JP2518771B2 - Non-aqueous secondary battery and negative electrode material for non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery and negative electrode material for non-aqueous secondary batteryInfo
- Publication number
- JP2518771B2 JP2518771B2 JP4170236A JP17023692A JP2518771B2 JP 2518771 B2 JP2518771 B2 JP 2518771B2 JP 4170236 A JP4170236 A JP 4170236A JP 17023692 A JP17023692 A JP 17023692A JP 2518771 B2 JP2518771 B2 JP 2518771B2
- Authority
- JP
- Japan
- Prior art keywords
- coke
- surface area
- secondary battery
- specific surface
- aqueous secondary
- 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.)
- Expired - Fee Related
Links
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- 239000000571 coke Substances 0.000 claims description 52
- 230000004913 activation Effects 0.000 claims description 21
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水系二次電池及び非
水系二次電池用負極材料に係わり、詳しくは負極材料と
してコークスを使用した非水系二次電池の当該コークス
の改良に関する。The present invention relates to a non-aqueous secondary battery and a non -aqueous secondary battery.
The present invention relates to a negative electrode material for a water-based secondary battery, and more specifically, to improvement of the coke in a non-aqueous secondary battery using coke as a negative electrode material.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
非水系二次電池の負極材料として、コークスが、可撓性
に優れること、モッシー状のリチウムが電析するおそれ
がないことなどの理由から、従来のリチウム金属に代わ
る材料として提案されている。2. Description of the Related Art
As a negative electrode material for a non-aqueous secondary battery, coke has been proposed as a material that replaces conventional lithium metal because of its excellent flexibility and the fact that mossy lithium is not likely to be electrodeposited.
【０００３】コークスは、非水系二次電池において、充
電時に細孔内や層間にリチウムを吸蔵し、放電時にその
吸蔵したリチウムを放出するところの、いわば充放電時
のリチウムイオン授受のための負極側ホストとして機能
するものである。In a non-aqueous secondary battery, coke occludes lithium in the pores or between layers during charging and releases the occluded lithium during discharging, so to speak, a negative electrode for giving and receiving lithium ions during charging and discharging. It functions as the host on the side.
【０００４】しかしながら、コークスの単位重量当たり
の容量は、ピッチコークス等の石油系コークスであるか
石炭系コークスであるかを問わず、通常１５０〜２００
ｍＡｈ／ｇ程度であり、充電間隔の長期化が求められて
いる非水系二次電池の負極材料としては未だ充分な容量
を有するものとは言い難い。However, the capacity per unit weight of coke is usually 150 to 200, regardless of whether it is petroleum-based coke such as pitch coke or coal-based coke.
It is about mAh / g, and it is hard to say that it has a sufficient capacity as a negative electrode material for a non-aqueous secondary battery in which a long charging interval is required.
【０００５】そこで、鋭意研究した結果、本発明者ら
は、コークスの容量とその比表面積及びＸ線回折パラメ
ータｄ002 （Ｘ線回折における格子面（００２）面のｄ
値）との間に、密接な関係が存在することを見出した。Then, as a result of intensive studies, the present inventors have found that the capacity of the coke and its specific surface area and the X-ray diffraction parameter d 002 (d of the lattice plane (002) plane in X-ray diffraction).
It has been found that there is a close relationship with (value).
【０００６】本発明は、かかる知見に基づきなされたも
のであって、その目的とするところは、電池容量の大き
い非水系二次電池及びそれに使用される非水系二次電池
用負極材料を提供するにある。The present invention was made on the basis of such findings, and an object of the present invention is to provide a non-aqueous secondary battery having a large battery capacity and a non-aqueous secondary battery used therein.
To provide a negative electrode material for use .
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水系二次電池（以下「本発明電池」と
称する。）は、負極材料として、ＢＥＴ法による比表面
積が１００ｍ２／ｇ以上であり、且つ、Ｘ線回折パラメ
ータｄ００２が３．３７Å以上であるコークスが使用さ
れてなる。また、本発明に係る非水系二次電池用負極材
料は、ＢＥＴ法による比表面積が１００ｍ ２ ／ｇ以上で
あり、且つ、Ｘ線回折パラメータｄ ００２ が３．３７Å
以上、Ｌｃが６００Å以下のコークスからなる。 A non-aqueous secondary battery according to the present invention (hereinafter referred to as "the present battery") for achieving the above object has a specific surface area of 100 m 2 by a BET method as a negative electrode material. Coke having an X-ray diffraction parameter d 002 of 3.37 Å or more is used. Further, the negative electrode material for a non-aqueous secondary battery according to the present invention
The material has a BET specific surface area of 100 m 2 / g or more.
