JPH11246209A - Negative electrode carbon material for lithium secondary cell and lithium secondary cell - Google Patents
Negative electrode carbon material for lithium secondary cell and lithium secondary cellInfo
- Publication number
- JPH11246209A JPH11246209A JP10053310A JP5331098A JPH11246209A JP H11246209 A JPH11246209 A JP H11246209A JP 10053310 A JP10053310 A JP 10053310A JP 5331098 A JP5331098 A JP 5331098A JP H11246209 A JPH11246209 A JP H11246209A
- Authority
- JP
- Japan
- Prior art keywords
- lithium secondary
- negative electrode
- graphite
- carbon
- carbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910021384 soft carbon Inorganic materials 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011295 pitch Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
Landscapes
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム二次電池用負
極炭素材およびそれを用いた、高い放電容量を有するリ
チウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode carbon material for a lithium secondary battery and a lithium secondary battery having a high discharge capacity using the same.
【０００２】[0002]
【従来の技術】負極炭素材として黒鉛を用いたリチウム
二次電池については、特開昭57-208079号公報（特公昭6
2-23433号公報）をはじめとして、数多くの公報類に開
示されている。2. Description of the Related Art A lithium secondary battery using graphite as a carbon material for a negative electrode is disclosed in Japanese Patent Application Laid-Open No. 57-208079 (Japanese Patent Publication No. Sho.
2-23433), and many other publications.
【０００３】しかしながら、負極炭素材(リチウム担持
体)として黒鉛を用いる場合に、担持状態での負極炭素
材の組成(LiC6)から求められるリチウム二次電池の理論
的最大容量は、372Ah/kg（炭素ベース）であると言われ
ており、放電容量に限界があるという問題点がある。However, when graphite is used as the negative electrode carbon material (lithium carrier), the theoretical maximum capacity of the lithium secondary battery obtained from the composition (LiC 6 ) of the negative electrode carbon material in the supported state is 372 Ah / kg (Carbon-based), which has a problem that the discharge capacity is limited.
【０００４】しかるに、リチウム二次電池を電源として
使用するノートパソコンなどの電子機器類の機能向上に
伴って、電池自体の性能をさらに一層向上させることが
求められており、その負極に対する要求性能も高くなっ
てきている。この様な技術的な状況を考慮すると、負極
容量に関して372Ah/kgという数値は、必ずしも満足すべ
き容量とはいえない。すなわち、従来から提唱されてい
るような黒鉛層間化合物の寄与だけでは、リチウムを貯
蔵できる量が充分ではないことが明らかとなってきた。However, with the improvement in the functions of electronic devices such as notebook personal computers using a lithium secondary battery as a power source, it is required to further improve the performance of the battery itself. It is getting higher. Considering such a technical situation, a value of 372 Ah / kg regarding the negative electrode capacity is not necessarily a satisfactory capacity. That is, it has become clear that the amount of lithium that can be stored is not sufficient only by the contribution of the graphite intercalation compound as conventionally proposed.
【０００５】この問題点を解決するために、特開平8-29
8114号公報は、黒鉛にハードカーボンをコーティングし
た負極炭素材を提案している。しかしながら、ハードカ
ーボンには必然的に細孔が多く存在しているために、こ
れをコーティングした負極炭素材の性能は、空気からの
吸湿などにより、次第に劣化するという大きな欠点を有
している。In order to solve this problem, Japanese Patent Laid-Open No. 8-29
No. 8114 proposes a negative electrode carbon material in which graphite is coated with hard carbon. However, since the hard carbon necessarily has many pores, the performance of the negative electrode carbon material coated with the hard carbon has a serious disadvantage that it gradually deteriorates due to moisture absorption from the air.
【０００６】また、容量が高くても、初期効率が88％未
満という低い負極炭素材を使用する場合には、正極のリ
チウムが失われるので、リチウム二次電池用負極材料と
しては不適である。When a negative electrode carbon material having a low initial efficiency of less than 88% is used even if the capacity is high, lithium of the positive electrode is lost, so that it is not suitable as a negative electrode material for a lithium secondary battery.
