JP5598368B2 - Lead acid battery and negative electrode active material thereof - Google Patents
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- 239000007773 negative electrode material Substances 0.000 title claims description 34
- 239000002253 acid Substances 0.000 title claims description 24
- 239000000835 fiber Substances 0.000 claims description 69
- 239000006229 carbon black Substances 0.000 claims description 60
- 239000003365 glass fiber Substances 0.000 claims description 38
- 239000002657 fibrous material Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000002482 conductive additive Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- 230000000694 effects Effects 0.000 description 17
- 239000006230 acetylene black Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000019635 sulfation Effects 0.000 description 8
- 238000005670 sulfation reaction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Description
この発明は鉛蓄電池の負極活物質に関する。 The present invention relates to a negative electrode active material for a lead-acid battery.
近年、自動車は燃費改善や排出ガスの削減が強く求められるようになり、鉛蓄電池はアイドリングストップに代表されるような不完全充電状態（PSOC：Partial State of Charge）で頻繁に充放電が繰り返されるといった、従来よりも過酷な条件で使用される機会が増加している。また、太陽光発電や風力発電などの自然エネルギーを蓄電池に貯蔵する場合も同様に、PSOC条件下での使用が繰り返される。PSOC条件下では、負極のサルフェーションにより鉛蓄電池が早期に寿命を迎えることがある。サルフェーションは還元困難な硫酸鉛が負極活物質に蓄積するため、鉛蓄電池の容量が低下する現象である。サルフェーションを抑制するため、カーボンブラックからなる導電性のネットワークを負極活物質中に設け、硫酸鉛を還元する際の電流経路とすることが知られている。 In recent years, there has been a strong demand for automobiles to improve fuel economy and reduce exhaust emissions, and lead-acid batteries are frequently charged and discharged repeatedly in an incompletely charged state (PSOC: Partial State of Charge) as represented by idling stop. The opportunity to be used under severer conditions than before is increasing. Similarly, when natural energy such as solar power generation or wind power generation is stored in a storage battery, use under PSOC conditions is repeated. Under PSOC conditions, lead-acid batteries may reach the end of their life due to negative electrode sulfation. Sulfation is a phenomenon in which the capacity of lead-acid batteries decreases because lead sulfate, which is difficult to reduce, accumulates in the negative electrode active material. In order to suppress sulfation, it is known that a conductive network made of carbon black is provided in the negative electrode active material to provide a current path for reducing lead sulfate.
しかしながらカーボンブラックの粒子は負極活物質細孔径よりも細かいので、充電時に水素ガスが発生する際等に負極活物質から流出し失効する。カーボンブラックを負極活物質に固定するため、特許文献１（特開2007-328979）は、繊維径が10μｍ、繊維長が2mmのポリプロピレン繊維をカーボンブラックと共に、負極活物質に添加することを開示している。そして繊維径は1〜50μｍが好ましく、繊維長は4mm以下が好ましいとしている。しかしながら発明者は、径が1μｍ以上の繊維ではサルフェーションの抑制効果が限られていることを確認した（図１，図３，図５）。 However, since the carbon black particles are finer than the pore diameter of the negative electrode active material, the hydrogen black gas flows out of the negative electrode active material when hydrogen gas is generated at the time of charging. In order to fix carbon black to the negative electrode active material, Patent Document 1 (Japanese Patent Laid-Open No. 2007-328979) discloses that polypropylene fiber having a fiber diameter of 10 μm and a fiber length of 2 mm is added to the negative electrode active material together with carbon black. ing. The fiber diameter is preferably 1 to 50 μm, and the fiber length is preferably 4 mm or less. However, the inventor has confirmed that the suppression effect of sulfation is limited for fibers having a diameter of 1 μm or more (FIGS. 1, 3 and 5).
特許文献２（特開平6-140043）はカーボンウィスカーあるいはグラファイトウィスカーを、カーボンブラックと共に負極活物質に添加することを開示している。カーボンウィスカー及びグラファイトウィスカーは導電性で、カーボンブラックと共に導電性のネットワークを構成する。しかしながらカーボンウィスカー及びグラファイトウィスカーは極めて高価な材料である。 Patent Document 2 (Japanese Patent Laid-Open No. 6-140043) discloses that carbon whiskers or graphite whiskers are added to the negative electrode active material together with carbon black. Carbon whiskers and graphite whiskers are conductive and form a conductive network with carbon black. However, carbon whiskers and graphite whiskers are extremely expensive materials.