Yes , and the X-ray diffraction parameter d 002 is 3.37Å
As described above, the coke has Lc of 600 Å or less.
【０００８】上記ＢＥＴ（Brunauer-Emmett-Teller）法
とは、吸着等温線上で単分子層吸着量を求め、吸着分子
の断面積から表面積を決定して比表面積を算出する方法
である。The BET (Brunauer-Emmett-Teller) method is a method of calculating the specific surface area by determining the adsorption amount of the monolayer on the adsorption isotherm and determining the surface area from the cross-sectional area of the adsorbed molecule.
【０００９】本発明電池において、コークスのＢＥＴ法
による比表面積が１００ｍ2 ／ｇ以上であり、且つ、Ｘ
線回折パラメータｄ002 が３．３７Å以上に限定される
のは、後述する実施例に示すように、コークスの比表面
積が１００ｍ2 ／ｇ未満、又は、Ｘ線回折パラメータｄ
002 が３．３７Å未満の場合は、容量が小さく、このた
め電池容量の大きい非水系二次電池が得られないからで
ある。また、さらにＸ線回折パラメータＬｃ（Ｘ線回折
におけるｃ軸方向の結晶子の大きさ）が６００Å以下の
ものが好ましい。In the battery of the present invention, the specific surface area of coke by the BET method is 100 m 2 / g or more, and X
The line diffraction parameter d 002 is limited to 3.37 Å or more because the specific surface area of coke is less than 100 m 2 / g, or the X-ray diffraction parameter d is
This is because when 002 is less than 3.37Å, the capacity is so small that a non-aqueous secondary battery having a large battery capacity cannot be obtained. Further, it is preferable that the X-ray diffraction parameter Lc (size of crystallite in the c-axis direction in X-ray diffraction) is 600 Å or less.
【００１０】通常のコークスの容量が小さい主な理由は
次の通りである。すなわち、コークスはその製造工程の
一つであるか焼工程において原料たる易黒鉛化炭素材料
をロータリーキルンにて１２００〜１４００°Ｃの温度
でか焼することにより作製されているが、か焼の際に炭
化水素（タール）が発生し、この炭化水素がコークスの
微小な細孔を閉塞してしまうため、充電時のリチウムイ
オンの細孔内への侵入が困難となりリチウム吸蔵放出量
が減少してしまうからである。因みに、生コークスの比
表面積は通常数十ｍ2 ／ｇ程度である。The main reasons why the capacity of ordinary coke is small are as follows. That is, coke is produced by calcining a graphitizable carbon material as a raw material in a calcination step, which is one of the manufacturing steps, in a rotary kiln at a temperature of 1200 to 1400 ° C. Hydrocarbons (tar) are generated in the pores, and these hydrocarbons block the minute pores of the coke, which makes it difficult for lithium ions to enter the pores during charging, reducing the amount of lithium storage and release. Because it will be. Incidentally, the specific surface area of raw coke is usually about several tens m 2 / g.
【００１１】本発明における高比表面積のコークスは、
たとえば活性炭の製造法としては既に公知である賦活処
理と同様の操作をコークスに施して細孔を閉塞している
炭化水素を酸化除去することにより得られる。なお、賦
活処理なる用語は、一般に活性炭の吸着能を高めるため
に細孔内面積を大きくする場合の操作をいうが、本明細
書では、同用語を、活性炭の賦活処理と同様の操作をコ
ークスの比表面積の増大化のために行うことを言うもの
と定義する。The high specific surface area coke in the present invention is
For example, as a method for producing activated carbon, the coke is subjected to the same operation as the already known activation treatment to oxidize and remove the hydrocarbon blocking the pores. Incidentally, the term activation treatment generally refers to an operation in the case of increasing the pore internal area in order to increase the adsorption capacity of activated carbon, but in the present specification, the term is the same operation as activated carbon activation coke. It is defined as what is done to increase the specific surface area of.
【００１２】賦活処理法により高比表面積のコークスを
製造する際の出発原料たる上記易黒鉛化炭素材料として
は、ピッチ類を加熱処理することにより得られる炭素質
メソフェースや、生コークスが好適である。As the above-mentioned graphitizable carbon material which is a starting material for producing a coke having a high specific surface area by an activation treatment method, carbonaceous mesophase obtained by heat-treating pitches and raw coke are suitable. .
