JP3577776B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
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- JP3577776B2 JP3577776B2 JP9260695A JP9260695A JP3577776B2 JP 3577776 B2 JP3577776 B2 JP 3577776B2 JP 9260695 A JP9260695 A JP 9260695A JP 9260695 A JP9260695 A JP 9260695A JP 3577776 B2 JP3577776 B2 JP 3577776B2
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- 239000000571 coke Substances 0.000 claims description 27
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004939 coking Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 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
- 239000003125 aqueous solvent Substances 0.000 description 3
- -1 etc. Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 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
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010959 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (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初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、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２／３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】
本発明者は、上記の課題を解決すべく種々検討を行ない、コーキング後の生コークス中の揮発分は初期充電容量を大きくするが、揮発分の炭化により生成される成分自体がコークスの容量の発現を阻害していること、さらに生コークスを微粉砕した後に仮焼すれば、揮発分を効率的に除去でき、揮発分炭化成分の残留も抑制できることを見出し、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、生コークスを微粉砕し、ついで不活性ガス雰囲気下に７００〜１，５００℃の温度で加熱処理したコークス、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。
以下、本発明を詳細に説明する。
【０００５】
まず本発明において用いられる生コークスとしては、ＦＣＣ（流動接触分解）残渣油、ＥＨＥ油（エチレン製造時の副生油）、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キルン、電気炉等により７００°未満の温度で仮焼した生コークスが挙げられる。
【０００６】
本発明におけるこのような生コークスは、好適には、揮発分が１５重量％以下、さらに好ましくは１０重量％以下であるものが用いられる。揮発分が１５重量％より多くなると、微粉砕した後に加熱処理しても除去されにくくなり、また微粉砕の際に粉塵爆発の恐れが生じうるからである。
本発明においては、後述する加熱処理に先立ち、この生コークスを微粉砕することが必要である。粉砕は、平均粒径が５００μｍ以下、好ましくは１００μｍ以下、より好ましくは５０μｍ以下となるように行なわれる。粉砕方法自体は、常法によることができるが、たとえばジェットミルを用いるのが好適である。なお、最大粒径は実質的に１ｍｍ以上のものを含まないようにするのが、揮発分の除去効率の点から好ましい。
【０００７】
そして、本発明においては、これらの微粉砕した生コークスは不活性ガス雰囲気下で７００〜１，５００℃の温度で加熱処理される。加熱は、ロータリーキルン、電気炉等により行なわれ、特に制限されない。加熱処理は、実質的に不活性雰囲気であることが必要であり、好ましくは８００〜１，２００℃の温度で行なわれる。
また、この加熱処理に際しては、揮発分の除去が行なわれやすいように、５０ｍｍ以下程度の薄い積層状態にしたり、撹拌等により微粉表面が気中にさらされるようにする、のが好適である。また、減圧下に加熱したり、不活性ガスをスイープしたりしてもよい。７００〜１，５００℃の温度で加熱処理されたコークスの揮発分は特に限定されないが、２回目以降の充・放電容量の点を考慮すると、０．１〜１．０ｗｔ％程度が好適である。得られたコークスは、リチウムイオン二次電池等非水系二次電池の負極材として用いられる。
【０００８】
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 Ｏ８ 、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。
【０００９】
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。
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。
【００１０】
【実施例】
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、以下実施例によって限定されるものでない。
実施例１
コールタールをコークドラムで、４５０〜５００℃で、２４時間コーキングして得た、揮発分５．８％の生コークスを、ジェットミルにて微粉砕して、平均８．８μｍ、最大粒度３５μｍ以下の生コークス微粉を得た。
この生コークス微粉を黒鉛製のトレイ中に入れ、箱型の電気炉中で窒素雰囲気下、昇温速度約１０℃／分で昇温して、表１に示すとおり６００〜１２００℃で２時間保持して加熱処理して、負極材料を得た。得られた負極材料を図１に示す構成のセルを使用してその性能を評価した。
負極材料は、１０％のＰＶＤＦ（ポリ弗化ビニリデン）をバインダーとして使用し、１５ｍｍφのステンレス金鋼上に圧着して負極（１）とした。対極としてはＬｉ金属箔を使用し、同じく１５ｍｍφのステンレス金鋼上に圧着して正極（３）とした。
【００１１】
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（２はセパレータと電解液を示す）。尚、この電池の容量に関しては正極に対して負極を十分に小さくしている。（４）はステンレス製の電池筐体、（５）は絶縁体（ポリ四フッ化エチレン製）、（６）は充放電端子である。
この電池を充電電流０．５ｍＡ／ｃｍ２ で、電圧（対Ｌｉ極）が０．０１Ｖになるまで充電し、さらに０．０１Ｖの電圧を保ったまま、充電電流が０．０３ｍＡ／ｃｍ２ 以下になるまで充電を続けた。次いで、放電電流０．５ｍＡ／ｃｍ２ で１．５Ｖまでの放電を行なった。容量（放電容量）と効率（放電容量／初充電容量）の結果を表−１に示す。
【００１２】
【表１】
比較例１
実施例１で得た生コークスを３０〜１５０ｍｍの大きさの塊状のまま、実施例１の場合と同じ様に加熱処理した。次いで、得られた加熱処理コークスをジェットミルで微粉砕し、平均９．４μｍ、最大粒度３５μｍ以下の負極材料を得た。実施例１と同様の電池性能評価をした結果を表−２に示す。
【００１４】
【表２】
【発明の効果】
本発明によれば、低コストのコークスから容易に、充・放電容量の大きな非水系二次電池用の負極材を提供しうる。
【図面の簡単な説明】
【図１】本発明の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
３ 正極
４ 電池筐体
５ 絶縁体
６ 充放電端子[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, coal-based or petroleum-based coke has a high initial charge capacity, but the subsequent charge / discharge capacity is about two-thirds of the value (372 mAh / g) proposed as the theoretical capacity of carbon. 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 inventor has conducted various studies in order to solve the above-mentioned problem, and the volatile matter in the raw coke after coking increases the initial charge capacity, but the component itself generated by carbonization of the volatile matter itself has a capacity of the coke. The present inventors have found that the expression is inhibited, and that if the raw coke is finely pulverized and calcined, volatile components can be efficiently removed and the residual carbonized components can be suppressed, and the present invention has been achieved.
