JP2020173926A - Additive for lead-acid battery, lead-acid battery, and method of recycling lead-acid battery - Google Patents
Additive for lead-acid battery, lead-acid battery, and method of recycling lead-acid battery Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 100
- 230000000996 additive effect Effects 0.000 title claims abstract description 93
- 239000002253 acid Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 28
- 238000004064 recycling Methods 0.000 title 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 46
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 230000001172 regenerating effect Effects 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 5
- 230000006866 deterioration Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 25
- 238000002484 cyclic voltammetry Methods 0.000 description 22
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 16
- 230000019635 sulfation Effects 0.000 description 16
- 238000005670 sulfation reaction Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
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- 230000003647 oxidation Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 229910000978 Pb alloy Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- -1 silver ions Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000010278 pulse charging Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Secondary Cells (AREA)
Abstract
Description
本発明は、鉛蓄電池用の添加剤および鉛蓄電池に関する。また、本発明は、鉛蓄電池の再生方法に関する。 The present invention relates to additives for lead-acid batteries and lead-acid batteries. The present invention also relates to a method for regenerating a lead storage battery.
鉛蓄電池は他の電池と比較して、安全性・信頼性が高い点、使用温度範囲が広い点、安価である点といった利点を有しており、自動車、非常用電源、電力貯蔵、太陽光発電システムなど多くの用途に現在も利用されている。 Compared to other batteries, lead-acid batteries have the advantages of high safety and reliability, a wide operating temperature range, and low cost. They have advantages such as automobiles, emergency power sources, power storage, and solar power. It is still used for many purposes such as power generation systems.
鉛蓄電池は、正極では、式（１）の反応が起こり、負極では、式（２）の反応が起こることで充電と放電が繰り返される。
・式（１）：ＰｂＯ2 ＋ ４Ｈ+ ＋ ＳＯ4 2- ＋ ２ｅ-
→ ＰｂＳＯ4 ＋ ２Ｈ2Ｏ
・式（２）：Ｐｂ ＋ ＳＯ4 2- →ＰｂＳＯ4 ＋ ２ｅ-
In a lead-acid battery, the reaction of the formula (1) occurs at the positive electrode, and the reaction of the formula (2) occurs at the negative electrode, so that charging and discharging are repeated.
- formula (1): PbO 2 + 4H + + SO 4 2- + 2e -
→ PbSO 4 + 2H 2 O
· Formula (2): Pb + SO 4 2- → PbSO 4 + 2e -
式（１）および式（２）に示すように、鉛蓄電池は、放電時には正極および負極で硫酸鉛が生成され、充電時には両極で生成された硫酸鉛は元の電極および電解液へ戻る。
しかしながら、鉛蓄電池の使用を重ねていくと、放電時に生成した硫酸鉛が充電時に戻りにくくなる。これは生成した硫酸鉛が硬質化したことによるものである。この硬質化した硫酸鉛は絶縁性の物質であり、電極表面において電気抵抗となる。これにより電池性能が低下してしまい、寿命を迎える要因の一つとなる。
このように、生成した硫酸鉛が硬質化し抵抗となることをサルフェーションという。
As shown in the formulas (1) and (2), in the lead-acid battery, lead sulfate is produced at the positive electrode and the negative electrode during discharge, and lead sulfate produced at both electrodes returns to the original electrode and the electrolytic solution during charging.
However, as the lead-acid battery is used repeatedly, it becomes difficult for lead sulfate generated during discharge to return during charging. This is due to the hardening of the produced lead sulfate. This hardened lead sulfate is an insulating substance and becomes an electric resistance on the electrode surface. As a result, the battery performance deteriorates, which is one of the factors that reach the end of its life.
The fact that the produced lead sulfate hardens and becomes resistance in this way is called sulfation.
サルフェーションを抑制したり、電池の寿命を向上させるための技術として、主に、パルス充電法と添加剤を投入する方法が知られている。
パルス充電法は、市販のバッテリーチャージャーにも機能がついており、入手が容易であることや、受電時に装着するのみで済み手間が少ないこと、比較的軽度の劣化に対して有効であり継続使用により劣化を抑制できることなどの利点がある。一方で、バッテリー容量や使用用途によりパルスの調整が必要となる。また、パルスの印加により硫酸鉛が脱落し電解液中に残ることがあったり、局所的に電流が流れ、電極にダメージを与える場合があるなど問題がある。また、既に劣化したバッテリーに対しては効果がないことや、再生までに時間を要するという問題がある。
As a technique for suppressing sulfation and improving the life of a battery, a pulse charging method and a method of adding an additive are mainly known.
The pulse charging method also has a function in a commercially available battery charger, it is easy to obtain, it only needs to be installed when receiving power, and it takes less time, and it is effective for relatively mild deterioration, and by continuous use. There are advantages such as being able to suppress deterioration. On the other hand, it is necessary to adjust the pulse depending on the battery capacity and usage. Further, there are problems that lead sulfate may fall off due to the application of a pulse and remain in the electrolytic solution, or a current may flow locally to damage the electrodes. In addition, there are problems that it is not effective for a battery that has already deteriorated and that it takes time to reproduce.
