JP5892429B2 - 液式鉛蓄電池 - Google Patents
液式鉛蓄電池 Download PDFInfo
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- JP5892429B2 JP5892429B2 JP2013523019A JP2013523019A JP5892429B2 JP 5892429 B2 JP5892429 B2 JP 5892429B2 JP 2013523019 A JP2013523019 A JP 2013523019A JP 2013523019 A JP2013523019 A JP 2013523019A JP 5892429 B2 JP5892429 B2 JP 5892429B2
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- 239000007788 liquid Substances 0.000 title claims description 28
- 239000002253 acid Substances 0.000 title claims description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 47
- 229930185605 Bisphenol Natural products 0.000 claims description 43
- 239000007773 negative electrode material Substances 0.000 claims description 39
- 239000006229 carbon black Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229920003086 cellulose ether Polymers 0.000 claims description 20
- 229920005610 lignin Polymers 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 230000009969 flowable effect Effects 0.000 claims 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 27
- 239000001768 carboxy methyl cellulose Substances 0.000 description 25
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 25
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 25
- 230000001172 regenerating effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 9
- 239000003273 ketjen black Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 229920002972 Acrylic fiber Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910014474 Ca-Sn Inorganic materials 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- -1 Na + ion Chemical class 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/627—Expanders for lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
(−(OH)(RSO3H)Ph−X−Ph(OH)(R'SO3H)CH2−)n
の化学式で表され、R,R'はメチレン基等の適宜のアルキル基、XはSO2基、アルキル基等でXを含まずに2個のフェニル基が直接結合していても良い。またSO3H基の水素は、負極活物質中でNa+イオン等の適宜の陽イオン、特にアルカリ金属イオンにより置換されていることがある。さらにRSO3H基、R'SO3H基、CH2基はフェニル基(Ph)のOH基に対してオルソの位置にあり、縮合物のモノマーはCH2基を介して互いに接続されている。市販のビスフェノール縮合物はモノマー当たり2個のスルホン酸基を有するものが多いが、モノマー当たりのスルホン酸基の数は1個〜4個等のように任意である。XがSO2基の場合がビスフェノールS、Xが −C(CH3)2− の場合がビスフェノールAで、実施例ではビスフェノールSを用いる例を示すが、ビスフェノールAを用いても結果は同等である。ビスフェノール縮合物の分子量は任意で、例えば4000〜250,000程度とし、分子量の影響は小さい。ビスフェノール縮合物は、芳香族環とスルホン酸基とを含む水溶性高分子である点で、リグニンスルホン酸と類似しているが、カルボキシ基とエーテル基及びアルコール性水酸基を持たない点と、網状ではなく直鎖状の高分子である点が異なる。
・ CMCもビスフェノール縮合物も含まないもの、及び
・ CMCを含むがビスフェノール縮合物を含まないもの、を調製した。
さらにビスフェノール以外に変わる材料としてリグニンを検討し、CMCを含むが、ビスフェノール縮合物の変わりにリグニンをカーボンペーストに含有させたものを調製した。なおケッチェンブラックに変えて他のカーボンブラックを含有させても良く、カーボンブラック以外にグラファイト、活性炭、炭素繊維等の他のカーボンを含有させても良い。カーボンペースト中のビスフェノール縮合物とリグニンをカーボン分散剤といい、鉛粉と共にカーボンペーストに練合した、もしくは鉛粉を練合した後にカーボンペーストに練合したリグニンを防縮剤という。後述の表1でも示すように、リグニンの含有目的は、カーボンの分散及び鉛活物質の防縮であり、これら異なる目的に対し効果を得る為には、ペーストへの投入も二段階で実施する必要がある。
・ 電解液の濁りを僅かにすることにより液面の視認性を高め、
・ 低温ハイレート放電性能と回生充電受入性能とを従来例と同等以上に保ち、
・ しかも充電不足な条件での耐久性能を向上させることができる。
Claims (5)
- 負極活物質と、二酸化鉛を主成分とする正極活物質と、硫酸を含有し流動自在な電解液とを備えている液式鉛蓄電池において、
前記負極活物質は、海綿状鉛100mass%当たりで、カーボンを0.5mass%以上で2.5mass%以下、スルホン酸基を有するビスフェノール縮合物から成る水溶性高分子を0.1mass%以上で0.9mass%以下、セルロースエーテルを0.01mass%以上で0.3mass%以下含有することを特徴とする、液式鉛蓄電池。 - 前記カーボンはカーボンブラックであることを特徴とする、請求項1の液式鉛蓄電池。
- 前記セルロースエーテルはカルボキシアルキルセルロースであることを特徴とする、請求項1または2の液式鉛蓄電池。
