JP3551490B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
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- JP3551490B2 JP3551490B2 JP23786594A JP23786594A JP3551490B2 JP 3551490 B2 JP3551490 B2 JP 3551490B2 JP 23786594 A JP23786594 A JP 23786594A JP 23786594 A JP23786594 A JP 23786594A JP 3551490 B2 JP3551490 B2 JP 3551490B2
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- negative electrode
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- 239000000571 coke Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims 3
- 238000010298 pulverizing process Methods 0.000 claims 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007849 furan resin Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000005011 phenolic resin Substances 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
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
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- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、非水系二次電池に関するものである。より詳しくは、特に小型、軽量の電子機器用として好適な、リチウム二次電池をはじめとする非水系二次電池に関するものである。
【０００２】
【従来の技術】
近年、電子機器等の小型軽量化、省電力化及び環境保全の立場から、鉛蓄電池やニッカド電池に替わるクリーンな非水系電池、特にリチウム二次電池が注目され、実用化段階にまで到達した。しかし、負極にリチウム金属を用いると、リチウム金属が充電時にデンドライト状に成長し、内部短絡を引き起こすという問題があった。その対策として、リチウム金属原子を吸収・放出することのできる材料の開発が盛んに行われ、その中でもコークスを用いたものは低コスト・高容量という点で有望視されている（特開昭６２−９０８６３号、特開平１−２２１８５９号、特開昭６３−１２１２５７号公報）。
【０００３】
【発明が解決しようとする課題】
しかしながら、石炭系または石油系のコークスは、初期充電容量は高いものの、その後の充・放電容量はカーボンの理論容量として提唱されている値（３７２ｍＡｈ／ｇ）の約半分程度で、電池を作成しても充・放電容量が充分満足するものでなく、高容量化への改質が望まれている。
【０００４】
【課題を解決するための手段】
本発明者等は、上記の課題を解決すべく鋭意検討した結果、本発明に到達した。
すなわち、本発明の要旨は、正極、負極および非水溶媒中に電解質を溶解させた電解液を備えてなる非水系二次電池において、４００〜７００℃の熱履歴を受けたコークスを、粉砕された状態で、かつ不活性ガス雰囲気中で９００〜１５００℃の温度で加熱処理したものを負極材料としてなることを特徴とする非水系二次電池にある。
【０００５】
以下、本発明を詳細に説明する。
まず本発明において用いられるコークスとしては、ＦＣＣ（流動接触分解）残渣油、ＥＨＥ油（エチレン製造時の副生物）、常圧残渣油、減圧残渣油等の石油系重質油やコールタール、コールタールピッチ等の石炭系重質油をディレードコーカー、オートクレーブ等により４００〜５００℃程度の温度でコーキングした生コークス、さらにはこの生コークスをロータリーキルン、電気炉等により７００°以下の温度で仮焼した仮焼コークスが挙げられる。
【０００６】
本発明の電池は、負極材料としてコークスを用いることを特徴とし、かつ該コークスは、以下に述べるように、４００〜７００℃の熱履歴を受けたコークスを粉砕された状態において不活性ガス雰囲気中で、９００〜１５００℃の温度で加熱処理されたものでなければならない。
該加熱処理前の熱履歴は４００〜７００℃でなければならず、熱履歴は低いほうが好ましいが、熱処理温度が４００℃未満のコークスはアントラセン油等の油分や未炭化のピッチ分を多く含んでおり、９００〜１５００℃の加熱処理の際、それらが、急激に炭化し結晶性が低く、かつ多孔質の炭素になるため、電池特性が悪化することになる。一方、７００℃を超える温度で熱履歴を受けたものは、本発明の粉砕された状態での９００〜１５００℃の加熱処理に対し、ほとんど効果がない。
【０００７】
すなわち、本発明においては、コークス中の未処理有機質を効率良く、コークス内から除去するかが重要であり、７００℃を超える熱履歴を受けたものがほとんど効果がないのは未処理有機質が７００℃を超える温度で電池特性に対して好ましくない炭素に変質したものと思われる。また、４００℃未満の熱履歴を受けたものは未処理有機質含有量が多すぎ、次工程の不活性雰囲気中、９００〜１５００℃の処理で未処理有機質が十分に除去できず、一部に未処理有機質の急速に炭化したものが残るためと思われる。
【０００８】
また、本発明において、９００〜１５００℃の加熱処理に供する粉砕されたコークスの粒径は、通常１ｍｍ以下程度から選ばれる。最大粒径が１００μｍ以下であることが好ましく、５０μｍ以下であるとさらに好ましい。
