JPH043065B2 - - Google Patents
Info
- Publication number
- JPH043065B2 JPH043065B2 JP60292082A JP29208285A JPH043065B2 JP H043065 B2 JPH043065 B2 JP H043065B2 JP 60292082 A JP60292082 A JP 60292082A JP 29208285 A JP29208285 A JP 29208285A JP H043065 B2 JPH043065 B2 JP H043065B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- less
- pores
- felt
- volume
- 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 - Lifetime
Links
- 239000011148 porous material Substances 0.000 claims description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 238000007600 charging Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- ZFNZJZZGQWBCDR-UHFFFAOYSA-N 4-methyl-1,3-dioxolan-2-one;perchloric acid Chemical compound OCl(=O)(=O)=O.CC1COC(=O)O1 ZFNZJZZGQWBCDR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MKCDXXDWWZVCJG-UHFFFAOYSA-M lithium;4-methyl-1,3-dioxolan-2-one;perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O.CC1COC(=O)O1 MKCDXXDWWZVCJG-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nonwoven Fabrics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
Description
（産業上の利用分野）
本発明は、電極材用活性炭素繊維、とりわけ、
電解質を溶解させた有機溶媒溶液を電解液とする
電気化学二次電池（以下「非水二次電池」と呼
ぶ。）の電極材用活性炭素繊維に関する。このも
のは、特に細孔分布、灰分量、ナトリウム、及び
カリウムの含有量を調整することにより、充放電
効率が高く、かつ、自己放電の小さな電池を可能
とする電極材用に使用されるものである。
（従来技術とその問題点）
従来、非水二次電池用の電極材としては、ポリ
アセチレン又は、一般の活性炭や、活性炭素繊維
が使用されてきた。これらのうち、ポリアセチレ
ンは、工業的規模の生産が困難である。また、一
般の活性炭素又は、一般の活性炭素繊維は、それ
らの細孔直径の分布が、広いものが多く、さら
に、灰分、特にナトリウム。カリウムなどの含有
量が大きい。直径が30Å以上の細孔が多いこれら
の活性炭又は、これらの活性炭素繊維を使用して
非水二次電池を組んだ場合、これらの電池は、自
己放電の大きいものとなる。
また、直径が17Å以下の細孔は、充電時には、
電解質のイオンが入つてこれるが、放電時にはこ
れらのイオンの放出を妨げるために電池の充放電
効率を低下させる要因となる。一方、これらの一
般の活性炭及び活性炭素繊維中の灰分（すなわ
ち、不揮発性の塩類）は、電池作製時にそれぞれ
電解液に溶出し、充放電時にそれぞれの塩類に含
まれる陽イオン、陰イオン特有の酸化還元電位の
附近で酸化又は還元する。このために、充放電効
率は低下する。ここで特にナトリウム、カリウム
の両イオンは、電解液中に溶出しやすいために有
害である。
（発明の目的）
本発明は、電解質を溶かした有機溶媒溶液を電
解質とする電池において、高充放電効率及び自己
放電の小さいことを可能とする電極材用活性炭素
繊維を提供することを目的とする。
（発明の構成）
本発明は、下記の構成からなる。
細孔容積が0.7〜1.5c.c.／ｇで、全細孔容積に対
し、細孔直径30Å以上の細孔の容積が30％以下で
あり、かつ、細孔直径17Å以下の細孔の容積が30
％以下であり、灰分量が0.2％以下で、かつ、ナ
トリウムの含有量が20ppm以下、及びカリウムの
含有量が10ppm以下であることを特徴とする電極
材用活性炭素繊維。
以上のような活性炭素繊維は、本発明の目的に
適合するものである。このものは、例えば、次の
ようにして得られる。
すなわち、レーヨン、ポリアクリロニトリル繊
維などから作つた酸化繊維、ピツチから作つた不
融化繊維及びフエノール繊維などの炭化可能な繊
維を、直接又は、600℃〜1300℃の不活性ガス下
で炭化を進めた後、600℃〜1200℃の炭酸ガスや
水蒸気などや、又はこれらの酸化性ガスを含むガ
ス中で、時間や温度を加減して賦活する。
ここでは、得られる活性炭素繊維の直径30Å以
上の細孔の容積が全細孔容積の20％を越えないよ
うに、賦活時間又は賦活温度を加減する。
ここで、直径30Å以上の細孔の容積が全細孔容
積の20％を大きく越えると、後で行う700℃〜
1050℃での不活性ガス中での熱処理中に、比較的
小さな細孔が減少するため、直径30Å以上の細孔
が相対的に増加してしまい、本発明の電極材に適
した活性炭素繊維を得ることができない。
このようにして得られた活性炭素繊維は、その
細孔直径17Å以下の細孔が多く、また、灰分（ナ
トリウム、カリウムを含む）が多い。
ここで、上記の活性炭素繊維を酸洗浄し、灰分
（ナトリウム、カリウムを含む）を除去する。
このとき、灰分量が0.2％以下で、かつ、ナト
リウムの含有量が20ppm以下、及び、カリウムの
含有量が10ppm以下になるように条件を調整す
る。
次に、このような灰分の少ない活性炭素繊維
を、700〜1050℃の不活性ガス中で熱処理する。
この熱処理により、直径17Å以下の細孔は減少す
る。
本発明で使用する原料繊維としては、炭化可能
なものであれば制限はないが、灰分量及び賦活後
の細孔直径の分布の状態からピツチ系繊維が特に
