JPH0831336B2 - Anode plate for a sealed lead-acid battery - Google Patents

Anode plate for a sealed lead-acid battery

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Publication number
JPH0831336B2
JPH0831336B2 JP60242443A JP24244385A JPH0831336B2 JP H0831336 B2 JPH0831336 B2 JP H0831336B2 JP 60242443 A JP60242443 A JP 60242443A JP 24244385 A JP24244385 A JP 24244385A JP H0831336 B2 JPH0831336 B2 JP H0831336B2
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Prior art keywords
anode plate
active material
discharge
battery
sealed lead
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JPS62103976A (en
Inventor
朝比古 三浦
敏夫 内田
容尚 和田
昭夫 小牧
健介 弘中
他▲く▼美 早川
敏 松林
庄吾 森本
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新神戸電機株式会社
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Publication of JPH0831336B2 publication Critical patent/JPH0831336B2/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/34Gastight accumulators
    • H01M10/342Gastight lead accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/14Electrodes for lead-acid accumulators
    • H01M4/16Processes of manufacture
    • H01M4/20Processes of manufacture of pasted electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/70Carriers or collectors characterised by shape or form
    • H01M4/72Grids
    • H01M4/73Grids for lead-acid accumulators, e.g. frame plates

Description

【発明の詳細な説明】 産業上の利用分野 本発明は密閉型鉛蓄電池用陽極板の特性改善、特に高率放電特性および過放電放置特性、寿命特性の改善に関するものである。 DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL APPLICABILITY The present invention is characteristic improvement of sealed lead acid battery anode plate, particularly high-rate discharge characteristics and overdischarge storage characteristics, it relates to improvements in life characteristics.

従来の技術 従来の密閉型鉛蓄電池用極板は鋳造もしくはエキスパンド加工した格子にペーストを充填し化成工程を経て極板としている。 Description of the Related Art Conventional sealed lead storage battery plates are electrode plate through a chemical conversion process by filling the paste into the casting or the expansion work lattice. そのため極板内部まで活物質が充填されている。 Therefore active material until the internal electrode plate is filled. 一方、NS40Z形鉛蓄電池(電解液を限定した密閉型鉛蓄電池ではなく過剰の電解液を使用する自動車用鉛蓄電池のJIS形式)用極板の格子として鉛又は鉛合金よりなる格子体の格子骨の一部を耐熱、耐酸、耐酸化性を有する不導電性もしくは導電性の織布又は不織布で置き換えることにより、軽量で且つ活物質の脱落を少なくしたものがある。 On the other hand, NS40Z Katachinamari battery grid bone grid made of lead or lead alloy as a grid for electrode plate (JIS format lead-acid batteries for vehicles using an excess of the electrolyte rather than a sealed lead-acid battery has a limited electrolyte) heat a portion of, acid, by replacing non-conductive or conductive woven or non-woven having oxidation resistance are those with a reduced and separation of the active material is lightweight.