これに対して、添加剤を投入する方法は、一度投入するだけでよく、新品のバッテリーに対しては劣化の抑制と回復効果が期待でき、劣化したバッテリーに対しては回復効果が期待できる。 On the other hand, the method of adding the additive is that it only needs to be added once, and the deterioration can be suppressed and the recovery effect can be expected for the new battery, and the recovery effect can be expected for the deteriorated battery.
添加剤を投入する方法として、特許文献１には、特定の負極と、特定の正極を有し、電解液には硫酸バンド、陽イオン系界面活性剤、硫酸から選ばれた化合物が添加された鉛蓄電池が開示されている。
また、鉛蓄電池を活性化させる添加剤として、ポリビニルアルコールが知られている。例えば、特許文献２には、分子量８万ないし２０万、好ましくは１０万ないし１５万、のポリビニルアルコールよりなることを特徴とする鉛電池活性化剤が開示されている。特許文献３には、有効成分としてポリビニルアルコールを含有する水系液からなる鉛蓄電池用寿命延長剤であって、ソルビン酸を含有している、鉛蓄電池用寿命延長剤が開示されている。特許文献４には、ポリビニルアルコールと、銀イオンとを電解液および／または電極活物質成形体中に含むことを特徴とする鉛蓄電池が開示されている。
As a method of adding an additive, Patent Document 1 has a specific negative electrode and a specific positive electrode, and a compound selected from a sulfuric acid band, a cationic surfactant, and sulfuric acid is added to the electrolytic solution. Lead-acid batteries are disclosed.
Further, polyvinyl alcohol is known as an additive for activating a lead storage battery. For example, Patent Document 2 discloses a lead battery activator characterized by being composed of polyvinyl alcohol having a molecular weight of 80,000 to 200,000, preferably 100,000 to 150,000. Patent Document 3 discloses a life-extending agent for lead-acid batteries, which comprises an aqueous solution containing polyvinyl alcohol as an active ingredient and contains sorbic acid. Patent Document 4 discloses a lead-acid battery characterized by containing polyvinyl alcohol and silver ions in an electrolytic solution and / or an electrode active material molded product.
また、使用中または使用済みの鉛蓄電池を再生や回復する技術として、特許文献５には、鉛電池の電解液中にポリビニルアルコール、ポリアクリル酸、リグニンからなる群のうちの少なくとも一つの有機添加剤を加え、０．３Ｃ以上、好ましくは１Ｃ以上の電流で該電池の公称容量の３％以上、好ましくは１０％以上の電気量を連続または断続して放電させることを特徴とする鉛電池の再生方法が開示されている。 Further, as a technique for regenerating or recovering a used or used lead-acid battery, Patent Document 5 states that at least one of the group consisting of polyvinyl alcohol, polyacrylic acid, and lignin is organically added to the electrolytic solution of the lead battery. A lead-acid battery characterized by continuously or intermittently discharging an electric amount of 3% or more, preferably 10% or more of the nominal capacity of the battery with a current of 0.3 C or more, preferably 1 C or more by adding an agent. The reproduction method is disclosed.
特許文献１〜５は、鉛蓄電池の寿命を延ばすことができるが、十分とはいえなかった。鉛蓄電池の電池性能の劣化をより長い時間にわたって抑制することができれば、鉛蓄電池の寿命をさらに長く伸ばすことができ、廃棄するまでの使用期間を延ばすことが可能になる。また、使用済みの鉛蓄電池を再生した鉛蓄電池の寿命をさらに伸ばすことで、廃棄される鉛蓄電池を減らすことができる。これにより、環境に対する負荷軽減をさらに図ることが可能となる。 Patent Documents 1 to 5 can extend the life of a lead storage battery, but it cannot be said to be sufficient. If the deterioration of the battery performance of the lead-acid battery can be suppressed for a longer period of time, the life of the lead-acid battery can be further extended, and the period of use until disposal can be extended. Further, by further extending the life of the lead-acid battery obtained by reusing the used lead-acid battery, the amount of the lead-acid battery discarded can be reduced. This makes it possible to further reduce the load on the environment.
係る状況下、本発明の目的は、鉛蓄電池の電池性能の劣化を抑制することができる、鉛蓄電池用の添加剤を提供することである。また、電池性能が劣化しにくい、鉛蓄電池を提供することである。さらに、本発明の目的は、鉛蓄電池の再生方法を提供することである。 Under such circumstances, an object of the present invention is to provide an additive for a lead storage battery, which can suppress deterioration of the battery performance of the lead storage battery. Another object of the present invention is to provide a lead storage battery whose battery performance does not easily deteriorate. Furthermore, an object of the present invention is to provide a method for regenerating a lead storage battery.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of diligent research to solve the above problems, the present inventor has found that the following invention meets the above object, and has reached the present invention.