有利である。
原料繊維は、トウ、スライバー、ヤーンなどの
紐、糸状でも布、フエルト、マツトなどのシート
状の形に加工されていてもさしつかえない。ま
た、本発明の活性炭素繊維にする過程において、
又は最後の段階でこのような形状に加工してもか
まわない。
本発明における活性炭素繊維の細孔直径及び細
孔容積は、常圧下の液体窒素の沸点における吸着
側の窒素ガス吸着等温線を用いて、クランスト
ン・インクレー（Cranston−Inkley）の計算法
を用いて求めた。
また、本発明における活性炭素繊維の灰分量は
活性炭素繊維を空気中700℃で24時間焼き、その
残渣の重量より求めた。また、ナトリウム、カリ
ウムの量はこの残渣から原子吸光法で求めた。
電池の電極材としての性能は以下の方法で求め
た。
過塩素酸リチウム−プロピレンカーボネート溶
液を電解液、金属リチウムを陰極、0.1gの活性炭
素繊維を陽極としてアルゴンボツクス中で第１図
のようなリチウム電池を組んだ。
次に、この電池を充電電圧が4.2Vになるまで
1mAで定電流充電し、その後1mAで定電流放電
を行つた。このような充放電を３回行つてエージ
ングした後、再び充電電圧が4.2Vになるまで
1mAで定電流充電した。このときの充電時間を
Tcとする。この後、ただちに1mAで定電流放電
を電圧が3.3Vになるまで行つた。このときの放
電時間をTdとする。この後、再び、1mAで、充
電電圧が4.2Vになるまで1mAで定電流充電した。
30日後、この電池を1mAで電圧が3.3Vになる
まで定電流放電を行つた。このときの充電時間を
Tdmとする。
このときの電池の放充電効率Ｅは、
Ｅ＝Td÷Tc×100
で求め、また、自己放電率Sd（％）は
Sd＝Tdm÷Td×100
で求めた。
（実施例及び比較例）
窒素ガス中、1000℃で焼成を行つたピツチ系炭
素繊維よりなるフエルトを920℃水蒸気下で15分
間賦活を行つた。（ここで得られたものをフエル
トＡとする。）フエルトＡを塩酸溶液（４％）で
30分間煮沸し、フエルトＢを得た。
このフエルトＢを1000℃窒素中で熱処理（10分
間）し、フエルトＣを得た。（フエルトＣは本発
明）
一方、フエルトＡで行つた賦活の時間より長め
に920℃水蒸気中で賦活を行つた。（20分間）この
フエルトをフエルトＣと同様に酸処理、1000℃窒
素処理を行つて、フエルトＤを得た。
また、フエルトＢを酸処理を行わずに1000℃窒
素処理を行いフエルトＥを得た。
第１表にフエルトＢ，Ｃ，Ｄ，Ｅの全細孔容
積、またそれに対する直径30Å以上の細孔による
容積の割合、直径17Å以下の細孔による容積の割
合、灰分量、ナトリウム及びカリウムの量を示
す。
(Industrial Application Field) The present invention relates to activated carbon fibers for electrode materials, particularly,
The present invention relates to activated carbon fibers for electrode materials of electrochemical secondary batteries (hereinafter referred to as "non-aqueous secondary batteries") whose electrolyte is an organic solvent solution in which an electrolyte is dissolved. This material is used for electrode materials that enable batteries with high charge/discharge efficiency and low self-discharge by adjusting the pore distribution, ash content, sodium, and potassium content. It is. (Prior Art and its Problems) Conventionally, polyacetylene, general activated carbon, or activated carbon fiber has been used as an electrode material for non-aqueous secondary batteries. Among these, polyacetylene is difficult to produce on an industrial scale. In addition, general activated carbon or general activated carbon fibers often have a wide distribution of pore diameters, and furthermore, they contain ash, especially sodium. High content of potassium etc. When non-aqueous secondary batteries are assembled using these activated carbons or activated carbon fibers that have many pores with a diameter of 30 Å or more, these batteries have a large self-discharge. In addition, pores with a diameter of 17 Å or less are