この発明の課題は、高価なカーボンウィスカーあるいはグラファイトウィスカーを用いず、かつ効果的に負極活物質からのカーボンブラックの流出を抑制することにある。 An object of the present invention is to suppress the outflow of carbon black from the negative electrode active material without using expensive carbon whiskers or graphite whiskers.
この発明は、0.1質量%以上のカーボンブラックと、平均繊維径が0.9μｍ以下であり、且つ、平均繊維長が5μｍ以上であり、且つ、0.05質量％以上の非導電性繊維物質と、を含有する（ただし、非導電性繊維物質にカーボンブラックを担持させて導電性添加剤を形成させたものを除く）鉛蓄電池の負極活物質にある。
また、この発明は、上記の負極活物質を保持する負極板と、正極板と、電解液とを備える、鉛蓄電池にある。
The present invention, carbon black of 0.1 weight%, average fiber diameter of not more than 0.9 .mu.m, and is the average fiber length of 5μm or more and containing a non-conductive fiber material of 0.05 mass% or more, the However, it is in the negative electrode active material of a lead storage battery (except for the case where carbon black is supported on a non-conductive fiber material to form a conductive additive) .
Moreover, this invention exists in a lead acid battery provided with the negative electrode plate holding said negative electrode active material, a positive electrode plate, and electrolyte solution.
この発明では、負極活物質の細孔に非導電性繊維物質を分散させて、カーボンブラックの流出を抑制する。非導電性繊維物質はカーボンブラックの流出を抑制する安価な材料で良く、細孔中にネットを構成することにより、カーボンブラックの流出を抑制する。以上のように、この発明での非導電性繊維物質は、カーボンウィスカー、グラファイトウィスカーのように、それ自体が導電性の経路となるものではない。また非導電性繊維物質は繊維径が0.9μｍ以下の小径の繊維なので、少量でも細孔からのカーボンブラックの流出を抑制できる。この結果、硫酸鉛の還元を容易にして、PSOC下での鉛蓄電池の寿命性能を向上させ、またカーボンブラックの流出による電解液の汚染を抑制する。 In the present invention, the non-conductive fiber material is dispersed in the pores of the negative electrode active material to suppress the outflow of carbon black. The non-conductive fiber substance may be an inexpensive material that suppresses the outflow of carbon black, and suppresses the outflow of carbon black by forming a net in the pores. As described above, the non-conductive fiber material in the present invention does not itself become a conductive path like carbon whisker and graphite whisker. Further, since the non-conductive fiber material is a small fiber having a fiber diameter of 0.9 μm or less, the outflow of carbon black from the pores can be suppressed even with a small amount. As a result, the reduction of lead sulfate is facilitated, the life performance of the lead storage battery under PSOC is improved, and the contamination of the electrolyte due to the outflow of carbon black is suppressed.