発明が解決しようとする問題点 ところで密閉型鉛蓄電池の放電反応は陽極活物質、陰極活物質および硫酸の反応であるが、密閉型鉛蓄電池では電解液が制限されているが故に、放電特性、特に電圧特性に大きく関与するのは硫酸の拡散である。 Invention discharge reaction anode active material will to problems Incidentally sealed lead-acid battery to solve, is a reaction of a cathode active material and sulfuric acid, in the sealed lead-acid battery because although the electrolyte is limited, discharge characteristics, of particular largely responsible voltage characteristic is the diffusion of sulfuric acid. 従来の極板では極板内部まで活物質が充填されているため、放電時内部まで硫酸の拡散が追従できず、結局極板表面での反応が主となり、内部の活物質はほとんど利用されない状態となっている。 Since the active material to the electrode plate inside the conventional electrode plate is filled, can not follow the diffusion of sulfuric acid into the interior during discharge, eventually reaction at the electrode plate surface becomes a main, not inside the active material is hardly available state It has become. この傾向は放電電流の増加、極板厚の増加にともない顕著になってくる。 This trend is an increase in the discharge current, it becomes significant with the increase of GokuitaAtsu. この現象は放電特性に影響するばかりでなく、電池寿命にも大きく関与する。 This phenomenon not only affects the discharge characteristics, involved significantly to battery life. なぜならば、放電時に表面近くの活物質が集中的に利用され、表面近くの活物質が泥状化をおこし脱落する。 Since the active material near the surface during discharge is intensively utilized, near the active material surface may drop cause slurried. そのためショートや泥状化のための容量低下をまねきやすい。 Therefore likely to lead to a reduction in capacity for the short and slurried. また密閉型鉛蓄電池におこりやすい格子の伸びによる格子と活物質との密着性低下による容量低下の問題も従来の極板では重要な問題である。 The problem of reduced capacity due to adhesion reduction of the lattice and the active material due to elongation of the prone lattice sealed lead-acid battery also in the conventional electrode plate is an important problem. さらに重要なことは、密閉型鉛蓄電池特有の過放電放置後充電が入らないという現象がある。 More importantly, it sealed lead-acid battery-specific over-discharge after standing charge is a phenomenon that does not enter. これは密閉型鉛電池の大きなる欠点であり、原因としては過放電放置中に格子と活物質界面に自己放電によって硫酸鉛の高抵抗層が形成されるためと考えられている。 This is Okinaru disadvantage of sealed lead batteries, it is believed to be due to the high-resistance layer of lead sulfate by self-discharge in a grid and the active material interface during overdischarge left is formed as the cause.

最近、密閉型鉛蓄電池はハンディクリーナ用、VTR Recently, sealed lead-acid batteries for Handy cleaner, VTR
(ブイティアール)用などの電源に代表されるように、 As represented by the power source, such as for (Buitiaru),
家電品への進出が著しい。 Foray into consumer electronics products is significant. そのため比較的高率放電でのサイクル用途が急激に要求されるようになってきている。 Therefore cycle applications at relatively high-rate discharge has come to be rapidly requested. その要求の中で、極板内の活物質を均一に利用させ、放電特性、特に電圧特性と高容量化への改善が望まれている。 In that request, evenly utilized an active material in the electrode plate, the discharge characteristics, particularly improvements to voltage characteristics and high capacity is desired. また家電品の場合、ユーザが不特定多数となるため、信頼性が強く望まれ、特に放電後長期にわたって使用を停止し、再度充電しようとしても充電が入らないのではニッケル・カドミウム電池、その他の電池に比べ使用上困難がある。 In the case of household appliances, because the user is unspecified, reliability is highly desirable, particularly for use over discharge after long stops, than neither enter charging trying again charged nickel-cadmium batteries, other some use on difficult compared to the battery. また当然のごとく寿命の面でも安定した寿命を有することが不可欠である。 Also it is essential that also has a stable lifetime in terms of natural as life.

このように密閉型鉛電池の要求に対し、従来の極板では上記の如く欠点があり満足の得られる特性を有していない。 To request thus sealed lead batteries, in the conventional electrode plate does not have the characteristics obtained satisfactory it has drawbacks as described above.

本発明は、陽極板内での活物質を均一に利用させ、しかも過放電放置状態でも容易に充電可能であるという密閉型鉛蓄電池の放電容量、放電特性、過放電放置特性さらに電流寿命を改善することを目的とする。 The present invention is an active material in the anode plate evenly utilized, yet the discharge capacity of the sealed lead-acid battery that can be easily charged even overdischarge standing state, discharge characteristic, improve the over-discharge storage characteristics further current life an object of the present invention is to.

