbon precursor and the carbon material obtained above are left in an atmosphere at a temperature of 40 ° C. and a relative humidity of 90% for 144 hours, and then the ratio of the weight increase of the carbon precursor to the weight increase of the carbon material. Is preferably 5: 5 to 9: 1.
本発明においては、前記炭素前駆体における吸湿率が低く、さらには前記炭素前駆体の重量増加と前記炭素材の重量増加との比において、より小さい方がより好ましい。これにより、充放電特性の高い負極材となる、良好な炭素材を得ることができる。
また、このような炭素材を用いると二次電池において正極材であるＬｉ複合金属や電解液の分解を引き起こし難く、良好な二次電池の特性を発現することができる。
In the present invention, the moisture absorption rate of the carbon precursor is low, and it is more preferable that the ratio of the increase in the weight of the carbon precursor and the increase in the weight of the carbon material is smaller. Thereby, the favorable carbon material used as a negative electrode material with a high charging / discharging characteristic can be obtained.
Further, when such a carbon material is used, it is difficult to cause decomposition of the Li composite metal that is the positive electrode material or the electrolytic solution in the secondary battery, and good secondary battery characteristics can be exhibited.
さらに、炭素材は、１〜１０ｍ2／ｇのＢＥＴ比表面積を有することが好ましく、３〜７ｍ2／ｇであることがより好ましい。このようなＢＥＴ比表面積とすることにより、前記炭素材をリチウムイオン二次電池用負極材に用いた場合、充放電特性およびサイクル性、負荷特性を更に優れたものにすることができる。 Further, the carbon material preferably has a BET specific surface area of 1 to 10 m 2 / g, more preferably 3~7m 2 / g. By setting it as such a BET specific surface area, when the said carbon material is used for the negative electrode material for lithium ion secondary batteries, a charge / discharge characteristic, cycling property, and a load characteristic can be made further excellent.
上気で得られた炭素材はリチウムイオン二次電池用負極材、電気二重層キャパシタ用電極材として用いることができる。 The carbon material obtained in the upper air can be used as a negative electrode material for lithium ion secondary batteries and an electrode material for electric double layer capacitors.
本発明の炭素材を用いたリチウムイオン二次電池用負極材電極としては、前記炭素材、結着剤及び導電剤などを含む負極材用組成物を用いて作製することができる。前記結着剤及び導電剤の量は特に限定されないが、通常、炭素材に対して１〜１０重量％用いることができる。結着剤については好ましくは１〜１５重量％が好ましく、さらに好ましくは３〜１０重量％である。前記範囲外でも使用できるが、結着剤量が、多すぎると、電極の抵抗が上がり電極として好ましくなくなる恐れがあり、少なすぎると、焦電体との密着性が低下することがあり、この場合、二次電池において、充放電を繰り返すにつれて炭素材が焦電体から剥れを生じことにより、短絡などの原因となる恐れがある。導電剤量については、好ましくは１〜１０％が好ましく、さらに好ましくは３〜７％が好ましい。前記範囲外でも使用できるが、導電剤量が多すぎると、電極中の炭素材量が減少し、電極として、体積当りの容量が低下する恐れがあり、導電剤量が少なすぎると、電極の抵抗が上がる恐れがある。 The negative electrode material electrode for a lithium ion secondary battery using the carbon material of the present invention can be prepared using the negative electrode material composition containing the carbon material, a binder, a conductive agent, and the like. Although the amount of the binder and the conductive agent is not particularly limited, it can usually be used in an amount of 1 to 10% by weight based on the carbon material. The binder is preferably 1 to 15% by weight, more preferably 3 to 10% by weight. Although it can be used outside the above range, if the amount of the binder is too large, the resistance of the electrode may increase and it may become unpreferable as an electrode, and if it is too small, the adhesion with the pyroelectric material may be reduced. In such a case, in the secondary battery, the carbon material may be peeled off from the pyroelectric body as charging and discharging are repeated, which may cause a short circuit. The amount of the conductive agent is preferably 1 to 10%, more preferably 3 to 7%. Although it can be used outside the above range, if the amount of the conductive agent is too large, the amount of the carbon material in the electrode decreases, and the capacity per volume as the electrode may be reduced. If the amount of the conductive agent is too small, Resistance may increase.