【０００７】さらに、炭素材の窒素吸着によるBET比表
面積値が3m2/gを超える場合には、電池としての安全性
に問題点が発生する確率が急激に高くなるので、リチウ
ム二次電池負極材料としては、不適である。[0007] Further, when the BET specific surface area value of the carbon material by nitrogen adsorption exceeds 3 m 2 / g, the probability of causing a problem in the safety of the battery increases sharply, so the lithium secondary battery negative electrode It is unsuitable as a material.
【０００８】[0008]
【発明が解決しようとする問題点】従って、本発明は、
リチウム二次電池の負極材として使用した場合に電池の
充放電容量が理論容量である372Ah/kgを超え、かつそれ
自身を空気中で放置しても著しい劣化を生じない様な改
質された炭素材、この炭素材からなるリチウム二次電池
用の負極および負極材料ならびにこの負極材料を使用す
るリチウム二次電池を提供することを主な目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention provides
When used as a negative electrode material of a lithium secondary battery, the battery was modified so that the charge / discharge capacity of the battery exceeded the theoretical capacity of 372 Ah / kg and did not cause any significant deterioration even if it was left in air. It is a main object to provide a carbon material, a negative electrode and a negative electrode material for a lithium secondary battery including the carbon material, and a lithium secondary battery using the negative electrode material.
【０００９】[0009]
【問題点を解決するための手段】本発明者は、上記の様
な技術の現状に鑑みて鋭意研究を重ねた結果、黒鉛とハ
ードカーボンとの複合体の表面を炭素の焼成体でコーテ
ィングすることにより、リチウム二次電池の負極材とし
て使用した場合に高容量かつ高初期効率を与える黒鉛系
炭素材料が得られることを見出した。Means for Solving the Problems The present inventor has conducted intensive studies in view of the state of the art as described above, and as a result, has coated the surface of a composite of graphite and hard carbon with a fired carbon material. As a result, it has been found that a graphite-based carbon material that provides high capacity and high initial efficiency when used as a negative electrode material of a lithium secondary battery can be obtained.
【００１０】即ち、本発明は、下記の炭素材を提供する
ものである； １．黒鉛とハードカーボンとの複合体の表面を炭素の焼
成体でコーティングしたリチウム二次電池用負極炭素
材。That is, the present invention provides the following carbon materials: A negative electrode carbon material for lithium secondary batteries in which the surface of a composite of graphite and hard carbon is coated with a fired carbon material.
【００１１】２．放電容量が372Ah/kgを超えることを特
徴とする上記項１に記載のリチウム二次電池用負極炭素
材。2. Item 2. The negative electrode carbon material for a lithium secondary battery according to Item 1, wherein the discharge capacity exceeds 372 Ah / kg.
【００１２】３．初期効率が88％以上であることを特徴
とする上記項１に記載のリチウム二次電池用負極炭素
材。3. Item 2. The negative electrode carbon material for a lithium secondary battery according to Item 1, wherein the initial efficiency is 88% or more.
【００１３】４．窒素吸着によるBET比表面積の値が、3
m2/ｇ以下であることを特徴とする上記項１に記載のリ
チウム二次電池用負極炭素材。4. The value of BET specific surface area by nitrogen adsorption is 3
Item 2. The negative electrode carbon material for a lithium secondary battery according to Item 1, wherein the carbon material is not more than m 2 / g.
【００１４】５．上記項１に記載の炭素材を構成要素と
して用いるリチウム二次電池用負極材料。5. Item 7. A negative electrode material for a lithium secondary battery using the carbon material according to Item 1 as a constituent element.
【００１５】６．上記項５に記載の負極材料を用いるリ
チウム二次電池用負極。6. Item 6. A negative electrode for a lithium secondary battery using the negative electrode material according to Item 5.
【００１６】７．上記項６に記載の負極を用いた非水系
リチウム二次電池。[7] Item 7. A non-aqueous lithium secondary battery using the negative electrode according to Item 6.