非導電性繊維物質は負極活物質の細孔に存在してカーボンブラックの流出を防ぐ、一種のネットとして作用する。従ってその種類は任意であるが、好ましくは非導電性繊維物質をグラスファイバーとする。グラスファイバーでは、繊維径が0.9μｍ以下のものを工業的に入手できるので、実用的である。また好ましくは、非導電性繊維物質の平均繊維径を0.1μｍ以上0.9μｍ以下とする。前記のように非導電性繊維物質はカーボンブラックの流出を防ぐネットとして作用するので、繊維径が小さいほど有効で、平均繊維径が0.9μｍ以下で大きな効果が得られ、1.2μｍ以上では効果が小さい（図１，図３，図５）。この一方で、繊維径が0.1μｍ未満のものは紡糸が難しい。そこで平均繊維径を0.1μｍ以上0.9μｍ以下とすることが好ましい。特に好ましくは、負極活物質は非導電性繊維物質を0.05質量%以上1.0質量%以下含有する。図１に示すように、0.05質量%の非導電性繊維物質で既に充分な効果があり、過剰量の含有は好ましくないので1.0質量%以下が好ましい。非導電性繊維物質は負極活物質の細孔からカーボンブラックが流出することを抑制するネットとして作用するので、非導電性物質自体の流出を防ぐために負極活物質の平均細孔径(1〜2μm)よりも長さのある5μｍ以上の平均繊維長が好ましく、活物質ペーストの作りやすさ等の理由から、5mm以下の平均繊維長が好ましい。 The non-conductive fiber material acts as a kind of net that exists in the pores of the negative electrode active material and prevents the outflow of carbon black. Therefore, although the kind is arbitrary, Preferably a nonelectroconductive fiber substance is used as a glass fiber. A glass fiber having a fiber diameter of 0.9 μm or less is industrially available, and is practical. Preferably, the average fiber diameter of the non-conductive fiber material is 0.1 μm or more and 0.9 μm or less. As described above, the non-conductive fiber material acts as a net for preventing the carbon black from flowing out. Therefore, the smaller the fiber diameter, the more effective, and the larger the average fiber diameter is 0.9 μm or less, the more effective is 1.2 μm or more. Small (FIGS. 1, 3 and 5). On the other hand, spinning is difficult when the fiber diameter is less than 0.1 μm. Therefore, the average fiber diameter is preferably 0.1 μm or more and 0.9 μm or less. Particularly preferably, the negative electrode active material contains 0.05% by mass or more and 1.0% by mass or less of the non-conductive fiber material. As shown in FIG. 1, 0.05% by mass of the non-conductive fiber material already has a sufficient effect, and excessive content is not preferred, so 1.0% by mass or less is preferred. Since the non-conductive fiber material acts as a net that suppresses the outflow of carbon black from the pores of the negative electrode active material, the average pore size (1-2 μm) of the negative electrode active material to prevent the non-conductive material itself from flowing out An average fiber length of 5 μm or more is preferable, and an average fiber length of 5 mm or less is preferable for reasons such as ease of making an active material paste.
好ましくは、負極活物質はカーボンブラックを0.1質量%以上10質量%以下含有する。なおカーボンブラックの種類は、アセチレンブラック、ファーネスブラック、ケッチェンブラック等任意である。図２，図４，図６に示すように、カーボンブラックが0.1質量%よりも多くなると、非導電性物質によりカーボンの流出を抑える効果が高くなり、過剰に含有すると非導電性物質では抑えきれない電解液の汚染、負極活物質中の鉛粉含有量の減少等の弊害が生じるので、好ましくは10質量%以下含有させる。 Preferably, the negative electrode active material contains 0.1% by mass or more and 10% by mass or less of carbon black. The type of carbon black is arbitrary such as acetylene black, furnace black, and ketjen black. As shown in FIGS. 2, 4, and 6, when the amount of carbon black exceeds 0.1% by mass, the effect of suppressing the outflow of carbon is increased by the non-conductive substance, and when it is excessively contained, the non-conductive substance can be suppressed. Since there are adverse effects such as contamination of the electrolyte solution and a decrease in the content of lead powder in the negative electrode active material, the content is preferably 10% by mass or less.
最も好ましくは、非導電性繊維物質の平均繊維径を0.5μｍ以上0.9μｍ以下、含有量を0.05質量%以上0.8質量%以下、カーボンブラックの含有量を1.0質量%以上3質量%以下とする。平均繊維径が0.5μｍ以上0.9μｍ以下の非導電性繊維物質は工業的に入手が容易である。また図３と図５の比較から明らかなように、含有量を0.3質量%から0.8質量%へと増しても効果は余り増さないので、非導電性繊維物質の含有量は0.05質量%以上0.8質量%以下が好ましい。またカーボンブラックの効果は1.5質量%付近から飽和するので、含有量は1.0質量%以上3質量%以下が好ましい。 Most preferably, the non-conductive fiber material has an average fiber diameter of 0.5 to 0.9 μm, a content of 0.05 to 0.8% by mass, and a carbon black content of 1.0 to 3% by mass. Nonconductive fiber materials having an average fiber diameter of 0.5 μm or more and 0.9 μm or less are easily available industrially. Further, as is clear from the comparison between FIG. 3 and FIG. 5, the effect is not so increased even if the content is increased from 0.3% by mass to 0.8% by mass, so the content of the non-conductive fiber material is 0.05% by mass or more. 0.8 mass% or less is preferable. Further, since the effect of carbon black is saturated from around 1.5% by mass, the content is preferably 1.0% by mass or more and 3% by mass or less.