本発明のリチウムイオン二次電池用負極材を用いた二次電池用電極の製造方法としては、前記結着剤と、活物質として前記炭素材と、更に導電剤を、適量秤量し、前記極性溶媒中で混合して、所定の粘度のスラリーとした後、これを、集電体用金属箔上に塗布する。前記極性溶媒としては、一般的にはＮ−メチルピロリドンなどが挙げられ、さらに、これに、メタノールおよびアセトニトリルなどの溶媒を添加することができるが、特に限定されない。また、これらを単独、もしくは２種以上併用しても良い。
そして、炭素材を固定化するために、前記極性溶媒を除去する工程として、５０〜２００℃で熱処理を行う。熱処理の時間は特に限定されないが、炭素材が酸化されず、極性溶媒が除去できる温度、時間で行うことが好ましい。
前記集電体用金属箔としては、銅箔などが挙げられる。
As a method for producing an electrode for a secondary battery using the negative electrode material for a lithium ion secondary battery of the present invention, an appropriate amount of the binder, the carbon material as an active material, and a conductive agent are weighed, and the polarity After mixing in a solvent to obtain a slurry having a predetermined viscosity, this is applied onto a metal foil for a current collector. As said polar solvent, N-methylpyrrolidone etc. are mentioned generally, Furthermore, although solvents, such as methanol and acetonitrile, can be added to this, it is not specifically limited. These may be used alone or in combination of two or more.
And in order to fix a carbon material, it heat-processes at 50-200 degreeC as a process of removing the said polar solvent. Although the heat treatment time is not particularly limited, it is preferably performed at a temperature and time at which the carbon material is not oxidized and the polar solvent can be removed.
Examples of the current collector metal foil include copper foil.
さらに、二次電池用電極の製造方法の具体例としては、負極の場合、集電体用金属箔として厚み２０μｍ程度の銅箔の所定の位置に、前記二次電池電極用スラリーを、ドクターブレード又はアプリケーターを用いて、均一に塗布して塗膜を形成し、次いで、前記塗膜を乾燥し、ロールプレス機で圧縮成形することにより得られる。 Further, as a specific example of the method for manufacturing the secondary battery electrode, in the case of the negative electrode, the slurry for the secondary battery electrode is placed on a predetermined position of a copper foil having a thickness of about 20 μm as the metal foil for the current collector. Or using an applicator, it coats uniformly and forms a coating film, Then, the said coating film is dried, It obtains by compression-molding with a roll press machine.
以下、本発明を実施例により説明する。しかし、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the examples.
得られた炭素前駆体及び炭素材の測定方法は、次のようにして行なった。
（１）吸湿率：前記方法により測定した。
（２）ＢＥＴ比表面積：ユアサ社製Ｎｏｖａ−１２００を用いて、前記ＢＥＴ法による比表面積の測定方法により測定した。
（３）平均粒子径：堀場製作所社製レーザー回折ＬＡ−９２０を用いて、レーザー回折散乱方式により測定した。
（４）炭素：水素比：得られた炭素前駆体、炭素材を、１１０℃／真空中、３時間乾燥処理後、パーキンエルナー社製元素分析測定装置を用い、炭素、水素の組成比を測定した。
The measurement method of the obtained carbon precursor and carbon material was performed as follows.
(1) Moisture absorption: measured by the above method.
(2) BET specific surface area: Measured by a specific surface area measurement method by the BET method using Nova-1200 manufactured by Yuasa Corporation.
(3) Average particle diameter: Measured by a laser diffraction scattering method using a laser diffraction LA-920 manufactured by Horiba, Ltd.
(4) Carbon: hydrogen ratio: After the obtained carbon precursor and carbon material are dried at 110 ° C./vacuum for 3 hours, the composition ratio of carbon and hydrogen is measured using an elemental analysis measuring device manufactured by Perkin Elner. did.
