JP4053272B2 - Negative electrode for lead acid battery - Google Patents
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- JP4053272B2 JP4053272B2 JP2001315036A JP2001315036A JP4053272B2 JP 4053272 B2 JP4053272 B2 JP 4053272B2 JP 2001315036 A JP2001315036 A JP 2001315036A JP 2001315036 A JP2001315036 A JP 2001315036A JP 4053272 B2 JP4053272 B2 JP 4053272B2
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- 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
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- Y02E60/10—Energy storage using batteries
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Description
【０００１】
【発明の属する技術分野】
本発明は、特にＰＳＯＣ状態でアイドルストップ、加速アシスト、回生充電等の高率充放電を繰り返すＨＥＶ用に適するシール型鉛蓄電池などの鉛蓄電池に関する。
【０００２】
【従来の技術】
最近、自動車用鉛蓄電池を従来の１２Ｖから３６Ｖに高電圧化する動きが活発化している。これは当初、利便性や低コスト化を目的とした自動車搭載機器の電動化に伴う電力需要急増への対応やワイヤーハーネス重量抑制を目的として進められていた。しかしその後、環境対策や低燃費化が大きな関心事となると共に、高効率スタータ・ジェネレータが開発された事で、３６Ｖでもアイドルストップ機能は勿論、スタート・アシストやブレーキ時のエネルギー回生が可能となり、従来のＨＥＶの範疇を大幅に拡げる事となった。その結果、安価でメンテナンスフリーのシール型鉛蓄電池をこの用途に用いる試みが活発化している。
ところで、これらの機能のうちアイドルストップやスタート・アシストは鉛蓄電池に高い放電性能を要求する。従来の鉛蓄電池は、この点において非常に優れていると言われていたが、後述するエネルギー回生では充電状態を低めにするため、電解液中の硫酸イオンは不足状態となり、特に急速放電時は極板近傍の硫酸イオンは急激に消費されて放電性能は著しく低下する。エネルギー回生は、高効率の急速充電性能を要求するが、鉛蓄電池はその要求に適さないと言われている。その理由は、高効率の急速充電を行うには電池の充電状態（ＳＯＣ）を例えば６０〜９０％と中途半端な充電状態（ＰＳＯＣ）にしておく必要があるが、鉛蓄電池はこの状態で充放電を繰り返すと負極に放電物質である硫酸鉛の結晶が成長・粗大化し、可逆性が失われたサルフェーションと言われる状態になるからである。特に、回生充電のように短時間に大電流で充電を行う場合には、僅か１００回程度の回生充電と放電の繰り返しで、即ち、ブレーキを１００回踏む操作で、負極の海綿状鉛の表面に生成した硫酸鉛の影響で負極の分極が水素発生電位まで増大し、充電効率は急速に低下する事になる。
これらの問題を解決するために、従来、その負極に導電剤として粒状や繊維状のカーボンを例えば０．５重量％以上或いはアセチレンブラックを０．４〜７．５重量％を添加することが提案されている。（特開平６−３４９４８６、特開平７−６７６７、特開平７−２０１３３１などの公報参照）。また、同様の目的で添加するカーボンを微細な繊維状とし、これを０．０１〜１０ｗｔ．％添加したり、粉末と組み合わせたりする事も提案されている。（特開平２−１７７２６０、特許第２７２９６４４号、特許第２８４７７６１号などの公報参照）。
【０００３】
【発明が解決しようとする課題】
しかし乍ら、上記の公知技術では、未だ、上記のようなＰＳＯＣの使用状態から満足なエネルギー回生特性が得られず、その改善が望まれていた。
本発明は、上記従来の鉛蓄電池の課題を解消し、ＰＳＯＣ状態での充電特性を大幅に改善し、ＰＳＯＣ状態からのエネルギー回生特性に優れ、特にＨＥＶ用に鉛蓄電池に適した鉛蓄電池をもたらす負極を開発したものである。
【０００４】
【課題を解決するための手段】
本発明は、上記従来の課題を解消し、回生充電特性の優れた鉛蓄電池用負極を提供するもので、負極活物質にアセチレンブラックとバリウム化合物を添加して成る鉛蓄電池用負極において、負極活物質１００重量部に対し、平均粒径３０ｎｍ以下、比表面積１００〜１５０ｍ2 ／ｇ、ＤＢＰ吸油量１５０ｍ3 ／１００ｇ以上であるアセチレンブラックを０．５〜４重量部添加し、更に、該アセチレンブラックと硫酸バリウムを、該アセチレンブラックと該硫酸バリウムの重量比率が１：１〜１．７で添加したことを特徴とする。