問題点を解決するための手段 本発明は上記の問題点に対し、陽極活物質を保持した2枚の格子間に、電解液を保持したカーボン繊維からなる不織布を介在させたことを特徴とするものである。 To the invention means for solving the problems above-mentioned problems, between two lattice which holds the anode active material, characterized in that by interposing a nonwoven fabric made of carbon fiber that holds the electrolyte it is intended.

作用 格子・カーボン不織布・格子の3層構造の基体を用いて陽極板を作成するため、活物質層が、活物質・電解液を含むカーボン不織布・活物質と3層構造となり、結局電解液の硫酸は極板外部からと、3層の基体の中央のカーボン不織布から供給され、極板中央での利用が従来の陽極板より高まり、極板全体に均一に利用されうる。 To create a positive plate with a base body of the three-layer structure of the working grid carbon nonwoven, lattice, the active material layer becomes a carbon nonwoven-active material and 3-layer structure including an active material-electrolyte, eventually electrolyte sulfuric acid from plate outside is supplied from a central carbon nonwoven substrate having a three-layer, growing from the conventional anode plate is utilized in the electrode plate center, it may be uniformly utilized throughout the electrode plate. さらにカーボン不織布は導電性を有しており、過放電放置後格子と活物質界面に硫酸鉛の高抵抗層が形成されてもカーボン不織布を通じて充電電流が流れ得る。 Further carbon nonwoven fabric has conductivity, the charging current can flow through the carbon nonwoven fabric be formed a high resistance layer of lead sulfate in the over-discharge after standing lattice and the active material interface. そのため充電回復性が従来の陽極板にくらべはるかにすぐれている。 Therefore charge recovery is much more valuable than conventional anode plate.