（実施例１）
ノボラック型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５０３９５」）１０００重量部に対してヘキサメチレンテトラミンを１００重量部加え均一に混合した後、工程（ａ）の第１の熱処理として電気炉中１３０℃で３時間、熱処理を行いながら硬化処理を行った。その後、電気炉にて４００℃まで１００℃／時で昇温し、４００℃で３時間保持後、室温まで冷却し炭素前駆体を得た。その後、工程（ｂ）の処理として静置型ボールミルを用いて平均粒子径が５．２μｍになるまで粉砕を行い粉末状の炭素前駆体を得た。この炭素前駆体の吸湿率は７％、ＢＥＴ比表面積は３５．２２ｍ2／ｇ、炭素：水素＝７９：２１であった。
得られた粉末状の炭素前駆体を、工程（ｃ）の第２の熱処理として窒素雰囲気下にて１００℃／時で昇温して、１１００℃に到達した後、３時間維持して炭素材を得た。得られた炭素材のＢＥＴ比表面積は６．５ｍ2／ｇ、吸湿率は１．７％、炭素：水素＝９９．２：０．８であった。
Example 1
After adding 100 parts by weight of hexamethylenetetramine to 1000 parts by weight of novolak-type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-50395”) and mixing them uniformly, as the first heat treatment in step (a), in an electric furnace Curing was performed while performing heat treatment at 130 ° C. for 3 hours. Thereafter, the temperature was raised to 400 ° C. at 100 ° C./hour in an electric furnace, kept at 400 ° C. for 3 hours, and then cooled to room temperature to obtain a carbon precursor. Then, it grind | pulverized until the average particle diameter was set to 5.2 micrometers using the stationary ball mill as a process of a process (b), and the powdery carbon precursor was obtained. The carbon precursor had a moisture absorption rate of 7%, a BET specific surface area of 35.22 m 2 / g, and carbon: hydrogen = 79: 21.
The obtained powdery carbon precursor was heated at 100 ° C./hour in a nitrogen atmosphere as the second heat treatment in step (c), reached 1100 ° C., and then maintained for 3 hours to obtain a carbon material. Got. The obtained carbon material had a BET specific surface area of 6.5 m 2 / g, a moisture absorption rate of 1.7%, and carbon: hydrogen = 99.2: 0.8.
（実施例２）
ノボラック型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５０３９５」）１０００重量部に対してヘキサメチレンテトラミンを１００重量部加え均一に混合した後、工程（ａ）の第１の熱処理として電気炉中１３０℃で３時間、熱処理を行いながら硬化処理を行った。その後、電気炉にて４００℃まで１００℃／時で昇温し、４００℃で６時間保持後、室温まで冷却し炭素前駆体を得た（平均粒子径５．３μｍ）。この炭素前駆体の吸湿率は５％、ＢＥＴ比表面積は４７．２ｍ2／ｇ、炭素：水素＝８３：１７であった。
これ以降は、実施例１と同様の処理を行い、炭素材を得た。得られた炭素材のＢＥＴ比表面積は５．５ｍ2／ｇ、吸湿率は１．３％、炭素：水素＝９８．８：１．２であった。
(Example 2)
After adding 100 parts by weight of hexamethylenetetramine to 1000 parts by weight of novolak-type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-50395”) and mixing them uniformly, as the first heat treatment in step (a), in an electric furnace Curing was performed while performing heat treatment at 130 ° C. for 3 hours. Thereafter, the temperature was raised to 400 ° C. at 100 ° C./hour in an electric furnace, held at 400 ° C. for 6 hours, and then cooled to room temperature to obtain a carbon precursor (average particle size 5.3 μm). The carbon precursor had a moisture absorption rate of 5%, a BET specific surface area of 47.2 m 2 / g, and carbon: hydrogen = 83: 17.
Thereafter, the same treatment as in Example 1 was performed to obtain a carbon material. BET specific surface area of the obtained carbon material is 5.5 m 2 / g, moisture absorption rate is 1.3%, carbon: hydrogen = 98.8: was 1.2.
（実施例３）
ノボラック型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５０３９５」）１０００重量部に対してヘキサメチレンテトラミンを１００重量部加え均一に混合した後、工程（ａ）の第１の熱処理として電気炉中１３０℃で３時間、熱処理を行いながら硬化処理を行った。その後、電気炉にて５００℃まで１００℃／時で昇温し、４００℃で５時間保持後、室温まで冷却し炭素前駆体を得た（平均粒子径５．７μｍ）。この炭素前駆体の吸湿率は４％、ＢＥＴ比表面積は６４．５ｍ2／ｇ、炭素：水素＝８５：１５であった。
これ以降は、実施例１と同様の処理を行い、炭素材を得た。得られた炭素材のＢＥＴ比表面積は８．３ｍ2／ｇ、吸湿率は１．４％、炭素：水素＝９９：１であった。
(Example 3)
After adding 100 parts by weight of hexamethylenetetramine to 1000 parts by weight of novolak-type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-50395”) and mixing them uniformly, as the first heat treatment in step (a), in an electric furnace Curing was performed while performing heat treatment at 130 ° C. for 3 hours. Thereafter, the temperature was raised to 500 ° C. at 100 ° C./hour in an electric furnace, kept at 400 ° C. for 5 hours, and then cooled to room temperature to obtain a carbon precursor (average particle size 5.7 μm). The carbon precursor had a moisture absorption rate of 4%, a BET specific surface area of 64.5 m 2 / g, and carbon: hydrogen = 85: 15.