【００１３】ところで、活性炭の賦活処理法には、大別
して、水蒸気、二酸化炭素、酸素、空気、塩素、二酸化
硫黄などのガスを使用するガス賦活法と、水酸化カリウ
ム、炭酸カリウム、塩化カルシウム、硫化カリウム、塩
化亜鉛、燐酸、燐酸塩などの薬品を原料に含浸させる薬
品賦活法とがあるが、本発明における比表面積の大きい
コークスを得るためには、これらいずれの方法をも使用
することができる。しかし、ガス賦活法の一種である水
蒸気を使用する賦活法が簡便さの点で有利である。The activated carbon activation treatment methods are roughly classified into gas activation methods using gases such as water vapor, carbon dioxide, oxygen, air, chlorine and sulfur dioxide, and potassium hydroxide, potassium carbonate, calcium chloride, There is a chemical activation method in which a raw material is impregnated with a chemical such as potassium sulfide, zinc chloride, phosphoric acid, or a phosphate, but in order to obtain coke having a large specific surface area in the present invention, any of these methods can be used. it can. However, the activation method using water vapor, which is one of the gas activation methods, is advantageous in terms of simplicity.
【００１４】コークスを賦活処理する際の賦活温度は、
賦活法により異なる。たとえば、水蒸気によるガス賦活
法においては、通常７００〜１１００°Ｃの温度に加熱
して行う。７００°Ｃ未満の場合は、炭化水素と水蒸気
との反応が進行せず、また１１００°Ｃを越えた場合
は、加熱設備、加熱源などがコスト高となり、不経済で
ある。また、薬品賦活法の場合は、使用する薬品によっ
ても異なるが、通常４００〜１０００°Ｃの温度に加熱
して行う。The activation temperature for activating the coke is
It depends on the activation method. For example, in the gas activation method using steam, heating is usually performed at a temperature of 700 to 1100 ° C. If the temperature is lower than 700 ° C, the reaction between hydrocarbon and water vapor does not proceed, and if the temperature exceeds 1100 ° C, the cost of heating equipment, heating source, etc. becomes high, which is uneconomical. In the case of the chemical activation method, it is usually heated to a temperature of 400 to 1000 ° C, though it depends on the chemical used.
【００１５】コークスを賦活処理する際の反応時間は、
活性炭の賦活処理時間に比し短くて済み、通常３０分〜
２時間程度である。The reaction time when activating the coke is
Shorter than activated carbon activation time, usually 30 minutes
It takes about 2 hours.
【００１６】賦活処理により得た高比表面積のコークス
に、負極材料として、さらに好適な物性を付与するため
に、必要に応じて、これを不活性ガス雰囲気下で焼成し
てもよい。しかし、焼成すると、結晶性が高くなるため
組織に収縮が起こり、その結果比表面積がかなり小さく
なる。したがって、賦活処理後にさらに焼成を施す場合
は、その焼成により比表面積が小さくなる分を見込ん
で、賦活処理後の比表面積を予め大きくしておくことが
必要となる。If necessary, the coke having a high specific surface area obtained by the activation treatment may be fired in an inert gas atmosphere in order to impart more suitable physical properties as a negative electrode material. However, upon firing, the crystallinity increases and the structure contracts, resulting in a considerably small specific surface area. Therefore, when further firing is performed after the activation treatment, it is necessary to increase the specific surface area after the activation treatment in advance in consideration of the decrease in the specific surface area due to the firing.
【００１７】本発明電池における負極は、上記した比表
面積及びｄ002 の大きいコークスを負極材料として使用
し、たとえばこれをポリテトラフルオロエチレン（ＰＴ
ＦＥ）、ポリフッ化ビニリデン（ＰＶｄＦ）等の結着剤
と混合して負極合剤とした後、所定の圧力で加圧成型す
ることにより作製される。必要に応じて、アセチレンブ
ラック、カーボンブラック等の導電剤を添加してもよ
い。The negative electrode in the battery of the present invention uses the above-mentioned coke having a large specific surface area and large d 002 as a negative electrode material. For example, this is made of polytetrafluoroethylene (PT).
FE), polyvinylidene fluoride (PVdF) or the like is mixed with a binder to form a negative electrode mixture, and then the mixture is produced by pressure molding at a predetermined pressure. If necessary, a conductive agent such as acetylene black or carbon black may be added.
