JP2021507537A - 電極素材用活性炭の製造方法 - Google Patents
電極素材用活性炭の製造方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims description 42
- 239000012190 activator Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003923 SiC 4 Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- C01B32/378—Purification
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
Description
石油系Coke材料を10時間の間に炭化して形成された炭化物及び活性化剤(KOH、NaOH=1、1(w/w))は1、5質量比(活性炭、KOH)をミキサー器に混合した。次に、混合物はるつぼに入れて1000℃の温度で不活性の雰囲気及び5時間の間に熱処理して活性化した。次に、塩酸水溶液で洗浄及び水洗を3回繰り返した後、100℃の温度で40時間の間乾燥させた。乾燥された活性炭をふるいに通過させて活性炭を取得した。
Cl2及び水素、窒素ガスの雰囲気(Cl220%、H210%、N270%)を適用したこと以外は実施例1と同一の方法で行った。
HCl及び水素、窒素ガスの雰囲気(HCl10%、H210%、N270%)を適用したこと以外は実施例1と同一の方法で行った。
HCl及び水素、窒素ガスの雰囲気(HCl20%、H210%、N270%)を適用したこと以外は実施例1と同一の方法で行った。
HCl及び水素、窒素ガスの雰囲気(HCl30%、H210%、N270%)を適用したこと以外は実施例1と同一の方法で行った。
HCl及び水素、窒素ガスの雰囲気(HCl60%、H210%、N270%)を適用したこと以外は実施例1と同一の方法で行った。
活性炭を水素及び窒素ガスの雰囲気(H230%、N270%)で熱処理して洗浄したこと以外は実施例1と同一の方法で行った。
活性炭を窒素ガスの雰囲気で熱処理して洗浄したこと以外は実施例1と同一の方法で行った。
実施例1〜2及び比較例1〜2で製造された活性炭のBET及び電気伝導度を測定し、ICP分析によって金属濃度を測定し、EA分析によって酸素濃度を測定し、表1に示した。
Claims (15)
- 活性化した炭素材料を塩素を含んでいるガスを含む雰囲気で熱処理するステップを含み、
前記熱処理ステップ以後の活性化した炭素材料のうち、金属の不純物の含量が0.1ppm〜20ppm以下である、電極素材用活性炭の製造方法。 - 前記製造方法は、
炭素材料を準備するステップと、
前記炭素材料を炭化するステップと、
前記炭化した炭素材料を活性化剤と混合するステップと、
前記活性化剤と混合した炭化した炭素材料を活性化するステップと、
前記活性化した炭素材料を洗浄して乾燥するステップと、
前記洗浄して乾燥するステップ以後に前記活性化した炭素材料を塩素を含んでいるガスを含む雰囲気で熱処理するステップと、
を含む、請求項1に記載の電極素材用活性炭の製造方法。 - 前記活性化剤と混合するステップにおいて、前記活性化剤はアルカリ水酸化物であり、前記活性化剤は、前記炭化した炭素材料に対して1〜5の重量比で投入される、請求項2に記載の電極素材用活性炭の製造方法。
- 前記活性化するステップは、500℃〜1000℃の活性化温度で行われる、請求項2に記載の電極素材用活性炭の製造方法。
- 前記活性化するステップ以後に、活性化した炭素材料で活性化剤の含量は、50ppm以下である、請求項2に記載の電極素材用活性炭の製造方法。
- 前記洗浄して乾燥するステップは、酸洗浄、蒸留水洗浄、及び不活性気体洗浄からなる群から選択された1種以上の方法で行われる、請求項2に記載の電極素材用活性炭の製造方法。
- 前記洗浄して乾燥するステップは、50℃〜200℃の温度で乾燥される、請求項2に記載の電極素材用活性炭の製造方法。
- 前記洗浄して乾燥するステップ以後に、前記活性化した炭素材料のpHは6.5〜7.5である、請求項2に記載の電極素材用活性炭の製造方法。
- 前記塩素を含んでいるガスは、HCl、Cl2、CHCl3、ClO2、BCl3、SiCl4、CCl4、CHCl3、COCl2、CHCl3及びCH2Cl2からなる群から選択された1種以上を含む、請求項1に記載の電極素材用活性炭の製造方法。
- 前記塩素を含んでいるガスは、不活性気体と混合して雰囲気を形成し、
前記塩素を含んでいるガスは、前記の雰囲気を形成するガスのうち1〜50体積%である、請求項1に記載の電極素材用活性炭の製造方法。 - 前記熱処理するステップは、500℃〜1000℃の温度で行われる、請求項1に記載の電極素材用活性炭の製造方法。
- 前記炭化するステップ以後に、前記炭化した炭素材料を平均3μm〜20μmで粉砕するステップをさらに含む、請求項2に記載の電極素材用活性炭の製造方法。
- 前記熱処理するステップ以後の活性化した炭素材料の比表面積は、前記熱処理するステップ以前の活性化した炭素材料の比表面積に比べて20%以下に減少したものである、請求項1に記載の電極素材用活性炭の製造方法。
- 前記熱処理するステップ以後の活性化した炭素材料のうち酸素含量は、1%以下である、請求項1に記載の電極素材用活性炭の製造方法。
- 前記熱処理するステップ以後の活性化した炭素材料のうち金属の不純物含量は、0.1ppm〜20ppm以下である、請求項1に記載の電極素材用活性炭の製造方法。
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KR1020170175062A KR102020126B1 (ko) | 2017-12-19 | 2017-12-19 | 전극소재용 활성탄의 제조방법 |
KR10-2017-0175062 | 2017-12-19 | ||
PCT/KR2018/014500 WO2019124777A1 (ko) | 2017-12-19 | 2018-11-23 | 전극소재용 활성탄의 제조방법 |
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JP2004107814A (ja) * | 2002-09-17 | 2004-04-08 | Kashima Oil Co Ltd | 活性炭素繊維の製造方法およびそれを用いた電気二重層キャパシタ |
JP2008037733A (ja) * | 2006-08-10 | 2008-02-21 | Sangyo Gijutsu Kenkyusho:Kk | 活性炭および電気二重層キャパシタの製造方法 |
JP2016076673A (ja) * | 2014-10-09 | 2016-05-12 | 株式会社キャタラー | ハイブリッドキャパシタ用の炭素材料 |
JP2017088443A (ja) * | 2015-11-09 | 2017-05-25 | 住友電気工業株式会社 | 多孔質炭素材料、その製造方法、それを用いた電極及びキャパシタ |
JP2017212433A (ja) * | 2016-05-18 | 2017-11-30 | 株式会社クラレ | 炭素質材料、ならびに該炭素質材料を含有する電気二重層キャパシタ用電極材料、電気二重層キャパシタ用電極および電気二重層キャパシタ |
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JP7130750B2 (ja) | 2022-09-05 |
CN111433872A (zh) | 2020-07-17 |
TWI687371B (zh) | 2020-03-11 |
US11072532B2 (en) | 2021-07-27 |
WO2019124777A1 (ko) | 2019-06-27 |
KR20190073855A (ko) | 2019-06-27 |
US20200317528A1 (en) | 2020-10-08 |
TW201940426A (zh) | 2019-10-16 |
CN111433872B (zh) | 2021-11-19 |
KR102020126B1 (ko) | 2019-09-10 |
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