【０００５】
【発明の実施の形態】
本発明の実施例を以下詳述する。
本発明の鉛蓄電池用負極を製造するに当たり、添加されるカーボン粉末としてアセチレンブラックに限定する理由は、カーボンブラックなどの他のカーボン粉末より高温に対し安定であり、而も製造過程で水素や酸素を取り込み難く、水素や酸素含有量が低いため、導電性に優れている基本的な特性を有するからである。
このアセチレンブラックにつき種々検討したところ、後記に明らかにするように、アセチレンブラックの平均粒径は、３０ｎｍ以下になると海綿状鉛活物質の表面に網目状の導電ネットワークを形成し、ＰＳＯＣ状態でも硫酸鉛の蓄積を抑制する効果があることが判った。また、一般に、微細なカーボンブラックは、通常比表面積が大きくなり、それに伴って水素過電圧の低下と水素発生の増大、即ち充電効率の低下を招くが、特に３０ｎｍ以下のアセチレンブラックはアグリゲート構造が非常に良く発達しているために比表面積が１００〜１５０ｍ2 ／ｇの範囲において特に水素過電圧がむしろ増加して、充電効率が向上することが判った。また、そのＤＢＰ吸油量は２００ｍ3 ／１００ｇ以上であると電解液を保持する効果が非常に高く、急速な充放電を行っても拡散律速による分極を低く抑える事ができることが判った。
【０００６】
而して、かゝる特定の条件を有するアセチレンブラックの負極活物質への添加量は、負極活物質１００重量部に対し０．５〜４重量部添加し、更に該アセチレンブラックと硫酸バリウムを重量比率１：１〜１．７で添加することにより、下記に詳述するように、回生特性の改善効果を発揮することが判った。
【０００７】
また、負極活物質には、アセチレンブラックと共にバリウム化合物を添加併用される。その使用されるバリウム化合物は、硫酸バリウムや炭酸バリウム等であるが、これらは電解液である硫酸と反応し、硫酸バリウムに変化する。そして、硫酸バリウムが有する硫酸鉛の核化剤として働き、即ち硫酸鉛の粗大化を抑制する作用にアセチレンブラックが影響する。この場合、該アセチレンブラックと硫酸バリウムの添加量の配合割合が、重量比でアセチレンブラック１対硫酸バリウム１〜１．７で添加するときは、最良の放電特性と回生特性の向上をもたらすことが判った。尚、硫酸バリウムとしては、平均粒径０．７μｍのものを使用することが好ましい。
【０００８】
次に、本発明の鉛蓄電池用負極の実施例として、その製造例とこれを用いた鉛蓄電池の諸特性を比較例と共に詳述する。
（１）未化成の負極板の製造：
負極活物質として、ボールミル法で製造した酸化鉛（ＰｂＯ）に、該酸化鉛１００重量部に対し、下記表１の実施例及び比較例に示すように、平均粒径、比表面積、ＤＢＰ吸油量を異にするアセチレンブラック（Ｃ）とその添加量と硫酸バリウム（ＢａＳＯ4 ）の添加量と添加されるＣとＢａＳＯ4 の配合比率を異にして添加し、次に、リグニンを水溶液として加え、続いてイオン交換水を加え乍ら混練して水ペーストを調製し、更に比重１．３６の希硫酸を加え乍ら混練し各種の負極活物質ペーストを調製した。このときに使用したイオン交換水の量は酸化鉛１００重量部に対しておよそ１０重量部、希硫酸の量は１０重量部であった。尚、出来上がったペーストのカップ密度が約１３５ｇ／２ｉｎ３となるようにイオン交換水の量を調製した。このように製造したペーストをカルシウム合金から成る鋳造基板に充填し、４０℃、湿度９５％の雰囲気で２４時間熟成し、その後乾燥して各種の未化成の負極板を製造した。
（２）未化成の正極板の製造：
酸化鉛１００重量部にイオン交換水１０重量部、続いて比重１．２７の希硫酸１０重量部を加え乍ら混練して正極用ペーストを調製した。このペーストのカップ密度は約１４０ｇ／２ｉｎ３であった。このペーストをカルシウム合金から成る鋳造基板に充填し、４０℃、湿度９５％の雰囲気で２４時間熟成し、その後乾燥して未化成の正極板を多数製造した。
（３）電池組立、電解液の調製の化成：
これらの未化成板に微細なガラス繊維に約１０％のシリカ粉末を加えて成る、２０ｋＰａ加圧時の厚みが０．８ｍｍのリテーナマットセパレータを組み合わせ、ＣＯＳ方式で極板同士を溶接して極板群とした。これをＰＰ製の電槽に入れ、ヒートシールによって蓋をした。次に、電槽化成に用いる比重１．２０の電解液を調製した。これに放電状態での短絡防止用に硫酸ナトリウムを添加して用いた。この電解液を電池に入れて４０℃の水槽中で理論容量の２００％過充電して電槽化成を行い、表１に示す実施例及び比較例の負極を用いた夫々の２Ｖのシール型鉛蓄電池を製造した。この電池の電解液比重は１．２６０であり、電解液量は極板群の理論空間体積の１００％に調製した。化成後に行った電池の容量試験で５時間率容量は２０Ａｈであった。