That is, the gist of the present invention is to finely pulverize raw coke in a non-aqueous secondary battery including an electrolyte solution in which an electrolyte is dissolved in a positive electrode, a negative electrode, and a non-aqueous solvent. A non-aqueous secondary battery characterized in that coke heat-treated at a temperature of about 1,500 ° C. is used as a negative electrode material.
Hereinafter, the present invention will be described in detail.
[0005]
First, raw coke used in the present invention includes petroleum heavy oils such as FCC (fluid catalytic cracking) residual oil, EHE oil (by-product oil at the time of ethylene production), atmospheric residual oil, and vacuum residual oil, and coal tar. Raw coke obtained by coking heavy coal oil such as coal tar pitch at a temperature of about 400 to 500 ° C. by a delayed coker, an autoclave or the like, and furthermore, a temperature of less than 700 ° by a raw kiln using a rotary kiln, an electric furnace or the like. Raw coke calcined at
[0006]
Such raw coke in the present invention preferably has a volatile content of 15% by weight or less, more preferably 10% by weight or less. If the volatile matter content is more than 15% by weight, it is difficult to remove the fine particles by heat treatment after pulverization, and there is a possibility of dust explosion during the fine pulverization.
In the present invention, it is necessary to finely pulverize the raw coke prior to the heat treatment described below. The pulverization is performed so that the average particle size is 500 μm or less, preferably 100 μm or less, and more preferably 50 μm or less. The pulverization method itself can be performed by a conventional method, but for example, it is preferable to use a jet mill. It is preferable that the maximum particle diameter does not substantially include a particle diameter of 1 mm or more from the viewpoint of the efficiency of removing volatile components.
[0007]
And in this invention, these finely ground raw coke is heat-processed at 700-1500 degreeC in inert gas atmosphere. The heating is performed by a rotary kiln, an electric furnace, or the like, and is not particularly limited. The heat treatment needs to be substantially in an inert atmosphere, and is preferably performed at a temperature of 800 to 1,200 ° C.
In this heat treatment, it is preferable to form a thin layer having a thickness of about 50 mm or less or to expose the fine powder surface to the air by stirring or the like so that volatile components can be easily removed. Further, heating may be performed under reduced pressure, or an inert gas may be swept. The volatile matter content of the coke heat-treated at a temperature of 700 to 1,500 ° C. is not particularly limited, but is preferably about 0.1 to 1.0 wt% in consideration of the charge / discharge capacity after the second time. . The obtained coke is used as a negative electrode material of a non-aqueous secondary battery such as a lithium ion secondary battery.
[0008]
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 8 , TeO 2 , GeO 2, etc., LiClO 4 , LiBF 4 , LiPF 6, etc. as the electrolyte, and propylene carbonate, tetrahydrofuran, 1,2-dimethoxyethane, dimethylsulfoxide as the non-aqueous solvent in which the electrolyte is dissolved , Dioxolane, dimethylformamide, dimethylacetamide, and a mixed solvent of two or more thereof.
[0009]
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.
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.
[0010]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples below unless it exceeds the gist thereof.
Example 1
Raw coke having a volatile content of 5.8%, obtained by coking coal tar with a coke drum at 450 to 500 ° C. for 24 hours, is finely pulverized with a jet mill to an average of 8.8 μm and a maximum particle size of 35 μm or less. Raw coke fine powder was obtained.
This raw coke fine powder is placed in a graphite tray, and heated in a box-type electric furnace under a nitrogen atmosphere at a heating rate of about 10 ° C./minute, and at 600 to 1200 ° C. for 2 hours as shown in Table 1. By holding and heat-treating, a negative electrode material was obtained. The performance of the obtained negative electrode material was evaluated using a cell having the configuration shown in FIG.