Electrolyte ions enter the battery, but during discharging, these ions are prevented from being released, resulting in a decrease in the charging and discharging efficiency of the battery. On the other hand, the ash content (i.e., non-volatile salts) in these general activated carbons and activated carbon fibers is eluted into the electrolytic solution during battery fabrication, and during charging and discharging, the ash content (i.e., nonvolatile salts) contained in each salt is unique to the cations and anions contained in each salt. Oxidizes or reduces near the redox potential. For this reason, charging and discharging efficiency decreases. In particular, both sodium and potassium ions are harmful because they easily dissolve into the electrolyte. (Object of the invention) The object of the present invention is to provide an activated carbon fiber for an electrode material that enables high charge/discharge efficiency and low self-discharge in a battery using an organic solvent solution containing an electrolyte as an electrolyte. do. (Structure of the Invention) The present invention consists of the following structure. The pore volume is 0.7 to 1.5 cc/g, the volume of pores with a pore diameter of 30 Å or more is 30% or less of the total pore volume, and the volume of pores with a pore diameter of 17 Å or less is 30% or less.
% or less, an ash content of 0.2% or less, a sodium content of 20ppm or less, and a potassium content of 10ppm or less. The activated carbon fibers described above are suitable for the purpose of the present invention. This can be obtained, for example, as follows. That is, oxidized fibers made from rayon, polyacrylonitrile fibers, etc., infusible fibers made from pitch, and carbonizable fibers such as phenol fibers were carbonized directly or under an inert gas at a temperature of 600°C to 1300°C. After that, it is activated in carbon dioxide gas, water vapor, etc. at 600°C to 1200°C, or in a gas containing these oxidizing gases by controlling the time and temperature. Here, the activation time or activation temperature is adjusted so that the volume of pores with a diameter of 30 Å or more in the obtained activated carbon fiber does not exceed 20% of the total pore volume. Here, if the volume of pores with a diameter of 30 Å or more greatly exceeds 20% of the total pore volume, it is necessary to
During heat treatment in an inert gas at 1050°C, relatively small pores decrease, and pores with a diameter of 30 Å or more increase relatively, making the activated carbon fiber suitable for the electrode material of the present invention. can't get it. The activated carbon fiber thus obtained has many pores with a pore diameter of 17 Å or less, and also has a high ash content (including sodium and potassium). Here, the activated carbon fibers are acid-washed to remove ash (including sodium and potassium). At this time, conditions are adjusted so that the ash content is 0.2% or less, the sodium content is 20ppm or less, and the potassium content is 10ppm or less. Next, such activated carbon fibers with a low ash content are heat-treated in an inert gas at 700 to 1050°C.