【０００９】
放電性能の評価：
次に、このように製造した上記の実施例及び比較例に示す各種の鉛蓄電池につき、２５℃、５時間率電流で完全充電した後、５時間率電流でＳＯＣを７０％に調製した。即ち６Ａｈ分の放電を行った。次に、電池を−１５℃で１６時間放置した。その後、３００Ａで５秒間放電し、５秒目の電圧を測定した。その放電特性の測定の結果を表１に示した。望ましい値は、１．４５Ｖ以上である。
【００１０】
また、上記の各電池を、２５℃、５時間率電流で完全充電した後、５時間率電流でＳＯＣを７０％に調製した。即ち６Ａｈ分の放電を行った。次に、電池温度が４０℃となるように雰囲気温度を調製し、６０Ａ、４０秒間の定電流放電と４０Ａ、５０秒間、８０Ａ、５秒間、上限電圧２．３３Ｖの定電流・定電圧充電の組み合わせを１サイクルとする回生充電繰り返し試験を行った。そして、８０Ａ、５秒間の回生充電時の電池電圧が２．３３Ｖの上限電圧に到達するまでの回数を測定した。この試験は、充電電気量と放電電気量が等しいため、回生充電に相当する８０Ａ、５秒間の充電が完全に行われないと充電不足となる。即ち、８０Ａ充電中に負極が分極して電池電圧が２．３３Ｖに達すると定電圧充電に切り替わり、電流が減衰して充電不足となる。その回生充電特性の測定の結果を表１に示した。望ましい値の目安は５００回である。
【００１１】
【表１】
上記表１から明らかなように、平均粒径３０ｎｍ以下、比表面積１００〜１５０ｍ2 ／ｇ、ＤＢＰ吸油量２００ｃｍ3 ／１００ｇ以上の特定の条件を有するアセチレンブラックを負極活物質１００重量部に対し０．５〜４重量部添加して、更に、上記の条件を満たしたアセチレンブラックと硫酸バリウムの配合割合を重量比で１対１〜１．７の配合で添加して製造した負極を鉛蓄電池に用いるときは、優れた放電特性とＰＳＯＣ状態からの優れた回生特性を有する鉛蓄電池を確実に製造することができることが判る。
【００１３】
【発明の効果】
このように請求項１に係る発明による負極を鉛蓄電池に用いるときは、上記従来の鉛蓄電池用負極の課題を解消し、優れた放電特性とＰＳＯＣ状態からの優れた回生特性を確保された鉛蓄電池をもたらし、ＨＥＶ用などに用い優れた鉛蓄電池を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lead-acid battery such as a sealed lead-acid battery suitable for HEV that repeats high-rate charging / discharging such as idle stop, acceleration assist, regenerative charging, etc., particularly in a PSOC state.
[0002]
[Prior art]
Recently, the movement to increase the voltage of lead-acid batteries for automobiles from the conventional 12V to 36V has been activated. This was initially promoted for the purpose of responding to the sudden increase in power demand accompanying the electrification of on-board equipment for the purpose of convenience and cost reduction, and reducing the weight of the wire harness. However, environmental measures and fuel efficiency have become a major concern since then, and the development of a high-efficiency starter / generator enables the idling stop function at 36V as well as energy recovery during start assist and braking. The category of conventional HEV was greatly expanded. As a result, attempts to use inexpensive, maintenance-free, sealed lead-acid batteries for this purpose have become active.