【００１７】[0017]
【発明の実施の態様】本発明において使用する黒鉛とし
ては、天然黒鉛、人造黒鉛、黒鉛化メソカーボンマイク
ロビーズ、黒鉛化ピッチ系炭素繊維などが挙げられる。
黒鉛の平均粒径は、通常1〜100μm程度であり、好まし
くは1〜40μm程度である。黒鉛の真密度は、通常2.0g/c
c以上であり、好ましくは2.2g/cc以上である。また、Ｘ
線広角回折法により得られる(002)面の面間隔は、0.338
nm以下であり、より好ましくは0.336nm以下である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Graphite used in the present invention includes natural graphite, artificial graphite, graphitized mesocarbon microbeads, graphitized pitch-based carbon fiber, and the like.
The average particle size of the graphite is usually about 1 to 100 μm, preferably about 1 to 40 μm. The true density of graphite is usually 2.0 g / c
c or more, preferably 2.2 g / cc or more. Also, X
The plane spacing of the (002) plane obtained by the line wide-angle diffraction method is 0.338.
nm or less, and more preferably 0.336 nm or less.
【００１８】一方、本発明において使用するハードカー
ボンとしては、炭素繊維の製造過程の中間生成物である
不融化糸を1000〜1400℃程度で炭化した炭素繊維、有機
化合物を150〜300℃程度で空気酸化した後、1000〜1400
℃程度で炭化した炭素材料などが例示できる。炭素材料
の製造原料として使用する有機化合物としては、石炭系
および石油系の等方性ピッチ、熱硬化性樹脂（フェノー
ル樹脂、フラン樹脂、フルフラール樹脂などが例示され
る。ハードカーボンを製造するに際し、炭化は、真空下
または不活性ガスの流通下に行うことが好ましい。ハー
ドカーボンの平均粒径は、通常1〜100μm程度であり、
好ましくは1〜40μm程度である。ハードカーボンの真密
度は、通常1.8g/cc以下である。また、Ｘ線広角回折法
により得られる(002)面の面間隔は、0.36nm以上であ
る。On the other hand, as the hard carbon used in the present invention, carbon fibers obtained by carbonizing infusible yarn, which is an intermediate product in the process of producing carbon fibers, at about 1000 to 1400 ° C., and organic compounds at about 150 to 300 ° C. 1000-1400 after air oxidation
Examples thereof include carbon materials carbonized at about ° C. Examples of the organic compound used as a raw material for producing a carbon material include coal-based and petroleum-based isotropic pitches and thermosetting resins (phenol resins, furan resins, furfural resins, and the like. In the production of hard carbon, The carbonization is preferably performed under vacuum or under a flow of an inert gas.The average particle size of the hard carbon is usually about 1 to 100 μm,
Preferably it is about 1 to 40 μm. The true density of hard carbon is usually 1.8 g / cc or less. The plane spacing of the (002) plane obtained by the X-ray wide-angle diffraction method is 0.36 nm or more.
【００１９】本発明において、「黒鉛とハードカーボン
との複合体」とは、二層構造体（粒径1〜40μm程度の黒
鉛を芯材として、ハードカーボンを厚さ0.01〜4μm程度
でコーティングした構造体：前者と後者の割合は、複合
体重量を100部として、前者：後者＝60:40〜80:20程度
（重量比）である）および黒鉛とハードカーボンとの混
合物を意味する。二層構造体は、例えば、軟化点以上の
等方性ピッチと黒鉛とを混合して、黒鉛表面にピッチを
コーティングさせた後、空気酸化し、窒素などの不活性
雰囲気中で炭化することにより製造することができる。
また、黒鉛とハードカーボンとの混合物は、両者を混合
機などにより物理的に混合することにより、調製でき
る。この混合物において、前者と後者との割合は、前者
の量が後者の量よりも大きいことを必要とし、通常前
者：後者＝51:49〜90:10程度（重量比）であり、より好
ましくは前者：後者＝60:40〜80:20程度（重量比）であ
る。本発明で使用する複合体において、黒鉛の割合が低
すぎる場合には、電極特性として、急激な初期効率の低
下を引き起こすことがある。In the present invention, the term "composite of graphite and hard carbon" refers to a two-layer structure (hard carbon coated to a thickness of about 0.01 to 4 μm using graphite having a particle size of about 1 to 40 μm as a core material). Structure: The ratio of the former to the latter means that the weight of the composite is 100 parts, and the former: the latter is about 60:40 to 80:20 (weight ratio) and a mixture of graphite and hard carbon. The two-layer structure, for example, by mixing graphite with an isotropic pitch equal to or higher than the softening point, coating the graphite surface with the pitch, oxidizing air, and carbonizing in an inert atmosphere such as nitrogen. Can be manufactured.