【００１８】本発明電池は、このように負極材料とし
て、比表面積及びｄ002 の大きいコークスを使用した点
に特徴を有するものであり、正極材料、非水系電解質、
セパレータ（液体電解質を使用する場合）などの電池を
構成する他の部材については、従来非水系二次電池用と
して実用され、或いは提案されている種々の材料を使用
することが可能である。The battery of the present invention is characterized in that coke having a large specific surface area and large d 002 is used as the negative electrode material in this manner. The positive electrode material, the non-aqueous electrolyte,
For the other members constituting the battery such as the separator (when the liquid electrolyte is used), various materials that have been practically used or proposed for the conventional non-aqueous secondary battery can be used.
【００１９】[0019]
【作用】本発明電池においては、比表面積及びｄ002 が
それぞれ特定値以上であるコークスが負極材料として使
用されているので、充放電時における負極のリチウム吸
蔵放出可能な量が多くなる。In the battery of the present invention, since the coke having a specific surface area and d 002 that are equal to or more than the specific values is used as the negative electrode material, the amount of lithium that can be stored and released in the negative electrode during charging and discharging increases.
【００２０】[0020]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００２１】（製造例１）ディレードコーカー法で得た
石油系生コークス（元素組成；Ｃ：９５．１重量％、
Ｈ：３．１重量％、Ｎ：０．６重量％）を粒子径０．３
５ｍｍ以下に粉砕し、この粉末２５０ｇと水酸化カリウ
ム（試薬特級）１２５０ｇとを、２リットルのステンレ
ス製容器中で充分に攪拌混合した。Production Example 1 Petroleum raw coke obtained by the delayed coker method (elemental composition; C: 95.1% by weight,
H: 3.1% by weight, N: 0.6% by weight) with a particle size of 0.3
The powder was crushed to a size of 5 mm or less, and 250 g of this powder and 1250 g of potassium hydroxide (special grade reagent) were sufficiently stirred and mixed in a 2-liter stainless steel container.
【００２２】次いで、このようにして得た混合物を上記
ステンレス製容器ごと、密閉蓋を備えた鉄製容器内に入
れて密閉し、１リットル／分の通流速度で鉄製容器内に
窒素ガスを通流させつつ、１００°Ｃ／ｈの割合で６５
０°Ｃまで昇温して、同温度に１時間保持した。Then, the mixture thus obtained, together with the above stainless steel container, is placed in an iron container equipped with a sealing lid and sealed, and nitrogen gas is passed into the iron container at a flow rate of 1 liter / min. While flowing, 65 at a rate of 100 ° C / h
The temperature was raised to 0 ° C and the temperature was maintained for 1 hour.
【００２３】次いで、室温付近まで冷却した後、内容物
を少量ずつ４リットルの水中に入れ、攪拌後、ガラスフ
ィルター（１７Ｇ４）で濾過した。さらに、濾液のｐＨ
が１０になるまで濾過物を水洗した後、２リットルの２
０％塩酸中に移し、約５時間還流させつつ煮沸した。そ
の後、これをガラスフィルタ（１７Ｇ４）で濾過し、得
られた濾過物を１．５リットルの水中へ入れて１時間煮
沸し、再び濾過する操作を５回繰り返し行った後、１２
０°Ｃで１２時間乾燥した。このときのコークスの収率
は７４重量％（対生コークス）であり、また比表面積は
１２７０ｍ2 ／ｇであった。Then, after cooling to around room temperature, the contents were put into 4 liters of water little by little, stirred and filtered with a glass filter (17G4). In addition, the pH of the filtrate
After washing the filtrate with water until the value becomes 10, 2 liters of 2
It was transferred to 0% hydrochloric acid and boiled under reflux for about 5 hours. Thereafter, this was filtered through a glass filter (17G4), the obtained filtered product was put into 1.5 liter of water, boiled for 1 hour, and filtered again, which was repeated 5 times.
It was dried at 0 ° C for 12 hours. The coke yield at this time was 74% by weight (against raw coke), and the specific surface area was 1270 m 2 / g.