すなわち、本発明は、以下の発明に係るものである。
＜１＞ ポリビニルアルコールを含む鉛蓄電池用の添加剤であって、前記ポリビニルアルコールの５質量%水溶液の粘度が、１〜３０ｍＰａ・ｓである鉛蓄電池用の添加剤。
＜２＞ 前記ポリビニルアルコールのケン化度が、９０〜９９.５ｍｏｌ％である、前記＜１＞の添加剤。
＜３＞ 前記ポリビニルアルコールが、日本合成化学社製ゴーセノールＣ−５００、ゴーセノールＮ−３００およびゴーセノールＡ−３００からなる群から選択される１以上である、前記＜１＞または＜２＞に記載の添加剤。
＜４＞ 正極、負極、セパレーター、および電解液が収容された電槽と、蓋とを備えた鉛蓄電池であって、前記電解液が、前記＜１＞から＜３＞のいずれかに記載の添加剤と、硫酸とを含む水溶液である、鉛蓄電池。
＜５＞ 前記鉛蓄電池の電気容量に対する前記添加剤の質量が、１／１８０［ｇ／Ａｈ］〜１／２２０［ｇ／Ａｈ］である、前記＜４＞に記載の鉛蓄電池。
＜６＞ 正極、負極、セパレーター、および電解液が収容された電槽と、蓋とを備えた鉛蓄電池の再生方法であって、前記電解液と、前記＜１＞から＜３＞のいずれかに記載の添加剤とを混合した後に、電圧を印加する工程Ａを有する、再生方法。
＜７＞ 前記工程Ａにおいて、前記鉛蓄電池の電気容量に対する前記添加剤の質量が１／１８０［ｇ／Ａｈ］〜１／２２０［ｇ／Ａｈ］となるように、前記添加剤と前記電解液とを混合する、前記＜６＞に記載の再生方法。
That is, the present invention relates to the following invention.
<1> An additive for a lead storage battery containing polyvinyl alcohol, wherein the viscosity of the 5% by mass aqueous solution of the polyvinyl alcohol is 1 to 30 mPa · s.
<2> The additive according to <1>, wherein the degree of saponification of the polyvinyl alcohol is 90 to 99.5 mol%.
<3> The above-mentioned <1> or <2>, wherein the polyvinyl alcohol is one or more selected from the group consisting of Gosenol C-500, Gosenol N-300 and Gosenol A-300 manufactured by Nippon Synthetic Chemistry Co., Ltd. Additive.
<4> The lead-acid battery including a positive electrode, a negative electrode, a separator, an electric tank containing an electrolytic solution, and a lid, wherein the electrolytic solution is any one of <1> to <3>. A lead-acid battery, which is an aqueous solution containing an additive and sulfuric acid.
<5> The lead-acid battery according to <4>, wherein the mass of the additive with respect to the electric capacity of the lead-acid battery is 1/180 [g / Ah] to 1/220 [g / Ah].
<6> A method for regenerating a lead-acid battery including a positive electrode, a negative electrode, a separator, an electric tank containing an electrolytic solution, and a lid, wherein the electrolytic solution and any one of <1> to <3> are used. A regeneration method comprising the step A of applying a voltage after mixing with the additive according to.
<7> In the step A, the additive and the electrolytic solution so that the mass of the additive with respect to the electric capacity of the lead storage battery is 1/180 [g / Ah] to 1/220 [g / Ah]. The reproduction method according to <6>, wherein the above-mentioned <6> is mixed with.
本発明によれば、鉛蓄電池の電池性能の劣化を抑制することができる、鉛蓄電池用の添加剤が提供される。特に、優れたサルフェーション抑制効果を有する、サルフェーション抑制剤が提供される。また、電池性能が劣化しにくい、鉛蓄電池が提供される。さらに、鉛蓄電池の再生方法が提供される。 According to the present invention, there is provided an additive for a lead storage battery capable of suppressing deterioration of the battery performance of the lead storage battery. In particular, a sulfation inhibitor having an excellent sulfation inhibitory effect is provided. Further, a lead storage battery is provided in which the battery performance is not easily deteriorated. Further provided is a method for regenerating a lead-acid battery.
以下に本発明の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を変更しない限り、以下の内容に限定されない。なお、本明細書において「〜」という表現を用いる場合、その前後の数値を含む表現として用いる。 Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described below unless the gist thereof is changed. It is not limited to the contents of. In addition, when the expression "~" is used in this specification, it is used as an expression including numerical values before and after it.