また、不活性ガスとしては、窒素ガス、アルゴンガス、ヘリウムガス等が挙げられるが、実用的には窒素が好ましい。該流量は、焼成炉の形式、コークスの充填状態、コークス量、コークスの粒径、コークスの熱履歴、不活性ガスの吹き込み状態、炉の換気状況、炉内圧力、焼成温度等に応じて、未処理有機質が炭化せずに除去できるように適宜設定すればよく、特に限定されない。
【０００９】
また、最後の加熱処理（焼成）は、９００〜１５００℃で行われる。９００℃未満では、初期充電容量に対する２回目以降の充放電容量の比が低く、１５００℃を超える温度では容量が低下してしまう。そして、９００〜１５００℃の温度範囲内では、加熱温度が高ければ加熱時間は相対的に短くてよく、逆に加熱温度が低ければ加熱時間を長くすればよい。
【００１０】
本発明においては、このようにして得られたコークスを非水系二次電池の負極材料として用いられる。
正極および非水溶媒中に電解質を溶解させてなる電解液については、従来、非水系二次電池に用いられているものでよく、特に限定されない。具体的には、正極としては、ＬｉＣｏＯ２ 、ＭｎＯ２ 、ＴｉＳ２ 、ＦｅＳ２ 、Ｎｂ３ Ｓ４ 、Ｍｏ３ Ｓ４ 、ＣｏＳ２ 、Ｖ２ Ｏ５ 、Ｐ２ Ｏ５ 、ＣｒＯ３ 、Ｖ３ Ｏ３ 、ＴｅＯ２ 、ＧｅＯ２ 等が、電解質としては、ＬｉＣｌＯ４ 、ＬｉＢＦ４ 、ＬｉＰＦ６ 等が、電解液を溶解する非水溶媒としては、プロピレンカーボネート、テトラヒドロフラン、１，２−ジメトキシエタン、ジメチルスルホキシド、ジオキソラン、ジメチルホルムアミド、ジメチルアセトアミド、およびこれらの２種以上の混合溶媒等が用いられる。
【００１１】
中でも、最も好ましい組合せは、ＬｉＣｏＯ２ −ＬｉＰＦ６ −プロピレンカーボネートと１，２−ジメトキシエタンである。
セパレータは、電池の内部抵抗を小さくするために多孔体が好適であり、ポリプロピレン等の不織布、ガラスフィルターなどの耐有機溶媒性材料のものが用いられる。
これらの負極、正極、電解液及びセパレータは、たとえばステンレススチールまたはこれにニッケルメッキした電池ケースに組み込むのが一般的である。
【００１２】
電池構造としては、帯状の正極、負極をセパレータを介してうず巻き状にしたスパイラル構造またはボタン型ケースにペレット状の正極、円盤状の負極をセパレータを介して挿入する方法などが採用される。
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例によって限定されるものでない。
【００１３】
【実施例】
（実施例１）
コールタールピッチをオートクレーブで４８０℃、３０時間熱処理して、生コークスを得た。該生コークスをハンマーミルにて４４μｍ以下に粉砕し、窒素気流中、１１００℃にて３時間焼成し本発明のコークスを得た。
図１に本発明の実施例としてのボタン型非水系二次電池の半断面図を示す。ここで、負極１は本発明のコークスから構成される。この負極は、負極集電体２の内面に接合されており、この集電体２はフェライト系ステンレス鋼（ＳＵＳ４３０）からなる負極缶３の内部に固着されている。
【００１４】
前記負極缶３の周端は、ポリプロピレン製の絶縁パッキング４の内部に固定されており、絶縁パッキング４の外周には、ステンレスからなる前記負極缶３とは反対方向に正極缶５が固定されている。この正極缶５の内底面には正極集電体６が固定されており、この正極集電体６の内面には正極７が固定されている。この正極７と前記負極１との間には、セパレータが介在されており、ここには電解質が溶解された電解液が含浸されている。
【００１５】
そして、前記負極は本発明コークスとポリプロピレン粉末と９０：１０の重量比で混合したものを加圧成形して作成した。また、正極はＬｉＣｏＯ２ と導電剤としてのアセチレンブラックと結着剤としてのフッ素樹脂とを、８５：１０：５の重量比で混合したものを加圧成形して作成した。
また、電解液にはプロピレンカーボネート（ＰＣ）に、電解質としてＬｉＰＦ６ を１モル／リットルの割合で溶解したものを用いた。尚、この電池の容量に関しては、正極に比べて、負極を十分小さくし、負極支配になるように設定している。この電池を充電電流及び放電電流１ｍＡ／ｃｍ２ とし、充電は３．６Ｖまで、放電は２．５Ｖまで行った。結果を表１に示す。
【００１６】
（実施例２）
実施例１の生コークス粉を不活性雰囲気下で６００℃加熱処理後、窒素気流中１１００℃にて３時間焼成後、実施例１と同様の評価をした。結果を表１に示す。
（比較例１）
実施例１の生コークス粉を不活性雰囲気下で８００℃加熱処理後、窒素気流中１１００℃にて３時間焼成後、実施例１と同様の評価をした。結果を表１に示す。
（比較例２）
実施例１の生コークス粉を窒素気流中１６００℃にて３時間焼成後、実施例１と同様の評価をした。結果を表１に示す。
【００１７】
【表１】
【発明の効果】
本発明によれば、低コストのコークスを負極材料として、充・放電容量の大きな非水系二次電池を提供しうる。
【図面の簡単な説明】
【図１】本発明非水二次電池の一例であるボタン型非水電解液二次電池の断面説明図である。
【符号の説明】
１ 負極
２ 負極集電体
３ 負極缶
４ 絶縁パッキング
５ 正極缶
６ 正極集電体
７ 正極[0001]
[Industrial applications]
The present invention relates to a non-aqueous secondary battery. More specifically, the present invention relates to a non-aqueous secondary battery such as a lithium secondary battery, which is particularly suitable for small and lightweight electronic devices.