Further, a mixture of graphite and hard carbon can be prepared by physically mixing both with a mixer or the like. In this mixture, the ratio between the former and the latter requires that the amount of the former is larger than the amount of the latter, and usually the former: the latter = about 51:49 to 90:10 (weight ratio), more preferably The former: the latter = approximately 60:40 to 80:20 (weight ratio). In the composite used in the present invention, if the proportion of graphite is too low, the electrode characteristics may cause a sharp decrease in initial efficiency.
【００２０】以下に、この様な複合体の表面を炭素の焼
成体でコーティングする工程について説明する。The step of coating the surface of such a composite with a carbon fired body will be described below.
【００２１】先ず、上記の様にして得られる複合体を下
記に示す有機化合物に温度10〜300℃程度で、より好ま
しくは100〜200℃程度で5〜30分間程度浸漬し、次いで
有機化合物から分離した後、有機溶媒を加えて10〜300
℃程度、より好ましくは10〜100℃程度で洗浄処理し、
次いで非酸化性雰囲気中で炭化することにより、所望の
炭素焼成体コーティング層(低結晶性炭素乃至ソフトカ
ーボンからなる被覆層)を備えた炭素材を得ることがで
きる。First, the composite obtained as described above is immersed in the following organic compound at a temperature of about 10 to 300 ° C., more preferably at about 100 to 200 ° C. for about 5 to 30 minutes. After separation, add an organic solvent and add 10-300
Washing at about 10 ° C, more preferably about 10-100 ° C,
Then, by carbonizing in a non-oxidizing atmosphere, a carbon material having a desired carbon fired body coating layer (a coating layer made of low crystalline carbon or soft carbon) can be obtained.
【００２２】この複合体の浸漬工程で用いる有機化合物
としては、炭化時に複合体表面にソフトカーボンのコー
ティング層を形成し得る材料、例えば、ピッチ、タール
などが挙げられる。Examples of the organic compound used in the immersion step of the composite include materials capable of forming a soft carbon coating layer on the surface of the composite during carbonization, such as pitch and tar.
【００２３】洗浄用の有機溶媒としては、特に限定され
ず、トルエン、メタノール、アセトン、ヘキサン、ベン
ゼン、キシレン、メチルナフタレン、タール中油などを
使用することができる。この洗浄は、複合体表面に付着
した有機化合物の厚さを調整し、かつ均一とするために
行う。The organic solvent for washing is not particularly limited, and toluene, methanol, acetone, hexane, benzene, xylene, methylnaphthalene, tar oil and the like can be used. This washing is performed to adjust the thickness of the organic compound attached to the surface of the composite and to make the thickness uniform.
【００２４】洗浄処理した複合体の炭化は、例えば、60
0〜1500℃程度、好ましくは800〜1200℃程度の温度で、
1〜20時間程度、好ましくは3〜12時間程度処理すること
により実施できる。炭化を真空下で行う場合には、放電
容量および初期効率をより一層改善することができる。The carbonization of the complex subjected to the washing treatment may be, for example, 60
At a temperature of about 0 to 1500 ° C, preferably about 800 to 1200 ° C,
It can be carried out by treating for about 1 to 20 hours, preferably for about 3 to 12 hours. When carbonization is performed under vacuum, the discharge capacity and the initial efficiency can be further improved.