By the way, among these functions, idle stop and start assist require high discharge performance for lead-acid batteries. Conventional lead-acid batteries were said to be very good in this regard, but in order to lower the state of charge in energy regeneration, which will be described later, the sulfate ions in the electrolyte became insufficient, especially during rapid discharge. Sulfate ions in the vicinity of the electrode plate are consumed rapidly, and the discharge performance is significantly reduced. Energy regeneration requires high-efficiency rapid charging performance, but lead-acid batteries are said to be unsuitable. The reason for this is that in order to perform high-efficiency rapid charging, the state of charge (SOC) of the battery needs to be half-way charged (PSOC), for example, 60 to 90%, but the lead storage battery is charged in this state. This is because if the discharge is repeated, crystals of lead sulfate, which is a discharge substance, grow and coarsen on the negative electrode, and a state called sulfation is lost. In particular, when recharging with a large current in a short time, such as regenerative charging, the surface of the sponge lead of the negative electrode is obtained by repeating regenerative charging and discharging only about 100 times, that is, by stepping on the brake 100 times. Due to the effect of lead sulfate formed on the electrode, the polarization of the negative electrode increases to the hydrogen generation potential, and the charging efficiency rapidly decreases.
In order to solve these problems, it has been proposed to add 0.5% by weight or more of granular or fibrous carbon or 0.4 to 7.5% by weight of acetylene black as a conductive agent to the negative electrode. Has been. (See JP-A-6-349486, JP-A-7-6767, JP-A-7-201331, etc.). Moreover, carbon added for the same purpose is made into a fine fiber, and this is 0.01 to 10 wt. % Addition or combination with powder is also proposed. (See JP-A-2-177260, Japanese Patent No. 2729644, Japanese Patent No. 2847761, etc.).
[0003]
[Problems to be solved by the invention]
However, in the above-described known technology, satisfactory energy regenerative characteristics are not yet obtained from the use state of PSOC as described above, and an improvement thereof has been desired.
The present invention eliminates the above-mentioned problems of the conventional lead storage battery, greatly improves the charge characteristics in the PSOC state, has excellent energy regeneration characteristics from the PSOC state, and brings about a lead storage battery suitable for lead storage batteries, particularly for HEVs. The negative electrode was developed.
[0004]
[Means for Solving the Problems]
The present invention solves the above-mentioned conventional problems and provides a negative electrode for a lead storage battery having excellent regenerative charge characteristics. In a negative electrode for a lead storage battery comprising acetylene black and a barium compound added to a negative electrode active material, relative to material 100 parts by weight, average particle size below 30 nm, the acetylene black is a specific surface area of 100-150 2 / g, DBP oil absorption of 150 meters 3/100 g or more was added 0.5 to 4 parts by weight, further, the acetylene black And barium sulfate are added at a weight ratio of 1: 1 to 1.7 of the acetylene black and the barium sulfate .
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the present invention are described in detail below.
The reason for limiting the added carbon powder to acetylene black in the production of the negative electrode for a lead storage battery of the present invention is that it is more stable at higher temperatures than other carbon powders such as carbon black. This is because it has a basic characteristic of being excellent in conductivity because it is difficult to incorporate hydrogen and has a low content of hydrogen and oxygen.
As a result of various studies on this acetylene black, as will be clarified later, when the average particle size of acetylene black is 30 nm or less, a network-like conductive network is formed on the surface of the spongy lead active material, and sulfuric acid is also in the PSOC state. It was found that there is an effect of suppressing lead accumulation. In general, fine carbon black usually has a large specific surface area, which causes a decrease in hydrogen overvoltage and an increase in hydrogen generation, that is, a decrease in charging efficiency. Particularly, acetylene black of 30 nm or less has an aggregate structure. It has been found that because of its very well developed specific surface area in the range of 100 to 150 m 2 / g, the hydrogen overvoltage is rather increased and the charging efficiency is improved. Further, the DBP oil absorption was found that can effect of retaining the the electrolyte is 200 meters 3/100 g or more is suppressed very high, even if rapid charge and discharge lower polarization due diffusion control.
[0006]
Thus, the amount of acetylene black having such specific conditions added to the negative electrode active material is 0.5 to 4 parts by weight with respect to 100 parts by weight of the negative electrode active material, and the acetylene black and barium sulfate are further added. It has been found that by adding at a weight ratio of 1: 1 to 1.7, the effect of improving the regeneration characteristics is exhibited as described in detail below.