実施例 本発明の詳細を実施例をもって説明する。 The details of the embodiments the present invention will be described with examples. 第1図に本発明の格子・カーボン不織布・格子の3層構造の基体を示す。 It shows the base of the three-layer structure of the lattice-carbon non-woven fabric, grid of the present invention in Figure 1. 1が格子、2がカーボン細繊維からなる不織布である。 1 lattice, 2 is a nonwoven fabric made of carbon fine fibers. 第2図は格子の平面図、第3図は3層構造の基体にペーストを充填し、化成して活物質化した本発明の陽極板の断面図である。 Figure 2 is a plan view of a grid, FIG. 3 is a paste was filled in a substrate having a three-layer structure, a cross-sectional view of an anode plate of the present invention as the active material of in conversion. 3が活物質である。 3 is an active material. この構造の陽極板は40mm×100mm×3mmの大きさとした。 The anode plate of the structure was the size of 40mm × 100mm × 3mm. 厚みの内訳は格子厚1.5mm×2、カーボン不織布0.4mm×1である。 Breakdown of thickness grating thickness 1.5 mm × 2, a carbon nonwoven 0.4 mm × 1. 作成はまずカーボン不織布2を格子1と格子1の間に挿入し、格子1と格子1はその耳部同志をアーク溶接にて接合一体とした。 Creating first carbon nonwoven fabric 2 is inserted between the grating 1 and the grating 1, the grating 1 and the grating 1 was joined together their ears comrades at arc welding. その後ペーストを両面より充填し、乾燥後通常の化成工程を施して陽極板とした。 Then paste was filled from both sides, and the anode plate by preparation After the usual formation process. その時の活物質量は28gであった。 Amount of the active material at that time was 28g. この陽極板1枚と通常の陰極板2 The anode plate 1 sheet and ordinary cathode plate 2
枚を用いて密閉型鉛蓄電池を作成した。 We have created a sealed lead-acid battery using a sheet. 電解液は比重1. Electrolyte specific gravity 1.
320硫酸16mlを用い、陰、陽極板間に介在させるリテーナは通常のものを用いた。 Using 320 sulfate 16 ml, a retainer to be interposed shade, the anode plates were used conventional. 比較のため陽極板として従来型の通常使用品、格子厚3.0mm、活物質量34gを用いて該陽極板以外まったく同型の従来の密閉型鉛蓄電池も作成した。 Conventional normal use article as an anode plate for comparison, grating thickness 3.0 mm, was also created at all conventional sealed lead-acid battery of the same type than the anode plate with an active material amount 34g. 以下従来の陽極板を使用した電池(以下「従来の電池」という)をb、本発明の陽極板を使用した電池(以下「本発明の電池」という)をaと記す。 The following battery using a conventional anode plate (hereinafter referred to as "conventional batteries") b, a battery using the anode plate of the present invention (hereinafter referred to as "battery of the present invention") referred to as a. 第4図に In Figure 4
2A放電の試験結果を記す。 Mark the test results of 2A discharge. 図からわかるように、本発明の電池aは従来の電池bよりはるかにすぐれた電圧特性を示し、特に放電終期で差が大きくみられる。 As can be seen, the battery a of the present invention shows the voltage characteristics far superior to the conventional battery b, the difference is seen largely particular discharge end. これは電解液の供給が放電終期まで安定して行なわれていることに対応し、反応が陽極板全体で起っていることによる。 This is because the response to being executed supply of the electrolytic solution is stable until the discharge end, the reaction is happening throughout the anode plate.
第5図、第6図はその証拠となる、2A放電後の陽極板内の反応分布を示す。 Figure 5, Figure 6 is the evidence indicates the reaction distribution in the anode plate after 2A discharge. ここでは反応生成物であるPbSO 4のSに注目し、PbSO 4の量をSのKα強度に対応させて示す。 Here, paying attention to S of PbSO 4 which is the reaction product are shown the amount of PbSO 4 in correspondence with the Kα strength S. 第5図は従来の陽極板の反応分布で、陽極板表面付近に反応分布が集中し、中央部の利用が少ない。 In Figure 5 the reaction distribution of the conventional anode plate, reaction distributed near the anode plate surface is concentrated, the use of the central portion is small. これに対し第6図に示す本発明の陽極板の反応分布は中央に電解液を有しているため、ほぼ全体的に反応していることが解る。 Reaction distribution of the anode plate of contrast present invention shown in FIG. 6, because it has a center electrolyte, it can be seen that almost totally reacted. さらに本発明陽極板の特性を把握するため、過放電放置後の容量回復性と寿命特性を調べた。 To further understand the characteristics of the present invention the anode plate was examined capacity recovery and lifetime characteristics after overdischarge standing. 容量回復性については2A放電後、2.45V定電圧充電を8時間行い、5Ωの抵抗にて定抵抗放電を5日間連続して行った。 After 2A discharge for capacitive recovery, it performed 8 hours 2.45V constant voltage charging was carried out with constant resistance discharge for five consecutive days at 5Ω resistor. その後周囲温度45℃の条件下で14日間放置し、再び Was then left under the conditions of ambient temperature 45 ° C. 14 days, again
2.45V定電圧充電を8時間行った。 2.45V constant voltage charging was carried out for eight hours. 充電終了後2A放電を行い、初期の容量と比較した。 It was charged after the end 2A discharge was compared with the initial capacity.