[0002]
[Prior art]
In recent years, from the standpoint of reducing the size and weight of electronic devices and the like, saving power and protecting the environment, clean non-aqueous batteries, particularly lithium secondary batteries, replacing lead-acid batteries and nickel-cadmium batteries have attracted attention and have reached the stage of practical use. However, when lithium metal is used for the negative electrode, there is a problem that the lithium metal grows in a dendrite shape during charging, causing an internal short circuit. As a countermeasure, a material capable of absorbing and releasing lithium metal atoms has been actively developed, and among them, a material using coke is considered to be promising in terms of low cost and high capacity (Japanese Patent Laid-Open No. Sho 62). -90863, JP-A-1-221859, JP-A-63-12257).
[0003]
[Problems to be solved by the invention]
However, although coal-based or petroleum-based coke has a high initial charge capacity, the subsequent charge / discharge capacity is about half of the value (372 mAh / g) proposed as the theoretical capacity of carbon, and a battery is prepared. However, the charge / discharge capacity is not sufficiently satisfied, and reforming to a higher capacity is desired.
[0004]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the gist of the present invention is that in a non-aqueous secondary battery including a positive electrode, a negative electrode, and an electrolyte solution in which an electrolyte is dissolved in a non-aqueous solvent, coke that has received a heat history of 400 to 700 ° C. is pulverized. A non-aqueous secondary battery characterized in that a material subjected to a heat treatment at a temperature of 900 to 1500 ° C. in an inert gas atmosphere in an inert gas atmosphere is used as a negative electrode material.
[0005]
Hereinafter, the present invention will be described in detail.
First, as the coke used in the present invention, petroleum heavy oils such as FCC (fluid catalytic cracking) residual oil, EHE oil (by-product of ethylene production), atmospheric residual oil, and vacuum residual oil, coal tar, coal Raw coke obtained by coking heavy coal oil such as tar pitch with a delayed coker or autoclave at a temperature of about 400 to 500 ° C. Further, this raw coke is calcined at a temperature of 700 ° or less by a rotary kiln, an electric furnace or the like. And calcined coke.
[0006]
The battery of the present invention is characterized in that coke is used as a negative electrode material, and the coke is subjected to a heat history of 400 to 700 ° C. in an inert gas atmosphere in a crushed state, as described below. And heat-treated at a temperature of 900 to 1500 ° C.
The heat history before the heat treatment must be 400 to 700 ° C., and the heat history is preferably low. However, coke having a heat treatment temperature of less than 400 ° C. contains a large amount of oil such as anthracene oil and uncarbonized pitch. At the time of heat treatment at 900 to 1500 ° C., these are rapidly carbonized and have low crystallinity and become porous carbon, so that battery characteristics are deteriorated. On the other hand, those subjected to a heat history at a temperature exceeding 700 ° C. have almost no effect on the heat treatment at 900 to 1500 ° C. in the pulverized state of the present invention.
[0007]
That is, in the present invention, it is important to efficiently remove the untreated organic matter in the coke from the coke. Those that have received a heat history exceeding 700 ° C. have almost no effect because the untreated organic matter is 700%. It is considered that the carbon changed to carbon which is not preferable for battery characteristics at a temperature exceeding ℃. Further, those that have received a heat history of less than 400 ° C. have too much untreated organic content, and the untreated organics cannot be sufficiently removed by the treatment at 900 to 1500 ° C. in an inert atmosphere in the next step, and some This is probably because untreated organic matter rapidly carbonized remains.