This heat treatment reduces pores with a diameter of 17 Å or less. The raw material fibers used in the present invention are not limited as long as they can be carbonized, but pitch fibers are particularly advantageous in view of the ash content and the distribution of pore diameters after activation. The raw material fiber may be in the form of a string or thread such as tow, sliver, or yarn, or may be processed into a sheet shape such as cloth, felt, or mat. In addition, in the process of making activated carbon fiber of the present invention,
Alternatively, it may be processed into such a shape at the final stage. The pore diameter and pore volume of the activated carbon fiber in the present invention are calculated using the Cranston-Inkley calculation method using the nitrogen gas adsorption isotherm on the adsorption side at the boiling point of liquid nitrogen under normal pressure. I asked. Further, the ash content of the activated carbon fiber in the present invention was determined from the weight of the residue after baking the activated carbon fiber in air at 700°C for 24 hours. In addition, the amounts of sodium and potassium were determined from this residue by atomic absorption spectrometry. The performance as a battery electrode material was determined by the following method. A lithium battery as shown in Figure 1 was assembled in an argon box using a lithium perchlorate-propylene carbonate solution as an electrolyte, metallic lithium as a cathode, and 0.1 g of activated carbon fiber as an anode. Next, charge this battery until the charging voltage reaches 4.2V.
Constant current charging was performed at 1 mA, and then constant current discharging was performed at 1 mA. After aging by performing charging and discharging three times in this way, the charging voltage will rise again until the charging voltage reaches 4.2V.
Constant current charging was performed at 1 mA. Charging time at this time
Let it be Tc. Immediately thereafter, constant current discharge was performed at 1 mA until the voltage reached 3.3V. The discharge time at this time is Td. After this, constant current charging was performed again at 1 mA until the charging voltage reached 4.2 V. After 30 days, this battery was subjected to constant current discharge at 1 mA until the voltage reached 3.3V. Charging time at this time
Tdm. The discharge/charging efficiency E of the battery at this time was determined by E=Td÷Tc×100, and the self-discharge rate Sd (%) was determined by Sd=Tdm÷Td×100. (Examples and Comparative Examples) Felts made of pitch-based carbon fibers fired at 1000°C in nitrogen gas were activated under steam at 920°C for 15 minutes. (The material obtained here is called Felt A.) Add Felt A to a hydrochloric acid solution (4%).
Felt B was obtained by boiling for 30 minutes. This felt B was heat treated (10 minutes) at 1000° C. in nitrogen to obtain felt C. (Felt C is the invention) On the other hand, activation was carried out in steam at 920°C for a longer period of time than the activation time carried out with Felt A. This felt was treated with acid and nitrogen at 1000° C. in the same manner as Felt C to obtain Felt D (for 20 minutes). Further, Felt B was subjected to nitrogen treatment at 1000° C. without acid treatment to obtain Felt E. Table 1 shows the total pore volume of Felts B, C, D, and E, as well as the proportion of the volume due to pores with a diameter of 30 Å or more, the volume proportion of pores with a diameter of 17 Å or less, the ash content, and the sodium and potassium content. Indicate quantity.
【表】
これらのフエルトＢ，Ｃ，Ｄ，Ｅを各々0.1g使
用し、リチウム二次電池を作り、それらの電池
の、充放電効率、自己放電率を求めた。これらの
電池の充放電効率、自己放電率をフエルトＣから
作つた電池の充放電効率及び自己放電率を各々
100とした比率で示したのが第２表である。[Table] Using 0.1 g each of these felts B, C, D, and E, lithium secondary batteries were made, and the charge/discharge efficiency and self-discharge rate of these batteries were determined. The charge-discharge efficiency and self-discharge rate of these batteries are respectively the charge-discharge efficiency and self-discharge rate of the battery made from felt C.
Table 2 shows the ratio set to 100.
【表】
この表から明らかなように、本発明にかかる電
極材は、それを使用した電池を充放電効率の高
く、かつ自己放電率の高い極めて優れた二次電池
とすることがわかる。
本発明の具体例について説明したが、本発明は
それらの例に限定されるものではない。[Table] As is clear from this table, it can be seen that the electrode material according to the present invention makes a battery using it an extremely excellent secondary battery with high charge/discharge efficiency and high self-discharge rate. Although specific examples of the present invention have been described, the present invention is not limited to those examples.