第7図に従来の電池bと本発明の電池aの容量回復率を示す。 Indicating the capacity recovery rate of the battery a conventional battery b and the present invention in FIG. 7. 図から明らかなように本発明の電池aは従来の電池bより容量回復率がすぐれている。 Cell a obvious way the invention from figure excellent capacity recovery rate than the conventional battery b. この理由は陽極板中央に導電性のカーボン不織布が存在するため過放電放置した後、格子と活物質界面に高抵抗層が存在しても、カーボン不織布から活物質へ電流が容易に流れ、充電受入性が良いためと考えられる。 The reason for this was allowed to stand over-discharge due to the presence of conductive carbon nonwoven anode plate center, even if the high-resistance layer is present in a grid and the active material interface, current easily flows from the carbon nonwoven fabric to the active material, the charge acceptance is considered to be for good. 寿命試験は2A30分放電、0.23A5時間充電で行った。 Life test 2A30 minutes discharge was performed at 0.23A5 hours charging. 温度は20℃である。 Temperature is 20 ℃. 第8 Eighth
図に100サイクル時点での結果を示す。 The results of 100 cycles point in FIG. 100サイクル時点では顕著な差はみられないが、従来の電池bは徐々に容量の低下がみられる。 Although not observed significant differences in the 100 cycle time, conventional battery b gradually decrease in volume is observed. これに対し本発明の電池aはこの時点で初期と変化がない。 Cell a of the present invention to which no initial a change at this point. なお容量確認は20サイクルごと2A完全放電で行った。 Incidentally capacity confirmation were carried out at every 20 cycles 2A full discharge. 寿命に関しては、100サイクルの時点ではわずかの差しか確認していないが、放電分布が均一的であり、局部的な活物質の劣化がないため、さらに格子の伸びに対し、たとえ格子と活物質界面にはがれが生じても中心部にカーボン不織布が存在することにより集電が可能であるため、100サイクル以降では差がでてくると思われる。 With regard to life, although not confirmed little difference at the time of 100 cycles, the discharge distribution is uniform manner, because there is no deterioration of the local active material, to further elongation of the grid, even if the lattice and the active substance because the interface is capable of current collection by the presence of carbon nonwoven fabric at the center even if peeling, in 100 cycles later seems to come out the difference.

発明の効果 以上の如く、本発明は、陽極活物質を保持した2枚の格子間に、電解液を保持したカーボン繊維からなる不織布を介在させたことを特徴とする密閉型鉛蓄電池用陽極板であって、これにより元来電解液が制限されている密閉型鉛蓄電池に使用される陽極板の活物質に、電解液が極板外部からだけでなく極板内部からも供給されるようになるため、陽極板全体に亘り活物質を均一に利用し得、放電特性、容量、寿命を改善でき、密閉型鉛蓄電池の過放電放置後の容量回復性、陽極格子の伸びによる容量低下を改善し得るものである。 As described above, according to the present, the present invention is between two grid holding the cathode active material, an anode plate for a sealed lead acid battery, characterized in that by interposing a nonwoven fabric made of carbon fiber that holds the electrolyte a is, thereby the active material of the anode plate to be used in sealed lead-acid batteries have limited originally electrolyte, such electrolyte is also supplied from the electrode plate inside as well as from the electrode plate outside becomes therefore, give uniformly utilizing an active material over the entire anode plate, discharge characteristics, capacity, it can improve the life, capacity recovery after overdischarge left of the sealed lead-acid battery, the capacity reduction due to elongation of the positive grids improvement it is capable of.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

第1図は本発明に使用する基体の説明図、第2図は第1 Figure 1 is an explanatory view of a substrate for use in the present invention, Figure 2 is the first
図の基体に使用する格子の平面図、第3図は本発明陽極板の断面図、第4図は本発明の電池と従来の電池の端子電圧と放電時間との関係特性比較曲線線、第5図は従来陽極板の反応分布図、第6図は本発明陽極板の反応分布図、第7図は本発明の電池と従来の電池の容量回復率の比較特性図、第8図は本発明の電池と従来の電池の放電持続時間と充放電サイクルとの関係特性比較曲線図である。 Plan view of a grating for use in the substrate of FIG, FIG. 3 is a cross-sectional view of the present invention an anode plate, Figure 4 is related characteristic comparison curves lines of the battery and the terminal voltage of a conventional battery of the present invention the discharge time, the 5 FIG reaction distribution diagram of a conventional anode plate, Figure 6 is a reaction distribution diagram of the present invention an anode plate, FIG. 7 is a battery and the comparative characteristic diagram of capacity recovery rate of the conventional battery of the present invention, FIG. 8 is present batteries and discharge duration of the conventional battery of the invention and the relationship characteristic comparison curves with charge and discharge cycles. 1:格子、2:カーボン不織布、3:活物質、a:本発明の電池、 1: lattice, 2: carbon nonwoven, 3: active material, a: battery of the present invention,