＜鉛蓄電池用の添加剤＞
本発明は、ポリビニルアルコールを含む鉛蓄電池用の添加剤であって、前記ポリビニルアルコールの５質量%水溶液の粘度が、１〜３０ｍＰａ・ｓである鉛蓄電池用の添加剤（以下、「本発明の添加剤」と記載する場合がある。）に関するものとすることができる。
本発明の添加剤を用いることで、電極に硫酸鉛が付着しにくくなる。また、電極に付着する硫酸鉛も繊維状など細かい状態で付着するため電極の導電性が阻害されにくく、電極の導電状態が良好に保たれる。結果として、サルフェーションが抑制され、電池性能の劣化が抑制される。
本発明の添加剤は、特に、優れたサルフェーション抑制効果を有する、サルフェーション抑制剤として好適である。
<Additives for lead-acid batteries>
The present invention is an additive for a lead storage battery containing polyvinyl alcohol, and the viscosity of the 5% by mass aqueous solution of the polyvinyl alcohol is 1 to 30 mPa · s (hereinafter, "the additive of the present invention". It may be described as "additive").
By using the additive of the present invention, lead sulfate is less likely to adhere to the electrode. Further, since lead sulfate adhering to the electrode also adheres in a fine state such as fibrous form, the conductivity of the electrode is not easily impaired, and the conductive state of the electrode is kept good. As a result, sulfation is suppressed and deterioration of battery performance is suppressed.
The additive of the present invention is particularly suitable as a sulfation inhibitor having an excellent sulfation inhibitory effect.
本発明者らは、サイクリックボルタンメトリー法（ＣＶ法）により得られる酸化波ピークの立ち上がり付近の電流変化と、負極の電極表面の硫酸鉛の付着量とはある程度相関があることを見出した。希硫酸と添加剤との混合液を電解液としてＣＶ法で評価したときに、酸化波ピークの立ち上がり付近の電流変化が大きいものほど、サルフェーションを抑制し、電池性能の劣化を抑制することができる。
また、本発明者らは、５質量%水溶液の粘度が１〜３０ｍＰａ・ｓであるポリビニルアルコールを含む添加剤を用いることで、ＣＶにより得られる酸化波ピークの立ち上がり付近の電流変化を大きくすることができ、従来の添加剤に比べて電池性能の劣化を抑制できることを見出した。その理由は明らかではないが、５質量%水溶液の粘度が１〜３０ｍＰａ・ｓであるポリビニルアルコールを含む添加剤を用いることで、ポリビニルアルコールが適度に電極表面にとどまり、サルフェーションの形成を抑制することができる一方で、正極と負極の間のイオンのやりとりを妨げないため、電池性能が劣化しにくいと推察される。
The present inventors have found that there is a certain degree of correlation between the current change near the rise of the oxidation wave peak obtained by the cyclic voltammetry method (CV method) and the amount of lead sulfate adhered to the electrode surface of the negative electrode. When the mixed solution of dilute sulfuric acid and the additive is evaluated by the CV method as an electrolytic solution, the larger the current change near the rise of the oxidation wave peak, the more the sulfation can be suppressed and the deterioration of the battery performance can be suppressed. ..
In addition, the present inventors increase the current change near the rise of the oxidation wave peak obtained by CV by using an additive containing polyvinyl alcohol having a viscosity of a 5% by mass aqueous solution of 1 to 30 mPa · s. It was found that the deterioration of battery performance can be suppressed as compared with the conventional additives. The reason is not clear, but by using an additive containing polyvinyl alcohol having a viscosity of 5% by mass aqueous solution of 1 to 30 mPa · s, the polyvinyl alcohol appropriately stays on the electrode surface and suppresses the formation of sulfation. On the other hand, it does not interfere with the exchange of ions between the positive electrode and the negative electrode, so it is presumed that the battery performance is unlikely to deteriorate.
本発明の添加剤に含まれるポリビニルアルコールは、５質量％水溶液の粘度が、１〜３０ｍＰａ・ｓである。
なお、本発明において、「ポリビニルアルコールの５質量％水溶液の粘度」とは、株式会社エーアンドデイ製の音叉型振動式粘度計（ＳＶ−１Ａ）を用いて、温度が２５〜３０℃の範囲内で５回測定を行い、その値を平均した平均値を意味する。
The polyvinyl alcohol contained in the additive of the present invention has a viscosity of a 5% by mass aqueous solution of 1 to 30 mPa · s.
In the present invention, the "viscosity of a 5% by mass aqueous solution of polyvinyl alcohol" is defined by using a tuning fork type vibration viscous meter (SV-1A) manufactured by A & D Co., Ltd., in a temperature range of 25 to 30 ° C. It means the average value obtained by averaging the values obtained by measuring 5 times.