Thereafter, the same treatment as in Example 1 was performed to obtain a carbon material. The obtained carbon material had a BET specific surface area of 8.3 m 2 / g, a moisture absorption rate of 1.4%, and carbon: hydrogen = 99: 1.
（実施例４）
レゾール型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５４７９４」）１０００重量部を、工程（ａ）の第１の熱処理として電気炉中１２０℃で３時間熱処理を行い、前記レゾール型フェノール樹脂中の水分を除去した後、４００℃まで１００℃／時で昇温し、４００℃で３時間保持後、室温まで冷却し炭素前駆体を得た。その後、工程（ｂ）の処理として静置型ボールミルを用いて平均粒子径が５．１μｍになるまで粉砕を行い、粉末状の炭素前駆体を得た。この炭素前駆体の吸湿率は６％、ＢＥＴ比表面積は３４．２ｍ2／ｇ、炭素：水素＝８０：２０であった。
これ以降は、実施例１と同様の処理を行い、炭素材を得た。得られた炭素材のＢＥＴ比表面積は４．７ｍ2／ｇ、吸湿率は０．９％、炭素：水素＝９８．１：１．９であった。
Example 4
1000 parts by weight of a resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-54794”) was subjected to a heat treatment in an electric furnace at 120 ° C. for 3 hours as a first heat treatment in the step (a). After removing the moisture, the temperature was raised to 400 ° C. at 100 ° C./hour, held at 400 ° C. for 3 hours, and then cooled to room temperature to obtain a carbon precursor. Then, it grind | pulverized until the average particle diameter became 5.1 micrometers using the stationary ball mill as a process of a process (b), and obtained the powdery carbon precursor. The carbon precursor had a moisture absorption rate of 6%, a BET specific surface area of 34.2 m 2 / g, and carbon: hydrogen = 80: 20.
Thereafter, the same treatment as in Example 1 was performed to obtain a carbon material. The obtained carbon material had a BET specific surface area of 4.7 m 2 / g, a moisture absorption rate of 0.9%, and carbon: hydrogen = 98.1: 1.9.
（実施例５）
レゾール型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−９４８０」）１０００重量部を工程（ａ）の第１の熱処理として電気炉中８０℃で３時間熱処理を行い、前記レゾール型フェノール樹脂中のアセトン、メタノールを除去した後、５００℃まで１００℃／時で昇温し、５００℃で１２時間保持後、室温まで冷却し炭素前駆体を得た。その後、工程（ｂ）の処理として卓上粉砕機を用いて平均粒子径が３．９μｍになるまで粉砕を行い、粉末状の炭素前駆体を得た。この炭素前駆体の吸湿率は４％、ＢＥＴ比表面積は４４．６ｍ2／ｇ、炭素：水素＝８５：１５であった。
これ以降は、実施例１と同様の処理を行い、炭素材を得た。得られた炭素材のＢＥＴ比表面積は５．７ｍ2／ｇ、吸湿率は１．３％、炭素：水素＝９８．５：１．５であった。
(Example 5)
1000 parts by weight of a resol type phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-9480”) was subjected to a heat treatment at 80 ° C. for 3 hours in the electric furnace as the first heat treatment in the step (a). After removing acetone and methanol, the temperature was raised to 500 ° C. at 100 ° C./hour, held at 500 ° C. for 12 hours, and then cooled to room temperature to obtain a carbon precursor. Then, it grind | pulverized until the average particle diameter was set to 3.9 micrometers using the desktop grinder as a process of a process (b), and the powdery carbon precursor was obtained. The carbon precursor had a moisture absorption rate of 4%, a BET specific surface area of 44.6 m 2 / g, and carbon: hydrogen = 85: 15.
Thereafter, the same treatment as in Example 1 was performed to obtain a carbon material. BET specific surface area of the obtained carbon material is 5.7 m 2 / g, moisture absorption rate is 1.3%, carbon: hydrogen = 98.5: was 1.5.