- 前記負極活物質はさらにリグニンスルホン酸を含有することを特徴とする、請求項1〜3のいずれかの液式鉛蓄電池。
- 前記電解液は、化成済みの段階において、カーボンブラック濃度が3massppm以下であることを特徴とする、請求項2の液式鉛蓄電池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2013523019A JP5892429B2 (ja) | 2011-07-05 | 2012-07-03 | 液式鉛蓄電池 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011148940 | 2011-07-05 | ||
JP2011148940 | 2011-07-05 | ||
PCT/JP2012/066949 WO2013005733A1 (ja) | 2011-07-05 | 2012-07-03 | 液式鉛蓄電池 |
JP2013523019A JP5892429B2 (ja) | 2011-07-05 | 2012-07-03 | 液式鉛蓄電池 |
Publications (2)
Publication Number | Publication Date |
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JPWO2013005733A1 JPWO2013005733A1 (ja) | 2015-02-23 |
JP5892429B2 true JP5892429B2 (ja) | 2016-03-23 |
Family
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Family Applications (1)
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Country Status (5)
Country | Link |
---|---|
US (1) | US20140134482A1 (ja) |
EP (1) | EP2731189A4 (ja) |
JP (1) | JP5892429B2 (ja) |
CN (1) | CN103582974A (ja) |
WO (1) | WO2013005733A1 (ja) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2650951B1 (en) * | 2010-12-09 | 2018-12-26 | Nec Corporation | Positive electrode active material for secondary battery and secondary battery using same |
JP5884528B2 (ja) * | 2012-02-03 | 2016-03-15 | 株式会社Gsユアサ | 液式鉛蓄電池 |
JP6066119B2 (ja) * | 2012-04-06 | 2017-01-25 | 株式会社Gsユアサ | 液式鉛蓄電池 |
WO2014050012A1 (ja) * | 2012-09-27 | 2014-04-03 | 株式会社Gsユアサ | 液式鉛蓄電池 |
JP6153072B2 (ja) * | 2013-08-02 | 2017-06-28 | 株式会社Gsユアサ | 液式鉛蓄電池 |
JP6153073B2 (ja) * | 2013-08-02 | 2017-06-28 | 株式会社Gsユアサ | 鉛蓄電池 |
JP6153074B2 (ja) * | 2013-08-02 | 2017-06-28 | 株式会社Gsユアサ | 液式鉛蓄電池 |
WO2015079631A1 (ja) * | 2013-11-29 | 2015-06-04 | 株式会社Gsユアサ | 鉛蓄電池 |
DE112014006702T5 (de) * | 2014-05-26 | 2017-02-16 | Gs Yuasa International Ltd. | Bleisäurebatterie |
JP6515935B2 (ja) * | 2015-01-14 | 2019-05-22 | 日立化成株式会社 | 鉛蓄電池、マイクロハイブリッド車及びアイドリングストップシステム車 |
JP6528436B2 (ja) * | 2015-02-12 | 2019-06-12 | 株式会社Gsユアサ | 鉛蓄電池とその負極板及び鉛蓄電池の製造方法 |
JP6775764B2 (ja) | 2016-09-30 | 2020-10-28 | 株式会社Gsユアサ | 鉛蓄電池 |
DE202018006602U1 (de) * | 2017-09-08 | 2022-08-11 | Daramic, Llc | Verbesserte Blei-Säure-Batterieseparatoren mit Kohlenstoff |
Family Cites Families (15)
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JP3493900B2 (ja) | 1995-07-04 | 2004-02-03 | 松下電器産業株式会社 | 鉛蓄電池用極板およびその製造方法 |
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2012
- 2012-07-03 CN CN201280026094.9A patent/CN103582974A/zh active Pending
- 2012-07-03 JP JP2013523019A patent/JP5892429B2/ja active Active
- 2012-07-03 EP EP12808012.4A patent/EP2731189A4/en not_active Withdrawn
- 2012-07-03 WO PCT/JP2012/066949 patent/WO2013005733A1/ja active Application Filing
- 2012-07-03 US US14/130,747 patent/US20140134482A1/en not_active Abandoned
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Publication number | Publication date |
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EP2731189A1 (en) | 2014-05-14 |
CN103582974A (zh) | 2014-02-12 |
JPWO2013005733A1 (ja) | 2015-02-23 |
EP2731189A4 (en) | 2015-04-08 |
WO2013005733A1 (ja) | 2013-01-10 |
US20140134482A1 (en) | 2014-05-15 |
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