ポリビニルアルコールは、粘度が小さいほど電極表面にとどまるポリビニルアルコールの量が少なくなり、サルフェーションの抑制効果が小さくなる傾向となる。そのため、ポリビニルアルコールの５質量％水溶液の粘度は、５ｍＰａ・ｓ以上が好ましく、１０ｍＰａ・ｓ以上がより好ましく、１５ｍＰａ・ｓ以上がさらに好ましい。
また、ポリビニルアルコールの粘度が大きいほど、正極および負極の電極表面に存在するポリビニルアルコールの量が増え、ポリビニルアルコールにより正極と負極との間のイオンのやりとりが妨げられる傾向となる。そのため、ポリビニルアルコールの５質量％水溶液の粘度は、２５ｍＰａ・ｓ以下が好ましく、２０ｍＰａ／ｓ以下がより好ましい。
As the viscosity of polyvinyl alcohol decreases, the amount of polyvinyl alcohol that stays on the electrode surface decreases, and the effect of suppressing sulfation tends to decrease. Therefore, the viscosity of the 5% by mass aqueous solution of polyvinyl alcohol is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and further preferably 15 mPa · s or more.
Further, as the viscosity of polyvinyl alcohol increases, the amount of polyvinyl alcohol present on the electrode surfaces of the positive electrode and the negative electrode increases, and the polyvinyl alcohol tends to hinder the exchange of ions between the positive electrode and the negative electrode. Therefore, the viscosity of the 5% by mass aqueous solution of polyvinyl alcohol is preferably 25 mPa · s or less, and more preferably 20 mPa / s or less.
ポリビニルアルコールは、水酸基の割合が少ない（ケン化度が小さい）ほど、疎水的になり、電解液の成分である硫酸水溶液と混ざりにくくなる。そのため、ポリビニルアルコールのケン化度は、７０ｍｏｌ％以上が好ましく、８０ｍｏｌ％以上がより好ましい。特に、９０ｍｏｌ％以上が好ましく、９３ｍｏｌ％以上がより好ましく、９５ｍｏｌ％以上がさらに好ましい。
また、ポリビニルアルコールは、水酸基の割合が多い（ケン化度が高い、酢酸基の割合が少ない）ほど、電極表面の導電性が低くなり、サルフェーションが起こりやすくなり、電解液抵抗が大きくなる傾向にある。そのため、ケン化度は、９９．５ｍｏｌ％以下であることが好ましく、９９ｍｏｌ％以下がより好ましく、９７ｍｏｌ％以下がさらに好ましい。
The smaller the proportion of hydroxyl groups (the smaller the degree of saponification), the more hydrophobic the polyvinyl alcohol becomes, and the less likely it is to mix with the sulfuric acid aqueous solution that is a component of the electrolytic solution. Therefore, the degree of saponification of polyvinyl alcohol is preferably 70 mol% or more, more preferably 80 mol% or more. In particular, 90 mol% or more is preferable, 93 mol% or more is more preferable, and 95 mol% or more is further preferable.
Further, in polyvinyl alcohol, as the proportion of hydroxyl groups is large (the degree of saponification is high and the proportion of acetic acid groups is small), the conductivity of the electrode surface is lowered, sulfation is likely to occur, and the electrolyte resistance tends to be increased. is there. Therefore, the degree of saponification is preferably 99.5 mol% or less, more preferably 99 mol% or less, and further preferably 97 mol% or less.
本発明の添加剤は、５質量%水溶液の粘度が１〜３０ｍＰａ・ｓであるポリビニルアルコールを１種含むものでも、２種以上含むものであってもよい。
また、本発明の添加剤に含まれるポリビニルアルコールは、市販のポリビニルアルコールを用いてもよい。
中でも、日本合成化学社製のゴーセノールＣ−５００、ゴーセノールＮ−３００およびゴーセノールＡ−３００からなる群から選択される１以上であることが好ましく、日本合成化学社製のゴーセノールＣ−５００、ゴーセノールＮ−３００およびゴーセノールＡ−３００からなる群から選択されるいずれかであることが好ましい。
The additive of the present invention may contain one type of polyvinyl alcohol having a viscosity of a 5% by mass aqueous solution of 1 to 30 mPa · s, or may contain two or more types of polyvinyl alcohol.
Further, as the polyvinyl alcohol contained in the additive of the present invention, commercially available polyvinyl alcohol may be used.
Among them, it is preferably one or more selected from the group consisting of Gosenol C-500, Gosenol N-300 and Gosenol A-300 manufactured by Nippon Synthetic Chemistry Co., Ltd., and Gosenol C-500 and Gosenol N manufactured by Nippon Synthetic Chemical Industry Co., Ltd. It is preferably any one selected from the group consisting of -300 and Gosenol A-300.