[0007]
The negative electrode active material is used in combination with acetylene black and a barium compound. The barium compound used is barium sulfate, barium carbonate, or the like, but these react with sulfuric acid as an electrolytic solution and change to barium sulfate. And acetylene black influences the effect | action which acts as a nucleating agent of the lead sulfate which barium sulfate has, ie, suppresses the coarsening of lead sulfate. In this case, when the addition ratio of the acetylene black and barium sulfate is added in a weight ratio of 1 acetylene black to 1 to 1.7 barium sulfate, the best discharge characteristics and regenerative characteristics can be improved. understood. As barium sulfate, it is preferable to use one having an average particle size of 0.7 μm.
[0008]
Next, as an example of the negative electrode for a lead storage battery of the present invention, its production example and various characteristics of a lead storage battery using the same will be described in detail together with a comparative example.
(1) Production of unformed negative electrode plate:
As a negative electrode active material, lead oxide (PbO) produced by a ball mill method, with respect to 100 parts by weight of the lead oxide, as shown in Examples and Comparative Examples in Table 1 below, average particle diameter, specific surface area, DBP oil absorption amount The acetylene black (C) and the addition amount thereof, and the addition amount of barium sulfate (BaSO 4 ) and the blending ratio of C and BaSO 4 to be added are added differently, and then lignin is added as an aqueous solution. Subsequently, ion exchange water was added and kneaded while preparing a water paste, and further dilute sulfuric acid having a specific gravity of 1.36 was added and kneaded while preparing various negative electrode active material pastes. The amount of ion-exchanged water used at this time was approximately 10 parts by weight with respect to 100 parts by weight of lead oxide, and the amount of dilute sulfuric acid was 10 parts by weight. The amount of ion-exchanged water was adjusted so that the cup density of the finished paste was about 135 g / 2 in3. The paste thus produced was filled into a cast substrate made of a calcium alloy, aged for 24 hours in an atmosphere of 40 ° C. and 95% humidity, and then dried to produce various unformed negative electrode plates.
(2) Production of unformed positive electrode plate:
A positive electrode paste was prepared by adding 10 parts by weight of ion-exchanged water to 100 parts by weight of lead oxide followed by 10 parts by weight of dilute sulfuric acid having a specific gravity of 1.27 and kneading. The cup density of this paste was about 140 g / 2 in3. This paste was filled in a cast substrate made of a calcium alloy, aged for 24 hours in an atmosphere of 40 ° C. and 95% humidity, and then dried to produce a large number of unformed positive plates.
(3) Formation of battery assembly and preparation of electrolyte:
These unformed sheets are combined with a retainer mat separator with a thickness of 0.8 mm when pressurized to 20 kPa, which is made by adding about 10% silica powder to fine glass fibers, and the electrodes are welded together by the COS method. A group of plates was used. This was put into a battery case made of PP and covered by heat sealing. Next, an electrolytic solution having a specific gravity of 1.20 used for battery case formation was prepared. To this, sodium sulfate was added to prevent short circuit in the discharged state. This electrolyte solution is put into a battery, overcharged by 200% of the theoretical capacity in a 40 ° C. water tank, and then formed into a battery case, and each 2V sealed lead using the negative electrodes of the examples and comparative examples shown in Table 1 A storage battery was manufactured. The specific gravity of the electrolyte of this battery was 1.260, and the amount of the electrolyte was adjusted to 100% of the theoretical space volume of the electrode plate group. In the battery capacity test conducted after the formation, the 5-hour rate capacity was 20 Ah.
[0009]
Evaluation of discharge performance:
Next, the various lead storage batteries shown in the above-described Examples and Comparative Examples were fully charged at 25 ° C. and a 5-hour rate current, and then the SOC was adjusted to 70% at the 5-hour rate current. That is, discharge for 6 Ah was performed. Next, the battery was left at −15 ° C. for 16 hours. Thereafter, the battery was discharged at 300 A for 5 seconds, and the voltage at 5 seconds was measured. The results of measurement of the discharge characteristics are shown in Table 1. A desirable value is 1.45V or more.