以下に、本発明の実施の態様を示す。本発明の実施に際しては、当業者の常識及び先行技術の開示に従い、実施の態様を適宜に変更できる。 Hereinafter, embodiments of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed according to common knowledge of the person skilled in the art and disclosure of prior art.
鉛蓄電池の試作
平均一次粒子径が35nmのアセチレンブラックをカーボンブラックとし、平均繊維径が0.5〜2.5μｍで平均繊維長が5μｍ〜5mmのグラスファイバーを非導電性繊維物質として、鉛粉、リグニン、硫酸バリウムを加えて負極活物質を製造した。カーボンブラックの種類と粒子径は任意で、ファーネスブラック、オイルブラック、ケッチェンブラック等でも良く、平均一次粒子径は10nm以上100nm以下が好ましい。非導電性繊維物質の種類は任意で、グラスファイバー以外に合成樹脂繊維等でも良い。非導電性繊維物質は平均繊維径が小さいほど、カーボンブラックの流出を防止する効果が高いので、平均繊維径は0.1μｍ以上で0.9μｍ以下とし、0.5μｍ未満のものは製造が困難なので、好ましくは平均繊維径を0.5μｍ以上0.9μｍ以下とする。非導電性繊維物質が負極活物質から流出することを抑制するため、その平均繊維長は負極活物質の平均細孔径よりも長さのある5μｍ以上が好ましく、例えば5μｍ以上5mm以下とする。
Trial production of lead-acid battery Acetylene black with an average primary particle size of 35 nm is carbon black, glass fiber with an average fiber diameter of 0.5 to 2.5 μm and an average fiber length of 5 μm to 5 mm is used as a non-conductive fiber material, lead powder, lignin, Barium sulfate was added to produce a negative electrode active material. The type and particle size of carbon black are arbitrary and may be furnace black, oil black, ketjen black, etc. The average primary particle size is preferably 10 nm or more and 100 nm or less. The type of the non-conductive fiber material is arbitrary, and synthetic resin fibers other than glass fibers may be used. The smaller the average fiber diameter of the non-conductive fiber material, the higher the effect of preventing the outflow of carbon black. Therefore, the average fiber diameter should be 0.1 μm or more and 0.9 μm or less. The average fiber diameter is 0.5 μm or more and 0.9 μm or less. In order to prevent the nonconductive fiber material from flowing out of the negative electrode active material, the average fiber length is preferably 5 μm or more, for example, 5 μm or more and 5 mm or less, which is longer than the average pore diameter of the negative electrode active material.
上記のアセチレンブラック（以下単にカーボンブラックということがある）の含有量を0〜10質量%の範囲で変え、また非導電性繊維物質の含有量を0〜5質量%の範囲で変え、非導電性繊維物質の平均繊維長と平均繊維径とを変えて、負極活物質原料を製造した。負極活物質原料は、アセチレンブラックと非導電性繊維物質の他に、リグニンを0.2質量%、硫酸バリウムを0.5質量%含有し、残部が鉛粉で、合計を100質量%とする。ここではボールミル法による鉛粉を用いたが、鉛粉の製造方法は任意である。またリグニン及び硫酸バリウムの有無は任意で、平均繊維径が1μｍ以上の他の非導電性繊維物質、例えばアクリル樹脂繊維を添加しても良い。負極活物質原料にイオン交換水と希硫酸とを滴下しつつ混練し、鉛合金からなる負極格子に塗布して負極板とし、定法に従って熟成と乾燥とを施した。 The content of the above acetylene black (hereinafter sometimes simply referred to as carbon black) is changed in the range of 0 to 10% by mass, and the content of the nonconductive fiber material is changed in the range of 0 to 5% by mass to The negative electrode active material raw material was manufactured by changing the average fiber length and the average fiber diameter of the conductive fiber material. The negative electrode active material raw material contains 0.2% by mass of lignin and 0.5% by mass of barium sulfate in addition to acetylene black and a non-conductive fiber material, and the balance is lead powder with a total of 100% by mass. Here, the lead powder by the ball mill method was used, but the method for producing the lead powder is arbitrary. The presence or absence of lignin and barium sulfate is optional, and other non-conductive fiber materials having an average fiber diameter of 1 μm or more, such as acrylic resin fibers, may be added. Ion exchange water and dilute sulfuric acid were added dropwise to the negative electrode active material raw material and kneaded, applied to a negative electrode lattice made of a lead alloy to form a negative electrode plate, and subjected to aging and drying according to a conventional method.