[0008]
In the present invention, the particle size of the pulverized coke subjected to the heat treatment at 900 to 1500 ° C. is usually selected from about 1 mm or less. The maximum particle size is preferably 100 μm or less, and more preferably 50 μm or less.
Examples of the inert gas include a nitrogen gas, an argon gas, a helium gas, and the like. Nitrogen is preferred for practical use. The flow rate depends on the type of the firing furnace, the filling state of coke, the amount of coke, the particle size of coke, the heat history of coke, the blowing state of inert gas, the state of ventilation of the furnace, the pressure in the furnace, the firing temperature, etc. There is no particular limitation as long as it is set appropriately so that untreated organic matter can be removed without carbonization.
[0009]
The final heat treatment (firing) is performed at 900 to 1500 ° C. When the temperature is lower than 900 ° C., the ratio of the charge / discharge capacity for the second and subsequent times to the initial charge capacity is low, and at a temperature higher than 1500 ° C., the capacity decreases. In the temperature range of 900 to 1500 ° C., the heating time may be relatively short if the heating temperature is high, and the heating time may be long if the heating temperature is low.
[0010]
In the present invention, the coke thus obtained is used as a negative electrode material of a non-aqueous secondary battery.
The electrolyte solution obtained by dissolving the electrolyte in the positive electrode and the non-aqueous solvent may be one conventionally used in non-aqueous secondary batteries, and is not particularly limited. Specifically, as the positive electrode, LiCoO 2 , MnO 2 , TiS 2 , FeS 2 , Nb 3 S 4 , Mo 3 S 4 , CoS 2 , V 2 O 5 , P 2 O 5 , CrO 3 , V 3 O 3 , TeO 2 , GeO 2, etc .; LiClO 4 , LiBF 4 , LiPF 6, etc. as the electrolyte; and propylene carbonate, tetrahydrofuran, 1,2-dimethoxyethane, dimethyl sulfoxide as the non-aqueous solvent in which the electrolytic solution is dissolved. , Dioxolane, dimethylformamide, dimethylacetamide, and a mixed solvent of two or more thereof.
[0011]
Of these, the most preferred combination, LiCoO 2 -LiPF 6 - propylene carbonate and 1,2-dimethoxyethane.
The separator is preferably made of a porous material in order to reduce the internal resistance of the battery, and is made of a nonwoven fabric such as polypropylene or an organic solvent-resistant material such as a glass filter.
The negative electrode, the positive electrode, the electrolytic solution and the separator are generally incorporated in a battery case made of, for example, stainless steel or nickel plated.
[0012]
As the battery structure, a spiral structure in which a strip-shaped positive electrode and a negative electrode are spirally wound with a separator interposed therebetween, or a method in which a pellet-shaped positive electrode and a disc-shaped negative electrode are inserted into a button-shaped case through a separator are adopted.
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
[0013]
【Example】
(Example 1)
The coal tar pitch was heat-treated in an autoclave at 480 ° C. for 30 hours to obtain raw coke. The raw coke was pulverized with a hammer mill to 44 μm or less and calcined at 1100 ° C. for 3 hours in a nitrogen stream to obtain the coke of the present invention.
FIG. 1 is a half sectional view of a button type non-aqueous secondary battery as an embodiment of the present invention. Here, the negative electrode 1 is composed of the coke of the present invention. This negative electrode is bonded to the inner surface of the negative electrode current collector 2, and the current collector 2 is fixed inside the negative electrode can 3 made of ferritic stainless steel (SUS430).
[0014]
A peripheral end of the negative electrode can 3 is fixed inside a polypropylene insulating packing 4, and a positive electrode can 5 is fixed to an outer periphery of the insulating packing 4 in a direction opposite to the negative electrode can 3 made of stainless steel. I have. A positive electrode
[0015]
The negative electrode was prepared by pressure molding a mixture of the coke of the present invention and polypropylene powder at a weight ratio of 90:10. The positive electrode was prepared by pressure-forming a mixture of LiCoO 2 , acetylene black as a conductive agent, and a fluororesin as a binder at a weight ratio of 85: 10: 5.
Further, as the electrolytic solution, a solution obtained by dissolving LiPF 6 as an electrolyte at a rate of 1 mol / liter in propylene carbonate (PC) was used. Note that the capacity of the battery is set so that the size of the negative electrode is sufficiently smaller than that of the positive electrode so that the battery is dominated by the negative electrode. This battery was set to a charging current and a discharging current of 1 mA / cm 2, and charged up to 3.6 V and discharged up to 2.5 V. Table 1 shows the results.