【００２５】負極炭素材表面に形成される炭化層(ソフ
トカーボン層)が厚い程、負極と非水系リチウム二次電
池に用いる電解液の有機溶媒とが反応し難くなる。従っ
て、リチウム二次電池の負極として用いる炭素材のソフ
トカーボン層が厚い程、電解液の分解および負極の破壊
が起こり難い。しかしながら、ソフトカーボン層が厚す
ぎる場合には、炭素材の負極材料としての充放電特性に
悪影響を与える恐れがある。本発明者の研究によれば、
ソフトカーボン層の厚さが0.1μm以下、通常0.01〜0.1
μm程度である炭素材を負極材料として用いる場合に
は、安全性と充放電特性とのバランスが良好なリチウム
二次電池を製造することができることが判明した。ソフ
トカーボン層の厚さは、使用する有機化合物の量、浸漬
温度、浸漬時間、有機溶媒による洗浄条件などを調節す
ることにより、制御することができる。The thicker the carbonized layer (soft carbon layer) formed on the surface of the negative electrode carbon material, the more difficult it is for the negative electrode to react with the organic solvent of the electrolytic solution used in the non-aqueous lithium secondary battery. Therefore, as the soft carbon layer of the carbon material used as the negative electrode of the lithium secondary battery is thicker, the decomposition of the electrolytic solution and the destruction of the negative electrode are less likely to occur. However, if the soft carbon layer is too thick, there is a possibility that the charge / discharge characteristics of the carbon material as a negative electrode material may be adversely affected. According to the inventor's research,
The thickness of the soft carbon layer is 0.1 μm or less, usually 0.01 to 0.1
It has been found that when a carbon material of about μm is used as a negative electrode material, a lithium secondary battery having a good balance between safety and charge / discharge characteristics can be manufactured. The thickness of the soft carbon layer can be controlled by adjusting the amount of the organic compound used, the immersion temperature, the immersion time, the conditions for washing with the organic solvent, and the like.
【００２６】このようにして得られた炭素材を粒度調整
することにより、リチウム二次電池用負極材料として好
適な炭素材を製造できる。粒度調整に際しては、例え
ば、フェザーミルと風力分級機を用いて、解砕・分級を
行うことにより、複数の炭素粒子(一次粒子)が相互に付
着して形成されている集合体(二次粒子)を分離させるこ
とができ、その結果、粒子径および粒子径分布をリチウ
ム二次電池用負極材料として好適な範囲に制御すること
ができる。炭素材は、数平均粒子径を5〜40μm程度、よ
り好ましくは5〜20μm程度とし、最大粒子径を50μm以
下、より好ましくは30μm以下とし、最小粒子径を3μm
以上、より好ましくは5μm以上とすることが望ましい。
この様に粒度調整を行うことにより、負極を作製する際
の取扱が容易となり、負極としたときに効率よく特性を
発現し得る負極材料を得ることができる。By adjusting the particle size of the carbon material thus obtained, a carbon material suitable as a negative electrode material for a lithium secondary battery can be manufactured. At the time of particle size adjustment, for example, by using a feather mill and an air classifier, by performing crushing and classification, aggregates (secondary particles) formed by adhering a plurality of carbon particles (primary particles) to each other ) Can be separated, and as a result, the particle size and the particle size distribution can be controlled in a range suitable for a negative electrode material for a lithium secondary battery. The carbon material has a number average particle diameter of about 5 to 40 μm, more preferably about 5 to 20 μm, a maximum particle diameter of 50 μm or less, more preferably 30 μm or less, and a minimum particle diameter of 3 μm.
More preferably, it is more preferably 5 μm or more.
By adjusting the particle size in this manner, handling during the production of the negative electrode becomes easy, and a negative electrode material that can exhibit characteristics efficiently when used as a negative electrode can be obtained.
【００２７】かくして、公知のリチウム二次電池におけ
ると同様にして、上記で得られた本発明のリチウム二次
電池用負極を正極・電解液と組み合わせることにより、
リチウム二次電池を作成することができる。Thus, by combining the negative electrode for a lithium secondary battery of the present invention obtained above with a positive electrode and an electrolyte in the same manner as in a known lithium secondary battery,
A lithium secondary battery can be created.
【００２８】[0028]
【発明の効果】本発明によれば、以下の様な顕著な効果
が達成される。According to the present invention, the following remarkable effects are achieved.