【００２４】次いで、上記コークスを黒鉛ルツボに入
れ、黒鉛ルツボごと、密閉蓋を備えた鉄製容器に入れて
密閉し、１リットル／分の通流速度で鉄製容器内に窒素
ガスを通流させつつ、２００°Ｃ／ｈの割合で１４００
°Ｃまで昇温して、同温度に１時間保持して焼成した。Next, the above coke was put into a graphite crucible, and the graphite crucible was put together with an iron container equipped with a sealing lid and sealed, and nitrogen gas was allowed to flow through the iron container at a flow rate of 1 liter / min. , 1400 at a rate of 200 ° C / h
The temperature was raised to ° C and the temperature was maintained for 1 hour for firing.
【００２５】この焼成したコークスをジェットミル粉砕
機（セイシン企業社製、型式「ＣＰＮ−０４」）を使用
して平均粒子径２０μｍに粉砕して負極材料としてのコ
ークスを作製した。The calcined coke was crushed to an average particle diameter of 20 μm using a jet mill crusher (manufactured by Seishin Enterprise Co., Ltd., model “CPN-04”) to prepare coke as a negative electrode material.
【００２６】以上の操作により得たコークスの収率は６
２重量％（対生コークス）であり、またその比表面積は
４２０ｍ2 ／ｇであった。さらに、Ｘ線回折パラメータ
ｄ002 及びＬｃはそれぞれ３．４５Å、４４Åであっ
た。The coke yield obtained by the above operation is 6
It was 2% by weight (against fresh coke), and its specific surface area was 420 m 2 / g. Further, the X-ray diffraction parameters d 002 and Lc were 3.45Å and 44Å, respectively.
【００２７】なお、比表面積は、カルロエルバ社製の表
面積測定機（商品コード「ソープトマチック１９０
０」）を使用してＢＥＴ法により求めたものであり、ま
たｄ002及びＬｃは、学振法に準拠して求めたものであ
る。以下の製造例における各値についても、同じ方法に
より求めたものである。The specific surface area is measured by Carlo Elba's surface area measuring device (product code "Sorptomatic 190").
0 ”) was used for the BET method, and d 002 and Lc were determined according to the Gakshin method. The values in the following production examples are also obtained by the same method.
【００２８】（製造例２〜１３）製造例１において、賦
活処理の条件（温度及び処理時間）を種々代えたこと以
外は製造例１と同様にして、比表面積のみが異なる１２
種のコークス（ｄ002 ：３．４５Å，Ｌｃ：４４Å）を
作製した。(Production Examples 2 to 13) In Production Example 1, only the specific surface area is different in the same manner as in Production Example 1 except that the activation conditions (temperature and treatment time) are changed.
Seed coke (d 002 : 3.45Å, Lc: 44Å) was prepared.
【００２９】（製造例１４）製造例１において、か焼温
度を６５０°Ｃに代えて９００°Ｃとしたこと以外は製
造例１と同様にして負極材料としてのコークスを作製し
た。このときの賦活処理後のコークスの収率は６１重量
％（対生コークス）、比表面積は２３５０ｍ2 ／ｇであ
り、また負極材料としてのコークスの収率は５１重量％
（対生コークス）、比表面積は１３２０ｍ2 ／ｇ、ｄ
002 及びＬｃはそれぞれ３．４１２Å、７６Åであっ
た。Production Example 14 A coke as a negative electrode material was produced in the same manner as in Production Example 1 except that the calcination temperature was changed from 650 ° C. to 900 ° C. At this time, the yield of coke after activation treatment was 61% by weight (against raw coke), the specific surface area was 2350 m 2 / g, and the yield of coke as a negative electrode material was 51% by weight.
(Against coke), specific surface area 1320 m 2 / g, d
002 and Lc were 3.412Å and 76Å, respectively.
【００３０】（製造例１５〜１９）製造例１において、
焼成温度を種々変えたこと以外は製造例１と同様にし
て、ｄ002 のみが異なる６種のコークス（比表面積：１
３２０ｍ2 ／ｇ，Ｌｃ：７６Å）を作製した。(Production Examples 15 to 19) In Production Example 1,
6 types of coke differing only in d 002 (specific surface area: 1) in the same manner as in Production Example 1 except that the firing temperature was changed variously.
320 m 2 / g, Lc: 76Å) was prepared.
【００３１】（製造例２０〜２５）製造例１において、
前処理加熱を行った後、賦活処理の条件（温度及び処理
時間）を種々変えて賦活処理を行ったこと以外は製造例
１と同様にして、比表面積のみが異なる６種のコークス
（ｄ002 ：３．３６Å，Ｌｃ：６５０Å）を作製した。(Production Examples 20 to 25) In Production Example 1,
Six kinds of coke (d 002) differing only in the specific surface area were prepared in the same manner as in Production Example 1 except that after the pretreatment heating, the activation treatment conditions (temperature and treatment time) were variously changed. : 3.36Å, Lc: 650Å) was prepared.