（比較例１）
レゾール型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５３６９２」）１０００重量部を、工程（ａ）の第１の熱処理として電気炉中８０℃で３時間、熱処理を行いながら、前記レゾール型フェノール樹脂中のメタノールを揮発除去させた後、４００℃まで１００℃／時で昇温し、６００℃で１時間保持後、室温まで冷却し炭素前駆体を得た。その後、工程（ｂ）の処理として卓上粉砕機を用いて平均粒子径が９．２μｍになるまで粉砕を行い、粉末状の炭素前駆体を得た。この炭素前駆体の吸湿率は１３％、ＢＥＴ比表面積は１７５．４ｍ2／ｇ、炭素：水素＝９１：９であった。
得られた粉末状の炭素前駆体を、工程（ｃ）の第２の熱処理として窒素雰囲気下にて１００℃／時で昇温して、９００℃に到達した後、１時間維持して炭素材を得た。得られた炭素材のＢＥＴ比表面積は１４．７ｍ2／ｇ、吸湿率は８．３％、炭素：水素＝９４．４：５．６であった。
(Comparative Example 1)
The resol type phenol resin (Sumitomo Bakelite Co., Ltd., “PR-53692”) 1000 parts by weight was subjected to heat treatment at 80 ° C. for 3 hours in the electric furnace as the first heat treatment in the step (a). After the methanol in the resin was volatilized and removed, the temperature was raised to 400 ° C. at 100 ° C./hour, held at 600 ° C. for 1 hour, and then cooled to room temperature to obtain a carbon precursor. Then, it grind | pulverized until the average particle diameter was set to 9.2 micrometers using the desktop grinder as a process of a process (b), and the powdery carbon precursor was obtained. The carbon precursor had a moisture absorption rate of 13%, a BET specific surface area of 175.4 m 2 / g, and carbon: hydrogen = 91: 9.
The obtained powdery carbon precursor was heated at 100 ° C./hour in a nitrogen atmosphere as the second heat treatment in step (c), reached 900 ° C., and then maintained for 1 hour to obtain a carbon material. Got. The obtained carbon material had a BET specific surface area of 14.7 m 2 / g, a moisture absorption rate of 8.3%, and carbon: hydrogen = 94.4: 5.6.
（比較例２）
レゾール型フェノール樹脂（住友ベークライト株式会社製・「ＰＲ−５３６９２」）１０００部を、工程（ａ）の第１の熱処理として電気炉中８０℃で３時間、熱処理を行いながら、前記レゾール型フェノール樹脂中のメタノールを揮発除去させた後、８００℃まで１００℃／時で昇温し、８００℃で１２時間保持後、室温まで冷却し炭素前駆体を得た。その後、工程（ｂ）の処理としてジェットミル粉砕機を用いて平均粒子径が１７．４μｍになるまで粉砕を行い、粉末状の炭素前駆体を得た。この炭素前駆体の吸湿率は１１％、ＢＥＴ比表面積は９５．０ｍ2／ｇ、炭素：水素＝９３：７であった。得られた粉末状の炭素前駆体を、工程（ｃ）の第２の熱処理として窒素雰囲気下にて１００℃／時で昇温して、１３００℃に到達した後、１時間維持して炭素材を得た。得られた炭素材のＢＥＴ比表面積は１１．７ｍ2／ｇ、吸湿率は７．５％、炭素：水素＝９９．８：０．２であった。
(Comparative Example 2)
The resol-type phenolic resin (Sumitomo Bakelite Co., Ltd., “PR-53692”) 1000 parts was subjected to heat treatment at 80 ° C. for 3 hours in the electric furnace as the first heat treatment in the step (a). After the methanol in the solvent was volatilized and removed, the temperature was raised to 800 ° C. at 100 ° C./hour, held at 800 ° C. for 12 hours, and then cooled to room temperature to obtain a carbon precursor. Then, it grind | pulverized until the average particle diameter became 17.4 micrometers using the jet mill grinder as a process of a process (b), and obtained the powdery carbon precursor. The carbon precursor had a moisture absorption rate of 11%, a BET specific surface area of 95.0 m 2 / g, and carbon: hydrogen = 93: 7. The obtained powdery carbon precursor was heated at 100 ° C./hour in a nitrogen atmosphere as the second heat treatment in step (c), reached 1300 ° C., and then maintained for 1 hour to obtain a carbon material. Got. BET specific surface area of the obtained carbon material is 11.7 m 2 / g, moisture absorption rate is 7.5%, carbon: hydrogen = 99.8: was 0.2.