【００２９】（１）黒鉛とハードカーボンとの複合体の
表面を炭素の焼成体でコーティングした炭素材をリチウ
ム二次電池の負極として使用する場合に、初期効率が88
％以上でかつ黒鉛の理論容量である372Ah/kgを超える高
い放電容量が得られるので、同じ性能ではリチウム二次
電池負極の体積および重量を著しく低減できるという効
果がある。(1) When a carbon material obtained by coating the surface of a composite of graphite and hard carbon with a fired carbon material is used as a negative electrode of a lithium secondary battery, the initial efficiency is 88.
%, And a high discharge capacity exceeding 372 Ah / kg, which is the theoretical capacity of graphite, can be obtained. Therefore, there is an effect that the volume and weight of the negative electrode of the lithium secondary battery can be significantly reduced with the same performance.
【００３０】（２）リチウム二次電池における上記の高
い放電容量は、10サイクル程度の充放電後にも殆ど低下
せず、100％あるいはそれに近い放電容量が維持され
る。(2) The above high discharge capacity of the lithium secondary battery hardly decreases even after about 10 cycles of charge and discharge, and the discharge capacity at or near 100% is maintained.
【００３１】（３）本発明による炭素材を空気中で放置
させた場合の性能劣化の度合いは、黒鉛単独の場合と同
様に小さいので、本発明炭素材を負極として使用するリ
チウム二次電池の放電容量維持率および初期効率維持率
は、９８％以上である。(3) Since the degree of performance degradation when the carbon material according to the present invention is left in the air is as small as that of graphite alone, the lithium secondary battery using the carbon material of the present invention as a negative electrode The discharge capacity maintenance ratio and the initial efficiency maintenance ratio are 98% or more.
【００３２】[0032]
【実施例】以下に実施例を挙げて本発明をさらに詳しく
説明する。The present invention will be described in more detail with reference to the following examples.
【００３３】実施例１ 1.黒鉛とハードカーボンとの複合、および表面コーティ
ング 黒鉛としては、マダガスカル産の天然黒鉛(平均粒径74
μm、真密度2.25g/cc、(002)面の面間隔0.335nm以下）
を用いた。Example 1 1. Composite of graphite and hard carbon, and surface coating As the graphite, natural graphite produced in Madagascar (average particle size of 74) was used.
μm, true density 2.25g / cc, spacing between (002) planes 0.335nm or less)
Was used.
【００３４】ハードカーボンとしては、軟化点280℃の
石炭系ピッチを空気雰囲気下250℃で2時間酸化処理を行
った後、真空下1100℃で1時間熱処理を行った材料(平均
粒径15μm、真密度1.7g/cc、(002)面の面間隔0.37nm以
上）を用いた。As the hard carbon, a material obtained by oxidizing a coal pitch having a softening point of 280 ° C. in an air atmosphere at 250 ° C. for 2 hours, and then performing a heat treatment in vacuum at 1100 ° C. for 1 hour (average particle size 15 μm, A true density of 1.7 g / cc and a (002) plane spacing of 0.37 nm or more) were used.
【００３５】複合は、黒鉛:ハードカーボン＝6:4（重量
比）となる様に両材料を配合し、物理的に混合すること
により、行った。The composite was prepared by blending both materials so that graphite: hard carbon = 6: 4 (weight ratio) and physically mixing them.
【００３６】得られた複合体をタールに150℃で20分間
浸漬し、次いでタールから分離し、トルエンを加えて約
50℃で洗浄した後、1100℃で２時間真空下に炭化を行る
ことにより、複合体表面を炭素の焼成体(ソフトカーボ
ン層)により被覆した。The obtained composite was immersed in tar at 150 ° C. for 20 minutes, then separated from the tar, and toluene was added thereto for about
After washing at 50 ° C., carbonization was performed under vacuum at 1100 ° C. for 2 hours, so that the surface of the composite was covered with a fired carbon material (soft carbon layer).