本発明の添加剤は、消泡剤などのその他の成分を含んでもよい。一方で、その他の成分が鉛蓄電池の電極表面の導電性に影響を及ぼす場合もあるため、ポリビニルアルコールを主成分とすることが好ましい。本発明の添加剤中のポリビニルアルコールの含有量は、５０質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上がさらに好ましく、９０質量％以上が特に好ましい。また、本発明の添加剤は、ポリビニルアルコールからなってもよい。ポリビニルアルコール中に不純物が含まれることもあるので、本発明の添加剤中のポリビニルアルコールの含有量は、９９質量％以下や９７質量％以下、９５質量％以下としてもよい。 The additive of the present invention may contain other components such as an antifoaming agent. On the other hand, since other components may affect the conductivity of the electrode surface of the lead storage battery, it is preferable to use polyvinyl alcohol as the main component. The content of polyvinyl alcohol in the additive of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Further, the additive of the present invention may consist of polyvinyl alcohol. Since impurities may be contained in the polyvinyl alcohol, the content of the polyvinyl alcohol in the additive of the present invention may be 99% by mass or less, 97% by mass or less, or 95% by mass or less.
本発明の添加剤の形態は液状であっても、固形物であってもよい。例えば、ポリビニルアルコールと水との混合液であるポリビニルアルコール水溶液を、本発明の添加剤としてもよい。
取り扱いのしやすさからは、本発明の添加剤は、微粉や顆粒、パウダーなどの固形物であることが好ましい。
The form of the additive of the present invention may be liquid or solid. For example, an aqueous polyvinyl alcohol solution, which is a mixture of polyvinyl alcohol and water, may be used as the additive of the present invention.
From the viewpoint of ease of handling, the additive of the present invention is preferably a solid substance such as fine powder, granules, or powder.
上記のように、添加剤のサルフェーション抑制の効果は、ＣＶ法により得られる酸化波ピークの立ち上がり付近の電流変化から評価することができる。具体的には、下記の測定条件の充放電サイクル試験後に得られるサイクリックボルタモグラム（ＣＶ）において、−０．９５Ｖ〜−０．８５Ｖの電位幅（ｄＶ）における電流変化（ｄＩ）（ｄＩ／ｄＶ）から、サルフェーション抑制の効果を評価することができる。
（充放電サイクル試験の測定条件）
０．５ｍｏｌ／Ｌの希硫酸に、硫酸の質量に対して０．０２質量％となるように添加剤を加えた水溶液を電解液とし、作用極：Ｐｂ、対極：Ｐｔ、参照極：Ｈｇ／ＨｇＳＯ4の３電極式の電解セルを用いて、掃引速度２０ｍＶ／ｓで−２Ｖ〜０の電位幅で電位走差を５００サイクル繰り返し行う。
なお、充放電サイクル試験における、５００サイクルは、自動車のバッテリー２〜３年の加速試験に相当し、上記の測定条件で評価することで、自動車のバッテリーの２〜３年の性能評価の代替とすることができる。
As described above, the effect of the additive on suppressing sulfation can be evaluated from the current change near the rise of the oxidation wave peak obtained by the CV method. Specifically, in the cyclic voltammogram (CV) obtained after the charge / discharge cycle test under the following measurement conditions, the current change (dI) (dI / dV) in the potential width (dV) of −0.95V to −0.85V. ), The effect of suppressing sulfation can be evaluated.
(Measurement conditions for charge / discharge cycle test)
An aqueous solution prepared by adding an additive to 0.5 mol / L dilute sulfuric acid so as to be 0.02% by mass based on the mass of sulfuric acid was used as an electrolytic solution, and the working electrode: Pb, counter electrode: Pt, reference electrode: Hg /. Using a 3-electrode electrolytic cell of HgSO 4 , the potential running difference is repeated for 500 cycles at a sweep rate of 20 mV / s and a potential range of -2 V to 0.
In the charge / discharge cycle test, 500 cycles correspond to an acceleration test of a car battery for 2 to 3 years, and by evaluating under the above measurement conditions, it can be used as a substitute for the performance evaluation of the car battery for 2 to 3 years. can do.
ＣＶ法では、電位を負に走査すると電極内電子エネルギーが高まり、電極から酸化体への電子移動が徐々に速くなり、還元電流（負電流）が増える。やがて還元電流は減少し、最終的に還元波ピークが形成される。また、電位を正へ走査すると、電極付近の還元体から電子移動がおこり、酸化電流（正電流）が流れる。電子移動が進行し、ほとんどが酸化体に戻ると、酸化電流が減り、酸化波ピークを形成する。鉛電極表面の反応においては、電流が負に流れる場合、上記式（２）に示す右から左への還元（充電）反応となり、電流が正に流れる場合、上記式（２）に示す左から右への酸化（放電）反応となる。ｄＩ／ｄＶ値から酸化反応の進行の速さ（酸化反応における電流の流れやすさ）を把握することが可能となる。 In the CV method, when the potential is negatively scanned, the electron energy in the electrode increases, the electron transfer from the electrode to the oxidant gradually increases, and the reduction current (negative current) increases. Eventually, the reduction current decreases, and finally a reduction wave peak is formed. Further, when the potential is scanned positively, electron transfer occurs from the reducing body near the electrode, and an oxidation current (positive current) flows. As the electron transfer progresses and most of it returns to the oxidant, the oxidation current decreases and an oxidation wave peak is formed. In the reaction on the surface of the lead electrode, when a current flows negatively, it becomes a reduction (charging) reaction from right to left shown in the above formula (2), and when a current flows positively, it starts from the left shown in the above formula (2). It becomes an oxidation (discharge) reaction to the right. From the dI / dV value, it is possible to grasp the speed of progress of the oxidation reaction (easiness of current flow in the oxidation reaction).