───────────────────────────────────────────────────── フロントページの続き (72)発明者 早川 他▲く▼美 東京都新宿区西新宿2丁目1番1号 新神 戸電機株式会社内 (72)発明者 小牧 昭夫 東京都新宿区西新宿2丁目1番1号 新神 戸電機株式会社内 (72)発明者 内田 敏夫 茨城県勝田市堀口832番地2号 株式会社 日立製作所日立研究所内 (72)発明者 森本 庄吾 茨城県勝田市堀口832番地2号 株式会社 日立製作所日立研究所内 審判の合議体 審判長 西 義之 審判官 小野 秀幸 審判官 相沢 旭 (56)参考文献 特公 昭52−29809(JP,B2) ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Hayakawa other ▲ ku ▼ beauty, Shinjuku-ku, Tokyo Nishi 2-chome No. 1 No. 1 Shin Kobe electric within Co., Ltd. (72) inventor Akio Komaki Tokyo Nishi-Shinjuku, Shinjuku-ku, in 2-chome No. 1 No. 1 Shin Kobe electric Co., Ltd. (72) inventor Toshio Uchida Ibaraki Prefecture Katsuta City Horiguchi 832 address No. 2 Hitachi, Ltd. Hitachi the laboratory (72) inventor Shogo Morimoto Ibaraki Prefecture Katsuta City Horiguchi 832 address No. 2 Hitachi, Ltd. Hitachi Research Laboratory within the referee collegial body Chief judge Yoshiyuki Nishi judge Hideyuki Ono judge Asahi Aizawa (56) references Tokuoyake Akira 52-29809 (JP, B2)

Claims (1)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】陽極活物質を保持した2枚の格子間に、電解液を保持したカーボン繊維からなる不織布を介在させたことを特徴とする密閉型鉛蓄電池用陽極板。 1. A between two lattice which holds the anode active material, an anode plate for a sealed lead acid battery, characterized in that by interposing a nonwoven fabric made of carbon fibers which holds the electrolytic solution.
JP60242443A 1985-10-29 1985-10-29 Anode plate for a sealed lead-acid battery Expired - Lifetime JPH0831336B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60242443A JPH0831336B2 (en) 1985-10-29 1985-10-29 Anode plate for a sealed lead-acid battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60242443A JPH0831336B2 (en) 1985-10-29 1985-10-29 Anode plate for a sealed lead-acid battery

Publications (2)

Publication Number Publication Date
JPS62103976A JPS62103976A (en) 1987-05-14
JPH0831336B2 true JPH0831336B2 (en) 1996-03-27

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KR20030005759A (en) * 2001-07-10 2003-01-23 한국전지주식회사 Electrode for lead storage battery and method for manufacturing thereof
AR067238A1 (en) 2007-03-20 2009-10-07 Commw Scient Ind Res Org Devices optimized for energy storage
CN105633416A (en) * 2008-11-18 2016-06-01 约翰逊控制技术公司 Electrical power storage devices
KR101827528B1 (en) 2009-02-26 2018-02-09 존슨 컨트롤스 테크놀러지 컴퍼니 Battery electrode and method for manufacturing same
AU2010292966B2 (en) * 2009-08-27 2014-07-24 Commonwealth Scientific And Industrial Research Organisation Electrical storage device and electrode thereof
JP2012133959A (en) 2010-12-21 2012-07-12 Commonwealth Scientific & Industrial Research Organisation Composite capacitor negative electrode plate for lead storage battery, and lead storage battery

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JPS5229809A (en) * 1975-09-02 1977-03-07 Tadashi Fukuyama Method of burning usual red bricks to dressing bricks

Also Published As

Publication number Publication date
JPS62103976A (en) 1987-05-14

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