電池特性の評価
（１）正極の作製
正極活物質としてコバルト酸リチウム（ＬｉＣｏＯ2）を用いた。
Evaluation of battery characteristics (1) Production of positive electrode Lithium cobaltate (LiCoO 2 ) was used as a positive electrode active material.
（２）負極の作製
上記で得られた炭素材を用い、これに対して結合剤としてポリフッ化ビニリデン１０％、アセチレンブラック３％の割合でそれぞれ配合し、さらに、希釈溶媒としてＮ−メチル−２−ピロリドンを適量加え混合し、スラリー状の負極混合物を調製した。
この負極スラリー状混合物を１０μｍの銅箔の両面に塗布し、その後、１１０℃で１時間真空乾燥した。真空乾燥後、ロールプレスによって電極を加圧成形した。これを幅４０ｍｍで長さ２９０ｍｍの大きさに切り出し負極を作製した。この負極の両端１０ｍｍの部分は銅箔が露出しており、この一方に負極タブを圧着した。
（３）電極の厚み・密度測定方法
電極の厚み、電極密度の測定方法について説明する。
電極の厚みについては、作製した負極の厚みをマイクロメーターにて測定した。電極について５点測定し、平均化した値を電極の厚みとした。電極密度については以下の計算式より算出した。
電極密度（ｇ／ｃｍ3）＝Ｔｃ／（ＰW×ＰL×ＰH）
式中、Ｔｃ：銅箔に塗布した炭素材量、ＰW：負極の幅、ＰL：負極の長さ、ＰH：負極の厚み
(2) Production of Negative Electrode The carbon material obtained above was used and blended in a proportion of 10% polyvinylidene fluoride and 3% acetylene black as a binder, and N-methyl-2 as a diluent solvent. -An appropriate amount of pyrrolidone was added and mixed to prepare a slurry-like negative electrode mixture.
This negative electrode slurry mixture was applied to both sides of a 10 μm copper foil, and then vacuum dried at 110 ° C. for 1 hour. After vacuum drying, the electrode was pressure-formed by a roll press. This was cut into a size of 40 mm in width and 290 mm in length to produce a negative electrode. The copper foil was exposed at the 10 mm both ends of the negative electrode, and a negative electrode tab was pressure-bonded to this one.
(3) Method for Measuring Electrode Thickness / Density A method for measuring electrode thickness and electrode density will be described.
About the thickness of the electrode, the thickness of the produced negative electrode was measured with the micrometer. Five points were measured for the electrode, and the averaged value was taken as the thickness of the electrode. The electrode density was calculated from the following calculation formula.
Electrode density (g / cm 3 ) = Tc / (P W × P L × P H )
In the formula, Tc: the amount of carbon material applied to the copper foil, P W : width of the negative electrode, P L : length of the negative electrode, P H : thickness of the negative electrode
（４）リチウムイオン二次電池の作製
上記正極、セパレータ（ポリプロピレン製多孔質フィルム：幅４５ｍｍ、厚さ２５μｍ）、上記負極、セパレータ、上記正極…の順で上記負極が外側になるよう渦巻き状に捲回して電極を作製した。作製した電極を単三型の電池缶に挿入して、負極タブを缶底と溶接した。さらに、電解液としてエチレンカーボネートとジエチレンカーボネートの混合液（体積比が１：１）に、過塩素酸リチウムを１［モル／リットル］の濃度で溶解させたものを用意し、これを上記電池缶内に注入した後、正極タブを正極蓋に溶接し、正極蓋をしめ付けてリチウムイオン二次電池を作製した。
(4) Production of Lithium Ion Secondary Battery In the order of the positive electrode, the separator (polypropylene porous film: width 45 mm, thickness 25 μm), the negative electrode, the separator, the positive electrode,. The electrode was produced by winding. The produced electrode was inserted into an AA type battery can, and the negative electrode tab was welded to the bottom of the can. Further, an electrolytic solution prepared by dissolving lithium perchlorate at a concentration of 1 [mol / liter] in a mixed solution of ethylene carbonate and diethylene carbonate (volume ratio is 1: 1) is prepared. After pouring in, the positive electrode tab was welded to the positive electrode cover, and the positive electrode cover was attached, and the lithium ion secondary battery was produced.