[0016]
(Example 2)
The raw coke powder of Example 1 was subjected to a heat treatment at 600 ° C. in an inert atmosphere, and then calcined at 1100 ° C. for 3 hours in a nitrogen stream, followed by the same evaluation as in Example 1. Table 1 shows the results.
(Comparative Example 1)
The raw coke powder of Example 1 was subjected to a heat treatment at 800 ° C. in an inert atmosphere, and then calcined at 1100 ° C. for 3 hours in a nitrogen stream, followed by the same evaluation as in Example 1. Table 1 shows the results.
(Comparative Example 2)
After the raw coke powder of Example 1 was calcined at 1600 ° C. for 3 hours in a nitrogen stream, the same evaluation as in Example 1 was performed. Table 1 shows the results.
[0017]
[Table 1]
【The invention's effect】
According to the present invention, a non-aqueous secondary battery having a large charge / discharge capacity can be provided using low-cost coke as a negative electrode material.
[Brief description of the drawings]
FIG. 1 is an explanatory cross-sectional view of a button-type nonaqueous electrolyte secondary battery which is an example of the nonaqueous secondary battery of the present invention.
[Explanation of symbols]
Reference Signs List 1 negative electrode 2 negative electrode current collector 3 negative electrode can 4 insulating packing 5 positive electrode can 6 positive electrode current collector 7 positive electrode
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23786594A JP3551490B2 (en) | 1994-09-30 | 1994-09-30 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23786594A JP3551490B2 (en) | 1994-09-30 | 1994-09-30 | Non-aqueous secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JPH08102324A JPH08102324A (en) | 1996-04-16 |
| JP3551490B2 true JP3551490B2 (en) | 2004-08-04 |
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| JP23786594A Expired - Fee Related JP3551490B2 (en) | 1994-09-30 | 1994-09-30 | Non-aqueous secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3577776B2 (en) * | 1995-04-18 | 2004-10-13 | 三菱化学株式会社 | Non-aqueous secondary battery |
| US5958622A (en) * | 1996-03-28 | 1999-09-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Negative electrode material for lithium secondary batteries |
| US20070009418A1 (en) * | 2003-09-09 | 2007-01-11 | Japan Energy Corporation | Nonaqueous electrolyte secondary cell, carbon material for use therein and precursor of said carbon material |
| JP5662698B2 (en) | 2009-05-15 | 2015-02-04 | 新日鉄住金化学株式会社 | Negative electrode active material for lithium secondary battery and in-vehicle lithium secondary battery using the same |
| JP5603589B2 (en) * | 2009-05-15 | 2014-10-08 | 新日鉄住金化学株式会社 | Negative electrode active material for lithium secondary battery and in-vehicle lithium secondary battery using the same |
| JP5697954B2 (en) | 2010-11-12 | 2015-04-08 | 新日鉄住金化学株式会社 | Negative electrode active material for lithium secondary battery and lithium secondary battery using the same |
| JP6444106B2 (en) * | 2014-09-19 | 2018-12-26 | コスモ石油株式会社 | Pigment, composition containing pigment and method for producing pigment |
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| JP3395200B2 (en) * | 1992-04-28 | 2003-04-07 | 三洋電機株式会社 | Non-aqueous secondary battery |
| JP2518771B2 (en) * | 1992-06-03 | 1996-07-31 | 興亜石油株式会社 | Non-aqueous secondary battery and negative electrode material for non-aqueous secondary battery |
| JPH0644958A (en) * | 1992-07-27 | 1994-02-18 | Fuji Elelctrochem Co Ltd | Manufacture of negative electrode for lithium secondary battery |
| JPH06236755A (en) * | 1992-12-16 | 1994-08-23 | Osaka Gas Co Ltd | Negative electrode material, its manufacture, and lithium secondary battery |
| JPH06187974A (en) * | 1992-12-16 | 1994-07-08 | Osaka Gas Co Ltd | Negative electrode material, manufacturing method thereof, and lithium secondary battery |
| JP3416180B2 (en) * | 1993-01-12 | 2003-06-16 | エフ・ディ−・ケイ株式会社 | Lithium secondary battery |
| JPH07302594A (en) * | 1994-05-09 | 1995-11-14 | Asahi Organic Chem Ind Co Ltd | Carbonaceous particles and negative electrode for lithium ion secondary battery using the same |
| JPH07307164A (en) * | 1994-05-11 | 1995-11-21 | Asahi Chem Ind Co Ltd | Lithium ion secondary battery |
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