第１図は活性炭素繊維の評価用リチウム二次電
池を示す。
１……活性炭素繊維、２……金属リチウム、３
……過塩素酸リチウム−プロピレンカーボネート
溶液、４……ガラス繊維製濾紙（セパレーター）、
５……リード線（白金）、６……テフロン製容器。
FIG. 1 shows a lithium secondary battery made of activated carbon fiber for evaluation. 1...Activated carbon fiber, 2...Metal lithium, 3
...Lithium perchlorate-propylene carbonate solution, 4...Glass fiber filter paper (separator),
5...Lead wire (platinum), 6...Teflon container.
Claims (1)
対し、細孔直径30Å以上の細孔の容積が30％以下
であり、かつ、細孔直径17Å以下の細孔の容積が
30％以下であり、灰分量が0.2％以下で、かつ、
ナトリウムの含有量が20ppm以下、及び、カリウ
ムの含有量が10ppm以下であることを特徴とする
電極材用活性炭素繊維。1 The pore volume is 0.7 to 1.5 cc/g, the volume of pores with a pore diameter of 30 Å or more is 30% or less of the total pore volume, and the volume of pores with a pore diameter of 17 Å or less is
30% or less, the ash content is 0.2% or less, and
An activated carbon fiber for an electrode material, characterized in that the content of sodium is 20 ppm or less and the content of potassium is 10 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292082A JPS62154461A (en) | 1985-12-26 | 1985-12-26 | Activated carbon fiber for electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292082A JPS62154461A (en) | 1985-12-26 | 1985-12-26 | Activated carbon fiber for electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62154461A JPS62154461A (en) | 1987-07-09 |
| JPH043065B2 true JPH043065B2 (en) | 1992-01-21 |
Family
ID=17777308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60292082A Granted JPS62154461A (en) | 1985-12-26 | 1985-12-26 | Activated carbon fiber for electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62154461A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3565994B2 (en) * | 1996-06-28 | 2004-09-15 | 呉羽化学工業株式会社 | Carbonaceous material for electrode of non-aqueous solvent secondary battery, method for producing the same, and non-aqueous solvent secondary battery |
| FR2771856B1 (en) | 1997-12-02 | 2000-02-25 | Messier Bugatti | CARBON FIBER ELECTRODE FOR SECONDARY BATTERY |
| FR2788168A1 (en) | 1998-12-30 | 2000-07-07 | Messier Bugatti | GAS DIFFUSION ELECTRODE SUPPORTING AN ELECTROCHEMICAL REACTION CATALYST |
| JP4916632B2 (en) * | 2001-09-10 | 2012-04-18 | 昭和電工株式会社 | Vapor grown carbon fiber and its use |
| US7154738B2 (en) | 2002-11-29 | 2006-12-26 | Honda Motor Co., Ltd. | Polarizing electrode for electric double layer capacitor and electric double layer capacitor therewith |
| WO2005038836A1 (en) * | 2003-10-17 | 2005-04-28 | Nippon Oil Corporation | Electric double layer capacitor, activated carbon for electrode thereof and method for producing same |
| JP5843107B2 (en) * | 2012-07-30 | 2016-01-13 | トヨタ自動車株式会社 | Method for producing non-aqueous electrolyte secondary battery |
| JP6500116B2 (en) * | 2015-09-10 | 2019-04-10 | 株式会社キャタラー | Lithium ion capacitor and carbon material used as positive electrode active material thereof |
| EP3579316A4 (en) * | 2017-01-31 | 2020-02-19 | Sumitomo Electric Industries, Ltd. | REDOX BATTERY ELECTRODE AND REDOX FLOW BATTERY |
| KR20220154689A (en) * | 2020-03-17 | 2022-11-22 | 주식회사 쿠라레 | Additive for electrochemical device positive electrode, composition for electrochemical device positive electrode containing the same, and electrochemical device |
-
1985
- 1985-12-26 JP JP60292082A patent/JPS62154461A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62154461A (en) | 1987-07-09 |
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