サルフェーション抑制の効果をより高めるためには、ＣＶ法により得られる酸化波ピークの立ち上がり付近の電流変化が大きいほど好ましい。例えば、本発明の添加剤は、上記の測定条件の充放電サイクル試験後に得られるサイクリックボルタモグラム（ＣＶ）において、−０．９５Ｖ〜−０．８５Ｖの電位幅（ｄＶ）における電流変化（ｄＩ）（ｄＩ／ｄＶ）が、１．０以上が好ましく、１．２以上がより好ましく、１．４以上がさらに好ましい。 In order to further enhance the effect of suppressing sulfation, it is preferable that the current change in the vicinity of the rise of the oxidation wave peak obtained by the CV method is large. For example, the additive of the present invention has a current change (dI) in a potential width (dV) of −0.95V to −0.85V in a cyclic voltammogram (CV) obtained after a charge / discharge cycle test under the above measurement conditions. (DI / dV) is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 1.4 or more.
また、本発明の添加剤は、上記の測定条件の充放電サイクル試験後に、ＡＣ振幅１０ｍＶ、測定周波数１０ｍＨｚ〜２０ｋＨｚの測定条件における交流（ＡＣ）インピーダンス法により算出される電解液抵抗が、小さいほど好ましい。例えば、電解液抵抗は、１．０以下が好ましく、０．７以下がより好ましく、０．６以下がさらに好ましい。
なお、交流インピーダンス法および電解液抵抗について、詳しくは実施例にて説明する。
Further, the additive of the present invention has a smaller electrolyte resistance calculated by an alternating current (AC) impedance method under measurement conditions of AC amplitude 10 mV and measurement frequency 10 MHz to 20 kHz after the charge / discharge cycle test under the above measurement conditions. preferable. For example, the electrolyte resistance is preferably 1.0 or less, more preferably 0.7 or less, and even more preferably 0.6 or less.
The AC impedance method and the electrolyte resistance will be described in detail in Examples.
また、本発明の添加剤は、上記の条件の充放電サイクル試験後の作用極をＥＤＸにより元素分析することで算出される鉛元素に対する硫黄元素の割合（Ｓ/Ｐｂ）が、小さいほど好ましい。例えば、鉛元素に対する硫黄元素の割合は、０．０３５以下が好ましく、０．０３０以下がより好ましく、０．０２５以下がさらに好ましい。 Further, in the additive of the present invention, the smaller the ratio (S / Pb) of the sulfur element to the lead element calculated by elemental analysis of the working electrode after the charge / discharge cycle test under the above conditions by EDX, the more preferable. For example, the ratio of the sulfur element to the lead element is preferably 0.035 or less, more preferably 0.030 or less, and even more preferably 0.025 or less.
＜鉛蓄電池＞
本発明の添加剤は、鉛蓄電池の電解液に投入して用いることができる。本発明は、正極、負極、セパレーター、および電解液が収容された電槽と、蓋とを備えた鉛蓄電池であって、前記電解液が、本発明の添加剤と、硫酸とを含む水溶液である、鉛蓄電池（以下、「本発明の鉛蓄電池」と記載する場合がある。）に関するものとすることができる。
<Lead-acid battery>
The additive of the present invention can be used by being charged into the electrolytic solution of a lead storage battery. The present invention is a lead-acid battery provided with a battery case containing a positive electrode, a negative electrode, a separator, and an electrolytic solution, and a lid, wherein the electrolytic solution is an aqueous solution containing the additive of the present invention and sulfuric acid. It can be related to a certain lead-acid battery (hereinafter, may be referred to as "lead-acid battery of the present invention").
本発明の鉛蓄電池は、本発明の添加剤と硫酸とを含む水溶液を電解液とすることが特徴である。つまり、本発明の鉛蓄電池の電解液は、ポリビニルアルコールを含む鉛蓄電池用の添加剤であって、前記ポリビニルアルコールの５質量%水溶液の粘度が、１〜３０ｍＰａ・ｓである鉛蓄電池用の添加剤と、硫酸とを含む水溶液である。
電解液に含まれる、本発明の添加剤の効果により、従来の鉛蓄電池に比べて、本発明の鉛蓄電池は、より長時間にわたって電気性能が劣化しにくい。
The lead-acid battery of the present invention is characterized in that an aqueous solution containing the additive of the present invention and sulfuric acid is used as an electrolytic solution. That is, the electrolytic solution of the lead storage battery of the present invention is an additive for a lead storage battery containing polyvinyl alcohol, and the viscosity of the 5% by mass aqueous solution of the polyvinyl alcohol is 1 to 30 mPa · s. It is an aqueous solution containing an agent and sulfuric acid.