正極活物質原料は、ボールミル法による鉛粉にイオン交換水と希硫酸とを滴下しつつ混練し、鉛合金からなる正極格子に塗布して正極板とし、熟成と乾燥とを施した。乾燥後の負極板を微孔性で袋状のポリエチレンセパレータに収容し、１枚の負極板を２枚の正極板で両側から挟んで電槽に挿入し、希硫酸を加えて電槽化成を行った。以上のようにして、実施例及び比較例の単セルから成る鉛蓄電池を試作した。 The raw material for the positive electrode active material was kneaded while dropping ion-exchanged water and dilute sulfuric acid into lead powder produced by a ball mill method, applied to a positive electrode grid made of a lead alloy to form a positive electrode plate, and subjected to aging and drying. The dried negative electrode plate is housed in a microporous, bag-like polyethylene separator, and one negative electrode plate is sandwiched between two positive electrode plates from both sides and inserted into a battery case, and dilute sulfuric acid is added to form a battery case. went. As described above, lead storage batteries made of single cells of the example and the comparative example were manufactured as a prototype.
試験法
同じ組成の鉛蓄電池を３個ずつ用い、25℃の水槽にセットして、１時間率電流（1CA）での移行放電を６分行った後に、1CAで18分間の放電と1CAで18分間の充電とから成るサイクル充放電を繰り返し、18分の放電中に鉛蓄電池の端子電圧が1.0V未満に低下すると寿命として、寿命に到るまでのサイクル数を求めた。そして試験後に、電解液中に流出したカーボンブラック量を測定した。結果は３個の鉛蓄電池の平均値で示し、非導電性繊維物質を含有しない鉛蓄電池が寿命に至るまでのサイクル数を100とする相対値により、寿命性能を示す。ここでの寿命性能はPSOC下での鉛蓄電池の耐久性を表す。なお試作の鉛蓄電池は液式であるが、制御弁式鉛蓄電池でも良い。カーボンブラックの流出量を、10%以上流出したものを×、流出量が10%未満のものを○と評価した。カーボンブラックの流出量が少ないことは、サルフェーションの抑制効果が持続していることの他に、電解液の汚染が少なく、液面レベルの視認性が高いことを意味する。
Test method Using three lead-acid batteries of the same composition, set them in a water bath at 25 ° C, perform a transition discharge at 1 hour rate current (1CA) for 6 minutes, then discharge at 1CA for 18 minutes and at 1CA for 18 minutes. The cycle charge and discharge consisting of charging for 1 minute was repeated, and when the terminal voltage of the lead storage battery decreased to less than 1.0 V during 18 minutes of discharge, the number of cycles until the end of the life was obtained. And the amount of carbon black which flowed out in electrolyte solution was measured after the test. The result is shown as an average value of three lead storage batteries, and the life performance is shown by a relative value where the number of cycles until the lead storage battery containing no non-conductive fiber material reaches the end of its life is 100. The life performance here represents the durability of the lead-acid battery under PSOC. The prototype lead-acid battery is a liquid type, but may be a control valve type lead-acid battery. The outflow amount of carbon black was evaluated as x when the outflow amount was 10% or more, and ○ when the outflow amount was less than 10%. The small amount of carbon black flowing out means that the effect of suppressing sulfation is sustained, and that the electrolyte is less contaminated and the liquid level is highly visible.