【００３２】〔３極式電池試験〕上記製造例１〜２５で
作製した各コークスを負極材料として使用し、それぞれ
に導電剤としてのアセチレンブラック及び結着剤として
のフッ素樹脂を、重量比８５：１０：５の比率で混練し
て負極合剤とした後、加圧成型して負極を作製した。[Tripolar Battery Test] Each of the cokes produced in the above Production Examples 1 to 25 was used as a negative electrode material, and acetylene black as a conductive agent and a fluororesin as a binder were mixed in a weight ratio of 85: After kneading at a ratio of 10: 5 to prepare a negative electrode mixture, pressure molding was carried out to produce a negative electrode.
【００３３】上記各電極を作用極とし、リチウム電極を
対極及び参照電極として３極式電池試験を行い、各電極
の単位重量当たりの容量を調べた。充放電は、電流密度
０．２ｍＡ／ｃｍ2 で行い、充電終止電位を０Ｖ（ｖｓ
リチウム単極電位）、放電終止電位を１Ｖ（ｖｓリチウ
ム単極電位）とした。結果を図１〜図３に示す。A three-pole battery test was conducted using each of the above electrodes as a working electrode and a lithium electrode as a counter electrode and a reference electrode, and the capacity per unit weight of each electrode was investigated. Charging / discharging was performed at a current density of 0.2 mA / cm 2 , and the end-of-charge potential was 0 V (vs
The lithium single electrode potential) and the discharge end potential were 1 V (vs lithium single electrode potential). The results are shown in FIGS.
【００３４】図１は、ｄ002 が３．３７Å以上であるコ
ークスの放電容量と比表面積との関係を、縦軸に放電容
量（ｍＡｈ／ｇ）を、横軸に比表面積（ｍ2 ／ｇ）をと
って示したグラフであり、同図より、ｄ002 が３．３７
Å以上であっても、比表面積が１００ｍ2 ／ｇ未満の場
合は、放電容量が小さいことが分かる。FIG. 1 shows the relationship between the discharge capacity and specific surface area of coke having d 002 of 3.37 Å or higher, the discharge capacity (mAh / g) on the vertical axis and the specific surface area (m 2 / g on the horizontal axis). ), The d 002 is 3.37.
Even if it is Å or more, it can be seen that the discharge capacity is small when the specific surface area is less than 100 m 2 / g.
【００３５】図２は、比表面積が１００ｍ2 ／ｇ以上で
あるコークスの放電容量とｄ002 との関係を、縦軸に放
電容量（ｍＡｈ／ｇ）を、横軸にｄ002 （Å）をとって
示したグラフであり、同図より、比表面積が１００ｍ2
／ｇ以上であっても、ｄ002が３．３７Å未満の場合、
放電容量が小さいことが分かる。FIG. 2 shows the relationship between the discharge capacity of coke having a specific surface area of 100 m 2 / g or more and d 002 , the discharge capacity (mAh / g) on the vertical axis and d 002 (Å) on the horizontal axis. The graph shows the specific surface area of 100 m 2
/ G or more, if d 002 is less than 3.37Å,
It can be seen that the discharge capacity is small.
【００３６】図３は、ｄ002 が３．３７Å未満であるコ
ークスの放電容量と比表面積との関係を、縦軸に放電容
量（ｍＡｈ／ｇ）を、横軸に比表面積（ｍ2 ／ｇ）をと
って示したグラフであり、同図より、ｄ002 が３．３７
Å未満の場合は、比表面積の如何を問わず、放電容量が
１００ｍＡｈ／ｇ程度と小さいことが分かる。FIG. 3 shows the relationship between the discharge capacity and specific surface area of coke having d 002 of less than 3.37Å, the discharge capacity (mAh / g) on the vertical axis and the specific surface area (m 2 / g on the horizontal axis). ), The d 002 is 3.37.
It can be seen that when it is less than Å, the discharge capacity is as small as about 100 mAh / g regardless of the specific surface area.
【００３７】なお、本発明は電池の形状に特に制限はな
く、円筒型、扁平型、角型など、種々の形状の非水系二
次電池に適用し得るものである。The present invention is not particularly limited in the shape of the battery, and can be applied to non-aqueous secondary batteries having various shapes such as a cylindrical shape, a flat shape and a square shape.