（５）評価
充電容量については、充電時の電流密度を２５ｍＡ／ｇとして定電流充電を行い、電位が０Ｖに達した時点から、０Ｖで定電圧充電を行い、電流密度が１．２５ｍＡ／ｇになるまでに充電した電気量を充電容量とした。
一方、放電容量については、放電時の電流密度も２５ｍＡ／ｇとして定電流放電を行い、電位が２．５Ｖに達した時点から、２．５Ｖで定電圧放電を行い、電流密度が１．２５ｍＡ／ｇになるまでに放電した電気量を放電容量とした。
また、以下の式により初回の充放電効率を定義した。
初回充放電効率（％）＝初回放電容量（ｍＡｈ／ｇ）／初回充電容量（ｍＡｈ／ｇ）×１００
(5) Evaluation Regarding the charging capacity, constant current charging is performed with a current density at the time of charging of 25 mA / g. When the potential reaches 0 V, constant voltage charging is performed at 0 V, and the current density is 1.25 mA / g. The amount of electricity charged up to is the charge capacity.
On the other hand, with respect to the discharge capacity, constant current discharge was performed with a current density at the time of discharge of 25 mA / g, and constant voltage discharge was performed at 2.5 V from the time when the potential reached 2.5 V, and the current density was 1.25 mA. The amount of electricity discharged up to / g was taken as the discharge capacity.
The initial charge / discharge efficiency was defined by the following equation.
Initial charge / discharge efficiency (%) = initial discharge capacity (mAh / g) / initial charge capacity (mAh / g) × 100
上記炭素前駆体の吸湿率、ＢＥＴ比表面積及び平均粒子径の測定結果を表１に示す。
表２の結果より、実施例１〜５はいずれも、フェノール樹脂類を工程（ａ）の熱処理条件、及び工程（ｂ）の物理的手法により粉砕によって得られる炭素前駆体の元素組成比を炭素：水素＝７：３〜９：１、ＢＥＴ比表面積を１０〜８５ｍ2／ｇ、平均粒子径を１〜７μｍに制御し、さらに工程（ｃ）の熱処理をして得られる炭素材の元素組成比を炭素：水素＝９５：５〜９９．７：０．３、炭素前駆体：炭素材の吸湿率の比を５：５〜９：１、比表面積を１〜１０ｍ2／ｇである本発明の炭素材から得られた負極材を備えるリチウムイオン二次電池であり、炭素前駆体の元素組成比、ＢＥＴ比表面積、平均粒子径を制御しなかった比較例１、２と比べて、充放電容量、充放電効率、サイクル性に優れ、リチウムイオン二次電池用負極に用いた場合に、電極の厚みが薄く、電極密度の高いものであった。 From the results in Table 2, in Examples 1 to 5, the elemental composition ratio of the carbon precursor obtained by pulverizing phenolic resins by the heat treatment conditions in step (a) and the physical method in step (b) is carbon. : Hydrogen = 7: 3 to 9: 1, BET specific surface area is controlled to 10 to 85 m 2 / g, average particle diameter is controlled to 1 to 7 μm, and the elemental composition of the carbon material obtained by heat treatment in step (c) The ratio of carbon: hydrogen = 95: 5 to 99.7: 0.3, carbon precursor: carbon material moisture absorption ratio of 5: 5 to 9: 1, and specific surface area of 1 to 10 m 2 / g. Compared with Comparative Examples 1 and 2 in which the element composition ratio, BET specific surface area, and average particle diameter of the carbon precursor were not controlled, which is a lithium ion secondary battery including a negative electrode material obtained from the carbon material of the invention. Excellent discharge capacity, charge / discharge efficiency, cycleability, used for negative electrode for lithium ion secondary battery If the thickness of the electrode is thin, it was those high electrode density.
Claims (9)
前記難黒鉛性炭素源を用いて、第１の加熱を行い、炭素前駆体を得る第１の熱処理工程、
及び前記炭素前駆体を用いて、第２の加熱を行い、炭素材を得る第２の熱処理工程、
を含むことを特徴とする炭素材の製造方法。 A method for producing a carbon material obtained by carbonizing a non-graphitizable carbon source,
A first heat treatment step of obtaining a carbon precursor by performing a first heating using the non-graphitizable carbon source;
And a second heat treatment step for obtaining a carbon material by performing a second heating using the carbon precursor,
The carbon material manufacturing method characterized by including.
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