結果
平均一次粒子径が35nmのアセチレンブラック（含有量：0.05〜1.5質量%）と、平均繊維長が5μｍのグラスファイバー（含有量：0.05質量%）とを用いた際の結果を、表１に示す。グラスファイバーの含有量を0.3質量%とし他は同様とした際の結果を表２に、グラスファイバーの含有量を0.8質量%とし他は同様とした際の結果を表３に示す。またグラスファイバーの含有量を0.05質量%とした際のグラスファイバーの平均繊維径の影響を図１に、アセチレンブラックの含有量の影響を図２に示す。同様に、グラスファイバーの含有量を0.3質量%とした際のグラスファイバーの平均繊維径の影響を図３に、アセチレンブラックの含有量の影響を図４に示し、グラスファイバーの含有量を0.8質量%とした際のグラスファイバーの平均繊維径の影響を図５に、アセチレンブラックの含有量の影響を図６に示す。アセチレンブラックを多量(15質量%)まで増加したときのアセチレンブラックの含有量の影響を図７に示し、グラスファイバーは平均繊維径が0.7μｍ、平均繊維長が5μｍで、含有量は0.3質量%である。図１〜図７では、アセチレンブラックの含有量が同じで、グラスファイバー無添加の試料でのサイクル数を100とする相対値により、寿命性能を示す。
Results Table 1 shows the results when acetylene black having an average primary particle size of 35 nm (content: 0.05 to 1.5% by mass) and glass fiber having an average fiber length of 5 μm (content: 0.05% by mass) are used. Show. Table 2 shows the results when the glass fiber content is 0.3% by mass and others are the same, and Table 3 shows the results when the glass fiber content is 0.8% by mass and others are the same. FIG. 1 shows the influence of the average fiber diameter of the glass fiber when the glass fiber content is 0.05% by mass, and FIG. 2 shows the influence of the acetylene black content. Similarly, FIG. 3 shows the influence of the average fiber diameter of the glass fiber when the glass fiber content is 0.3 mass%, FIG. 4 shows the influence of the acetylene black content, and the glass fiber content is 0.8 mass. FIG. 5 shows the influence of the average fiber diameter of the glass fiber when the content is%, and FIG. 6 shows the influence of the content of acetylene black. FIG. 7 shows the effect of the content of acetylene black when the amount of acetylene black is increased to a large amount (15% by mass). The glass fiber has an average fiber diameter of 0.7 μm, an average fiber length of 5 μm, and a content of 0.3% by mass. It is. In FIGS. 1-7, life performance is shown by the relative value which makes content of acetylene black the same, and makes the cycle number 100 by the sample without glass fiber addition.
図１、図３、図５に示すように、グラスファイバーの平均繊維径が小さい程、寿命性能（サイクル数比）が向上し、平均繊維径が0.9μｍでも寿命性能は充分に向上する。これに対して平均繊維径が1.2μｍ以上では、寿命性能は不十分である。平均繊維径が0.9μｍ以下で寿命性能が向上することは、グラスファイバーの含有量を0.05質量%から0.3質量%、0.8質量%へと変えても変わらない。以上のように、グラスファイバーの平均繊維径を0.9μｍ以下とすることにより高い寿命性能が得られ、平均繊維径が0.1μｍ未満のグラスファイバーは製造が困難なので、平均繊維径を0.1μｍ以上で0.9μｍ以下とし、好ましくは0.5μｍ以上で0.9μｍ以下とする。 As shown in FIGS. 1, 3, and 5, the life performance (cycle ratio) is improved as the average fiber diameter of the glass fiber is smaller, and the life performance is sufficiently improved even when the average fiber diameter is 0.9 μm. On the other hand, when the average fiber diameter is 1.2 μm or more, the life performance is insufficient. The improvement in the life performance when the average fiber diameter is 0.9 μm or less does not change even when the glass fiber content is changed from 0.05 mass% to 0.3 mass% and 0.8 mass%. As described above, high life performance can be obtained by setting the average fiber diameter of the glass fiber to 0.9 μm or less, and it is difficult to produce glass fibers having an average fiber diameter of less than 0.1 μm. 0.9 μm or less, preferably 0.5 μm or more and 0.9 μm or less.