【００３７】２．炭素極（作用極）の作成 上記で得られた被覆黒鉛複合体92重量部とポリフッ化ビ
ニリデン８重量部とを混合し、適量のＮ−メチルピロリ
ドンに加え、撹拌した後、スラリー状物とした。このス
ラリー状物を電解銅箔上にドクターブレードを用いて塗
布した後、110℃で30分間乾燥させ、ロールプレス機に
よりプレスして、電極材料を得た。この電極材料から1c
m２の塗布部だけを残した電極を切り出して炭素極と
し、さらに200℃で6時間真空乾燥した。2. Preparation of Carbon Electrode (Working Electrode) 92 parts by weight of the coated graphite composite obtained above and 8 parts by weight of polyvinylidene fluoride were mixed, added to an appropriate amount of N-methylpyrrolidone, and stirred to form a slurry. . The slurry was applied on an electrolytic copper foil using a doctor blade, dried at 110 ° C. for 30 minutes, and pressed by a roll press to obtain an electrode material. 1c from this electrode material
The electrode leaving only the coated part of m2 was cut out to make a carbon electrode, and further dried at 200 ° C. for 6 hours under vacuum.
【００３８】３．試験セルの組立 前記の様にして得られた炭素極に対し、対極として十分
な量のリチウム金属を使用し、電解液として1mol/lの濃
度にLiClO4を溶解させたエチレンカーボネートとジエチ
ルカーボネートとの混合溶媒(体積比1:1)を使用し、セ
パレータとしてポリプロピレン不織布を使用して、リチ
ウム二次電池(試験セル)を作成した。3. Test cell assembly For the carbon electrode obtained as described above, a sufficient amount of lithium metal was used as a counter electrode, and ethylene carbonate and diethyl carbonate in which LiClO 4 was dissolved at a concentration of 1 mol / l as an electrolyte were used. A lithium secondary battery (test cell) was prepared using a mixed solvent of (1: 1) and a polypropylene nonwoven fabric as a separator.
【００３９】４．電極特性の測定 上記で得られたリチウム二次電池の充放電特性を測定し
た。4. Measurement of electrode characteristics The charge / discharge characteristics of the lithium secondary battery obtained above were measured.
【００４０】充電は、リチウム極に対して1mVまで1mA/c
m2の定電流充電した後、1mVで定電位充電をトータルで1
2時間かけて行った。放電は、1mA/cm2の定電流放電でリ
チウム極に対して2.0Vまで行った。放電容量は、カット
電圧が1.0Ｖの時の容量である。Charging is 1 mA / c up to 1 mV with respect to the lithium electrode
After constant current charge m 2, 1 total constant potential charging at 1mV
It took two hours. The discharge was performed at a constant current of 1 mA / cm 2 up to 2.0 V with respect to the lithium electrode. The discharge capacity is the capacity when the cut voltage is 1.0V.
【００４１】また、上記の工程で作成した電極を空気中
で3日間放置した後、上記と同様にして試験セルを組立
て、上記と同様にして電極特性を測定した。After the electrodes prepared in the above steps were allowed to stand in air for 3 days, a test cell was assembled in the same manner as above, and the electrode characteristics were measured in the same manner as above.
【００４２】本実施例および実施例２〜３ならびに比較
例1〜４の結果を後記の表１に示す。The results of this example, Examples 2-3 and Comparative Examples 1-4 are shown in Table 1 below.
【００４３】実施例２ 黒鉛とハードカーボンとの複合体の調製に際して、両者
の複合割合を黒鉛:ハードカーボン＝7:3（重量比）に設
定した以外は実施例１と同様にして、順次所定の操作を
行い、試験セルの評価を行った。Example 2 In the preparation of a composite of graphite and hard carbon, the same procedure was followed as in Example 1, except that the composite ratio of graphite and hard carbon was set to 7: 3 (weight ratio). Was performed to evaluate the test cell.
【００４４】実施例３ 黒鉛とハードカーボンとの複合体の調製に際して、両者
の複合割合を黒鉛：ハードカーボン＝8:2（重量比）に
設定した以外は実施例１と同様にして、順次所定の操作
を行い、試験セルの評価を行った。Example 3 In the preparation of a composite of graphite and hard carbon, the same procedure as in Example 1 was repeated except that the composite ratio of graphite and hard carbon was set to 8: 2 (weight ratio). Was performed to evaluate the test cell.