As the negative electrode material, 10% PVDF (polyvinylidene fluoride) was used as a binder, and pressed on a 15 mmφ stainless steel steel to obtain a negative electrode (1). A Li metal foil was used as a counter electrode, which was similarly pressed on a stainless steel steel of 15 mmφ to obtain a positive electrode (3).
[0011]
As the electrolytic solution, a solution obtained by dissolving LiPF 6 as an electrolyte at a ratio of 1 mol / liter in propylene carbonate (PC) was used (2 indicates a separator and an electrolytic solution). In addition, regarding the capacity of this battery, the negative electrode is made sufficiently smaller than the positive electrode. (4) is a battery case made of stainless steel, (5) is an insulator (made of polytetrafluoroethylene), and (6) is a charge / discharge terminal.
This battery was charged at a charging current of 0.5 mA / cm 2 until the voltage (with respect to the Li electrode) became 0.01 V. Further, while maintaining the voltage of 0.01 V, the charging current was 0.03 mA / cm 2 or less. Charging was continued until. Next, discharge was performed up to 1.5 V at a discharge current of 0.5 mA / cm 2 . Table 1 shows the results of the capacity (discharge capacity) and efficiency (discharge capacity / initial charge capacity).
[0012]
[Table 1]
Comparative Example 1
The raw coke obtained in Example 1 was subjected to a heat treatment in the same manner as in Example 1 while maintaining a lump having a size of 30 to 150 mm. Next, the obtained heat-treated coke was finely pulverized with a jet mill to obtain a negative electrode material having an average of 9.4 μm and a maximum particle size of 35 μm or less. Table 2 shows the result of the same battery performance evaluation as in Example 1.
[0014]
[Table 2]
【The invention's effect】
According to the present invention, it is possible to easily provide a negative electrode material for a non-aqueous secondary battery having a large charge / discharge capacity from low-cost coke.
[Brief description of the drawings]
FIG. 1 is an explanatory cross-sectional view of a button-type non-aqueous electrolyte secondary battery which is an example of the non-aqueous secondary battery of the present invention.
[Explanation of symbols]
1
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9260695A JP3577776B2 (en) | 1995-04-18 | 1995-04-18 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9260695A JP3577776B2 (en) | 1995-04-18 | 1995-04-18 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08287911A JPH08287911A (en) | 1996-11-01 |
| JP3577776B2 true JP3577776B2 (en) | 2004-10-13 |
Family
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| Application Number | Title | Priority Date | Filing Date |
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| JP9260695A Expired - Lifetime JP3577776B2 (en) | 1995-04-18 | 1995-04-18 | Non-aqueous secondary battery |
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| JP (1) | JP3577776B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6150055A (en) * | 1997-08-05 | 2000-11-21 | Mitsubishi Chemical Corporation | Carbonaceous negative electrode material for nonaqueous secondary battery, process for producing the same, and nonaqueous secondary battery |
| 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 |
| JP5242210B2 (en) * | 2008-03-24 | 2013-07-24 | 新日鉄住金化学株式会社 | Non-aqueous electrolyte secondary battery negative electrode active material and method for producing non-aqueous electrolyte secondary battery |
| 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 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5861562A (en) * | 1981-10-08 | 1983-04-12 | Matsushita Electric Ind Co Ltd | Production method of anode active material for cell |
| JPH01221859A (en) * | 1988-02-29 | 1989-09-05 | Sony Corp | Secondary battery |
| JP3054473B2 (en) * | 1991-10-08 | 2000-06-19 | 三洋電機株式会社 | Rechargeable battery |
| 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 |
| JP3568563B2 (en) * | 1993-09-03 | 2004-09-22 | 呉羽化学工業株式会社 | Carbonaceous material for secondary battery electrode and method for producing the same |
| JPH07307164A (en) * | 1994-05-11 | 1995-11-21 | Asahi Chem Ind Co Ltd | Lithium ion secondary battery |
| FR2724490B1 (en) * | 1994-09-09 | 1996-10-25 | Lorraine Carbone | CARBON / POLYMER COMPOSITE ELECTRODE FOR LITHIUM RECHARGEABLE ELECTROCHEMICAL GENERATOR |
| JPH08102318A (en) * | 1994-09-30 | 1996-04-16 | Mitsubishi Chem Corp | Non-aqueous secondary battery |
| JP3551490B2 (en) * | 1994-09-30 | 2004-08-04 | 三菱化学株式会社 | Non-aqueous secondary battery |
| JPH08102319A (en) * | 1994-09-30 | 1996-04-16 | Mitsubishi Chem Corp | Non-aqueous secondary battery |
| JPH08287912A (en) * | 1995-04-18 | 1996-11-01 | Mitsubishi Chem Corp | Non-aqueous secondary battery |
-
1995
- 1995-04-18 JP JP9260695A patent/JP3577776B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| JPH08287911A (en) | 1996-11-01 |
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