【００３８】[0038]
【発明の効果】本発明電池は、負極材料たるコークスの
リチウム吸蔵放出量が多いので、電池容量が大きいな
ど、本発明は優れた特有の効果を奏する。Since the battery of the present invention has a large amount of lithium occlusion and release of coke, which is a negative electrode material, the present invention has excellent unique effects such as a large battery capacity.
【図１】ｄ002 ≧３．３７Åの場合の放電容量と比表面
積との関係を示すグラフである。FIG. 1 is a graph showing a relationship between a discharge capacity and a specific surface area when d 002 ≧ 3.37 Å.
【図２】比表面積≧１００ｍ2 ／ｇ以上の場合の放電容
量とｄ002 との関係を示すグラフである。FIG. 2 is a graph showing the relationship between the discharge capacity and d 002 when the specific surface area ≧ 100 m 2 / g or more.
【図３】ｄ002 ＜３．３７Åの場合の放電容量と比表面
積との関係を示すグラフである。FIG. 3 is a graph showing the relationship between the discharge capacity and the specific surface area when d 002 <3.37 Å.
フロントページの続き (72)発明者 藤本 正久 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 好永 宣之 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 古川 修弘 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (56)参考文献 特開 平５−299091（ＪＰ，Ａ)Front page continuation (72) Masahisa Fujimoto 2-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Noriyuki Yoshinaga 2-18-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Denki Incorporated (72) Inventor Koji Nishio 2-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Nobuhiro Furukawa 2-18-2 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (56) Reference JP-A-5-299091 (JP, A)
Claims (4)
が１００ｍ2 ／ｇ以上であり、且つ、Ｘ線回折パラメー
タｄ002 が３．３７Å以上であるコークスが使用されて
いることを特徴とする非水系二次電池。1. A coke having a specific surface area according to the BET method of 100 m 2 / g or more and an X-ray diffraction parameter d 002 of 3.37 Å or more is used as a negative electrode material. Aqueous secondary battery.
メータＬｃが６００Å以下である請求項１記載の非水系
二次電池。2. The non-aqueous secondary battery according to claim 1, wherein the coke has an X-ray diffraction parameter Lc of 600 Å or less.
炭化水素を除去して得たものである請求項１又は２記載
の非水系二次電池。3. The non-aqueous secondary battery according to claim 1, wherein the coke is obtained by removing hydrocarbons in the pores by activation treatment.
以上であり、且つ、Ｘ線回折パラメータｄ００２が３．
３７Å以上、Ｌｃが６００Å以下のコークスからなる非
水系二次電池用負極材料。4. A BET specific surface area of 100 m 2 / g.
Above, and the X-ray diffraction parameter d 002 is 3.
A negative electrode material for a non-aqueous secondary battery, comprising coke having a Lc of 37 Å or more and an Lc of 600 Å or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4170236A JP2518771B2 (en) | 1992-06-03 | 1992-06-03 | Non-aqueous secondary battery and negative electrode material for non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4170236A JP2518771B2 (en) | 1992-06-03 | 1992-06-03 | Non-aqueous secondary battery and negative electrode material for non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06187987A JPH06187987A (en) | 1994-07-08 |
| JP2518771B2 true JP2518771B2 (en) | 1996-07-31 |
Family
ID=15901195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4170236A Expired - Fee Related JP2518771B2 (en) | 1992-06-03 | 1992-06-03 | Non-aqueous secondary battery and negative electrode material for non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2518771B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3551490B2 (en) * | 1994-09-30 | 2004-08-04 | 三菱化学株式会社 | Non-aqueous secondary battery |
| WO1996030318A1 (en) * | 1995-03-30 | 1996-10-03 | Nippon Sanso Corporation | Porous carbonaceous material, process for producing the same, and use thereof |
| JP3577776B2 (en) * | 1995-04-18 | 2004-10-13 | 三菱化学株式会社 | Non-aqueous secondary battery |
| CN107408726B (en) * | 2015-03-16 | 2019-10-25 | 日立化成株式会社 | Lithium ion battery, negative electrode for lithium ion battery, battery module, automobile and electric storage device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05299091A (en) * | 1992-04-20 | 1993-11-12 | Hitachi Maxell Ltd | Carbon electrode and lithium secondary battery using same |
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1992
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| Publication number | Publication date |
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