【００４５】比較例１ 黒鉛とハードカーボンとの複合体の調製に際して、両者
の複合割合を黒鉛：ハードカーボン＝5:5（重量比）に
設定した以外は実施例１と同様にして、順次所定の操作
を行い、試験セルの評価を行った。Comparative Example 1 In preparing a composite of graphite and hard carbon, the same procedure as in Example 1 was repeated except that the composite ratio of graphite and hard carbon was set to 5: 5 (weight ratio). Was performed to evaluate the test cell.
【００４６】比較例２ 黒鉛とハードカーボンとの複合体に代えて、ハードカー
ボンのみを使用した以外は実施例１と同様にして、順次
所定の操作を行い、試験セルの評価を行った。Comparative Example 2 Test cells were evaluated in the same manner as in Example 1 except that only the hard carbon was used instead of the composite of graphite and hard carbon.
【００４７】比較例３ 複合体の表面をタール焼成体によりコーティングしなか
った以外は実施例１と同様にして、順次所定の操作を行
い、試験セルの評価を行った。Comparative Example 3 Test cells were evaluated in the same manner as in Example 1 except that the surface of the composite was not coated with the fired tar.
【００４８】比較例４ 黒鉛とハードカーボンとの複合体に代えて、黒鉛のみを
使用した以外は実施例１と同様にして、順次所定の操作
を行い、試験セルの評価を行った。Comparative Example 4 Test cells were evaluated in the same manner as in Example 1 except that only graphite was used instead of the composite of graphite and hard carbon.
【００４９】[0049]
【表１】 [Table 1]
【００５０】表１に示す結果から明らかな様に、本発明
によれば、初期効率が高く、黒鉛の理論容量を超える放
電容量を有するリチウム二次電池が得られる。また、本
発明によれば、リチウム二次電池の容量は、10サイクル
程度の充放電サイクルでは、殆ど低下しない。しかも、
本発明による電極は空気中での安定性に優れているの
で、空気中に３日間放置した後電池を組み立てても、電
池特性には、殆ど変化が生じない。As is clear from the results shown in Table 1, according to the present invention, a lithium secondary battery having a high initial efficiency and a discharge capacity exceeding the theoretical capacity of graphite can be obtained. Further, according to the present invention, the capacity of the lithium secondary battery hardly decreases in about 10 charge / discharge cycles. Moreover,
Since the electrode according to the present invention has excellent stability in the air, even if the battery is assembled after being left in the air for three days, the battery characteristics hardly change.
Claims (7)
炭素の焼成体でコーティングしたリチウム二次電池用負
極炭素材。1. A negative electrode carbon material for a lithium secondary battery, wherein the surface of a composite of graphite and hard carbon is coated with a fired carbon material.
する請求項１に記載のリチウム二次電池用負極炭素材。2. The negative electrode carbon material for a lithium secondary battery according to claim 1, wherein the discharge capacity exceeds 372 Ah / kg.
る請求項１に記載のリチウム二次電池用負極炭素材。3. The negative electrode carbon material for a lithium secondary battery according to claim 1, wherein the initial efficiency is 88% or more.
ｇ以下であることを特徴とする請求項１に記載のリチウ
ム二次電池用負極炭素材。4. The value of the BET specific surface area by nitrogen adsorption is 3 m 2 /
The negative electrode carbon material for a lithium secondary battery according to claim 1, wherein the carbon material is not more than g.
用いるリチウム二次電池用負極材料。5. A negative electrode material for a lithium secondary battery using the carbon material according to claim 1 as a constituent element.
ム二次電池用負極。6. A negative electrode for a lithium secondary battery using the negative electrode material according to claim 5.
ウム二次電池。7. A non-aqueous lithium secondary battery using the negative electrode according to claim 6.
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| JP05331098A JP4081621B2 (en) | 1998-03-05 | 1998-03-05 | Negative electrode carbon material for lithium secondary battery and lithium secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05331098A JP4081621B2 (en) | 1998-03-05 | 1998-03-05 | Negative electrode carbon material for lithium secondary battery and lithium secondary battery |
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|---|---|
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Family
ID=12939155
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