グラスファイバーの含有量の効果を表１〜表３に示し、カーボンブラックの含有量が0.1質量%以上であれば、0.05質量%の含有で大きな効果が得られ、0.8質量%付近で効果が飽和する。従ってグラスファイバーの含有量は0.05質量%以上で1質量%以下とし、好ましくは0.05質量%以上で0.8質量%以下とする。 The effects of the glass fiber content are shown in Tables 1 to 3. If the carbon black content is 0.1% by mass or more, a large effect is obtained at 0.05% by mass, and the effect is saturated at around 0.8% by mass. To do. Accordingly, the glass fiber content is 0.05% by mass or more and 1% by mass or less, preferably 0.05% by mass or more and 0.8% by mass or less.
図２、図４、図６、図７はカーボンブラックの含有量の影響を示し、カーボンブラックの含有量を0.1質量%以上に増すと、サイクル中のカーボン流出をグラスファイバーが抑えることで、寿命性能は向上する。詳細は省略するが、カーボンブラックの効果は含有量が1.5質量%程度で飽和し、3質量%を越えると流出量が徐々に増加する。これらのことから、カーボンブラックの含有量は0.1質量%以上とし、好ましくは1.0質量%以上10質量%以下とし、特に好ましくは1.0質量%以上3質量%以下とする。 2, 4, 6, and 7 show the influence of the carbon black content. When the carbon black content is increased to 0.1% by mass or more, the glass fiber suppresses the outflow of carbon during the cycle. Performance is improved. Although details are omitted, the effect of carbon black is saturated when the content is about 1.5% by mass, and when it exceeds 3% by mass, the outflow amount gradually increases. For these reasons, the carbon black content is 0.1% by mass or more, preferably 1.0% by mass or more and 10% by mass or less, and particularly preferably 1.0% by mass or more and 3% by mass or less.
カーボンブラック流出量の評価結果（表１〜表３）を検討する。なお表１〜表３では、グラスファイバーを無添加で、アセチレンブラックの含有量が0.05質量%の試料でのサイクル数を100として寿命性能を示し、寿命性能のデータは図１〜図７に示したものである。カーボンブラックの流出は含有量が0.1質量%よりも多くなると問題となり、平均繊維径が0.9μｍ以下の非導電性繊維物質を0.05質量%以上含有することにより抑制でき、平均繊維径が1.2μｍ以上の非導電性繊維物質では、0.8質量%含有してもカーボンブラックの流出を抑制できない。 The evaluation results (Tables 1 to 3) of the carbon black outflow amount are examined. In Tables 1 to 3, the life performance is shown with the number of cycles in a sample having no glass fiber added and an acetylene black content of 0.05 mass% as 100, and the data on the life performance is shown in FIGS. It is a thing. The outflow of carbon black becomes a problem when the content exceeds 0.1% by mass, and can be suppressed by containing 0.05% by mass or more of a non-conductive fiber material having an average fiber diameter of 0.9 μm or less, and the average fiber diameter is 1.2 μm or more. This non-conductive fiber material cannot suppress the outflow of carbon black even if it is contained in an amount of 0.8% by mass.
カーボンブラックの含有量を0.3質量%に固定し、グラスファイバーの平均繊維径を0.7μｍ、含有量を0.3質量%に固定しながら、グラスファイバーの平均繊維長を50μｍ、500μｍ、5mmに変えた際の結果を表４に示す。結果は平均繊維長によらずほぼ同等である。 When the carbon fiber content is fixed at 0.3% by mass, the average fiber diameter of the glass fiber is fixed at 0.7 μm, and the content is fixed at 0.3% by mass, while the average fiber length of the glass fiber is changed to 50 μm, 500 μm, 5 mm Table 4 shows the results. The results are almost the same regardless of the average fiber length.
カーボンブラックの種類を、平均一次粒子径が39.5nmのケッチェンブラックに変えた際の結果を表５に示す。ケッチェンブラックでは、同量のアセチレンブラック（表２の試料45）よりも僅かに寿命性能が高いが、カーボン流出量の評価結果は同じである。以上のように、カーボンブラックの種類を変えても、ほぼ同等の結果が得られる。 Table 5 shows the results when the type of carbon black was changed to Ketjen Black having an average primary particle size of 39.5 nm. Ketjen black has slightly higher life performance than the same amount of acetylene black (sample 45 in Table 2), but the evaluation results of carbon outflow are the same. As described above, almost the same result can be obtained even if the type of carbon black is changed.