[0010]
Moreover, after fully charging each said battery at 25 degreeC and 5 hour rate current, SOC was adjusted to 70% with 5 hour rate current. That is, discharge for 6 Ah was performed. Next, the ambient temperature is adjusted so that the battery temperature is 40 ° C., constant current discharge for 60 A for 40 seconds, and constant current / constant voltage charging for 40 A, 50 seconds, 80 A, 5 seconds, upper limit voltage 2.33 V. A regenerative charge repetition test was performed with the combination as one cycle. The number of times until the battery voltage at the time of regenerative charging at 80 A for 5 seconds reached the upper limit voltage of 2.33 V was measured. In this test, since the amount of charge electricity is equal to the amount of discharge electricity, 80A corresponding to regenerative charge and charging for 5 seconds are not fully performed, resulting in insufficient charge. That is, when the negative electrode is polarized during 80 A charging and the battery voltage reaches 2.33 V, switching to constant voltage charging is performed, the current is attenuated, and charging becomes insufficient. The measurement results of the regenerative charge characteristics are shown in Table 1. A desirable value is 500 times.
[0011]
[Table 1]
As is apparent from Table 1, average particle size below 30 nm, with respect to the negative electrode active material 100 parts by weight of acetylene black having a specific surface area of 100-150 2 / g, DBP oil absorption of 200 cm 3/100 g or more specified conditions 0 .5-4 parts by weight , and further, a negative electrode manufactured by adding a mixing ratio of acetylene black and barium sulfate satisfying the above conditions in a weight ratio of 1: 1 to 1.7 is used as a lead storage battery. case, it is Ru determine which can be produced reliably lead storage battery having excellent regeneration characteristics from excellent discharge characteristics and PSOC condition used.
[0013]
【The invention's effect】
When using a negative electrode according to the invention in this way according to claim 1 in lead-acid battery, and canceling the negative electrode challenges for the conventional lead-acid batteries, it is ensured a good regeneration properties from superior discharge characteristics and PSOC condition A lead storage battery can be provided, and an excellent lead storage battery used for HEV or the like can be provided.
Claims (1)
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| CN101309985B (en) | 2005-11-16 | 2011-10-12 | 精工爱普生株式会社 | Magenta ink composition, ink cartridge, and recording system and recorded matter using the same |
| JP2007173112A (en) * | 2005-12-22 | 2007-07-05 | Ntt Data Ex Techno Corp | Anode active material for secondary battery, secondary battery and their manufacturing method |
| JP5115695B2 (en) | 2006-04-03 | 2013-01-09 | セイコーエプソン株式会社 | Ink set |
| JP4523580B2 (en) * | 2006-12-19 | 2010-08-11 | エヌ・ティ・ティ・データ先端技術株式会社 | Negative electrode active material for secondary battery and intermediate kneaded material for producing them |
| JP5293987B2 (en) | 2007-07-19 | 2013-09-18 | セイコーエプソン株式会社 | Ink set, inkjet recording method |
| JP5365095B2 (en) | 2008-08-25 | 2013-12-11 | セイコーエプソン株式会社 | Ink set |
| JP5365111B2 (en) | 2008-09-10 | 2013-12-11 | セイコーエプソン株式会社 | Ink set, recording method, and recording apparatus |
| JP5387037B2 (en) | 2009-02-23 | 2014-01-15 | セイコーエプソン株式会社 | Ink set, recording apparatus, and recording method |
| JP2011116876A (en) | 2009-12-04 | 2011-06-16 | Seiko Epson Corp | Ink set, recording device, and recording method |
| JP5656116B2 (en) * | 2011-04-12 | 2015-01-21 | 株式会社Ｇｓユアサ | Lead acid battery |
| DE112013000779T5 (en) * | 2012-01-31 | 2014-10-30 | Panasonic Corporation | Lead-acid battery |
| JP6870207B2 (en) * | 2016-03-08 | 2021-05-12 | 昭和電工マテリアルズ株式会社 | Lead-acid battery |
| US10511016B2 (en) * | 2016-11-30 | 2019-12-17 | Global Graphene Group, Inc. | Graphene-protected lead acid batteries |
| JP6458829B2 (en) * | 2017-06-29 | 2019-01-30 | 株式会社Ｇｓユアサ | Lead acid battery |
| JP7196497B2 (en) * | 2018-09-25 | 2022-12-27 | 株式会社Ｇｓユアサ | Negative electrode for lead-acid battery and lead-acid battery |
| EP3891826A1 (en) * | 2018-12-04 | 2021-10-13 | Cabot Corporation | Compositions, electrodes and lead-acid batteries having improved low-temperature performance |
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