これ以外のデータを表６〜表９に示し、試料番号は表１〜表５と統一してある。またカーボンブラックの種類は特に記載が無い場合は、アセチレンブラックである。表６から、グラスファイバー含有無の場合、グラスファイバー含有の場合と比べ、同量のカーボンブラックを含有しても、カーボンブラックの流出を抑制できず、かつサイクル数の向上も小さいことが分かる。 The other data are shown in Tables 6 to 9, and the sample numbers are the same as those in Tables 1 to 5. The type of carbon black is acetylene black unless otherwise specified. From Table 6, it can be seen that when glass fiber is not contained, the outflow of carbon black cannot be suppressed and the improvement in the number of cycles is small even when the same amount of carbon black is contained as compared with the case where glass fiber is contained.
表７から、グラスファイバーの平均繊維径を0.7μｍから2.5μｍに変更すると、カーボンブラックの流出を抑制できず、かつサイクル数向上の効果も小さいことが分かる。さらにカーボンブラックを15質量%含有すると、10質量%の場合に比べ、サイクル数比が低下し、カーボンブラックの流出が著しくなることが分かる。 From Table 7, it can be seen that when the average fiber diameter of the glass fiber is changed from 0.7 μm to 2.5 μm, the outflow of carbon black cannot be suppressed and the effect of improving the cycle number is small. Further, it can be seen that when 15% by mass of carbon black is contained, the cycle number ratio is lowered and the outflow of carbon black becomes significant compared to the case of 10% by mass.
表８から、ケッチェンブラックを用いても、その含有量を15質量%とすると、大きなサイクル数比は得られず、かつカーボンブラックの流出が著しくなることが分かる。 From Table 8, it can be seen that even when ketjen black is used, if the content is 15% by mass, a large cycle number ratio cannot be obtained, and the outflow of carbon black becomes significant.
表９から、グラスファイバーの含有量を0.05質量%〜1.0質量%とすると、サイクル数比が向上し、カーボンブラックの流出も無いことが分かる。この場合も、カーボンブラックの含有量が適正で、グラスファイバーの平均繊維径と平均繊維長が適正であることが前提となることはいうまでもない。 From Table 9, it can be seen that when the glass fiber content is 0.05 mass% to 1.0 mass%, the cycle number ratio is improved and carbon black does not flow out. Also in this case, it is needless to say that the carbon black content is appropriate and the average fiber diameter and average fiber length of the glass fiber are appropriate.
実施例から、以下の効果が得られることが判明した。
1) 平均繊維径が0.9μｍ以下の非導電性繊維物質を、0.1質量%以上のカーボンブラックと共に、負極活物質に含有することにより、サルフェーションを抑制すると共に、カーボンブラックの流出を抑制できる。
2) 非導電性繊維物質の平均繊維径を1.2μｍ以上とすると、効果が小さい。
3) 平均繊維径が0.9μｍ以下の非導電性繊維物質の効果は、含有量が0.05質量%、0.3質量%、0.8質量%の何れでも得られる。
4) カーボンブラックの含有量を0.05質量%とすると、カーボンブラックの流出量は多くなく、非導電性繊維物質自体にサルフェーション抑制の効果はないため、平均繊維径が0.9μｍ以下の非導電性繊維物質を含有しても、サルフェーションは充分には抑制できない。
From the examples, it was found that the following effects can be obtained.
1) By containing a non-conductive fiber material having an average fiber diameter of 0.9 μm or less in the negative electrode active material together with 0.1% by mass or more of carbon black, sulfation can be suppressed and the outflow of carbon black can be suppressed.
2) The effect is small when the average fiber diameter of the non-conductive fiber material is 1.2 μm or more.
3) The effect of the non-conductive fiber material having an average fiber diameter of 0.9 μm or less can be obtained regardless of whether the content is 0.05 mass%, 0.3 mass%, or 0.8 mass%.
4) When the content of carbon black is 0.05 mass%, the outflow amount of carbon black is not large, and the nonconductive fiber material itself has no effect of suppressing sulfation, so the nonconductive fiber with an average fiber diameter of 0.9 μm or less Even if a substance is contained, sulfation cannot be sufficiently suppressed.
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