Due to the effect of the additive of the present invention contained in the electrolytic solution, the lead-acid battery of the present invention is less likely to deteriorate in electrical performance for a longer period of time than the conventional lead-acid battery.
電解液中の硫酸の濃度は、通常、３０〜４０質量％である。 The concentration of sulfuric acid in the electrolytic solution is usually 30 to 40% by mass.
また、電解液に含まれる本発明の添加剤の量は、電池の構成や使用目的などに応じて適宜選択されるものであるが、鉛蓄電池の電気容量に対する本発明の添加剤の質量が、１／１８０［ｇ／Ａｈ］〜１／２２０［ｇ／Ａｈ］であることが好ましい。 The amount of the additive of the present invention contained in the electrolytic solution is appropriately selected according to the configuration of the battery, the purpose of use, and the like, but the mass of the additive of the present invention with respect to the electric capacity of the lead storage battery is determined. It is preferably 1/180 [g / Ah] to 1/220 [g / Ah].
本発明の鉛蓄電池の正極や負極、セパレーターなどの構成は、従来公知の鉛蓄電池と同様の構成とすることができる。 The configuration of the positive electrode, the negative electrode, the separator, and the like of the lead-acid battery of the present invention can be the same as that of the conventionally known lead-acid battery.
通常、正極、負極、およびセパレーターは、正極と負極とをセパレーターを介して交互に複数積層した極板群として、電解液と共に電槽に収容された構成とすることができる。 Usually, the positive electrode, the negative electrode, and the separator can be configured to be housed in an electric tank together with an electrolytic solution as a group of electrode plates in which a plurality of positive electrodes and negative electrodes are alternately laminated via a separator.
正極は、正極活物質が正極格子間に充填された構成とすることができる。正極格子は、鉛または鉛合金で形成することができる。鉛合金は、鉛元素と、カルシウムや錫、ビスマスなどの元素を含んだ合金などを用いることができる。正極活物質は、通常、二酸化鉛である。また、正極活物質として、カルシウムなどの元素を添加した二酸化鉛を用いることもできる。極板群を構成する各正極は、集電のための耳部を有しており、これらの耳部がストラップ部分で一体化され、プラス端子に連結されている。 The positive electrode may be configured such that the positive electrode active material is filled between the positive electrode lattices. The positive electrode grid can be made of lead or a lead alloy. As the lead alloy, an alloy containing a lead element and an element such as calcium, tin, or bismuth can be used. The positive electrode active material is usually lead dioxide. Further, as the positive electrode active material, lead dioxide to which an element such as calcium is added can also be used. Each positive electrode constituting the electrode plate group has an ear portion for collecting current, and these ear portions are integrated by a strap portion and connected to a positive terminal.
負極は、負極活物質が負極格子間に充填された構成とすることができる。負極格子は、鉛または鉛合金で形成することができる。鉛合金は、鉛元素と、カルシウムや錫、ビスマスなどの元素を含んだ合金などを用いることができる。負極活物質は、通常、鉛である。また、極板群を構成する各負極は、集電のための耳部を有しており、これらの耳部がストラップ部分で一体化され、マイナス端子に連結されている。 The negative electrode may be configured such that the negative electrode active material is filled between the negative electrode lattices. The negative electrode grid can be made of lead or a lead alloy. As the lead alloy, an alloy containing a lead element and an element such as calcium, tin, or bismuth can be used. The negative electrode active material is usually lead. Further, each negative electrode forming the electrode plate group has an ear portion for collecting current, and these ear portions are integrated by a strap portion and connected to a negative terminal.
セパレーターは、正極と負極との間に配置されるものであり、正極と負極の接触による短絡の防止や、電解液を保持して硫酸イオンおよび水素イオンを透過させる役割を有する。セパレーターとしては、通常、化学繊維やガラス繊維を主体とする不織布シートが用いられる。また、合成樹脂や無機フィラーで形成された微多孔質シートなどを用いてもよい。
負極と正極との間に介在させるセパレーターの厚さや枚数は、極間距離に応じて適宜選択すればよい。
The separator is arranged between the positive electrode and the negative electrode, and has a role of preventing a short circuit due to contact between the positive electrode and the negative electrode and holding an electrolytic solution to allow sulfate ions and hydrogen ions to permeate. As the separator, a non-woven fabric sheet mainly composed of chemical fibers or glass fibers is usually used. Further, a microporous sheet formed of a synthetic resin or an inorganic filler may be used.
The thickness and the number of separators interposed between the negative electrode and the positive electrode may be appropriately selected according to the distance between the electrodes.
電槽は、上側に開口部を有する容器であり、極板群および電解液を収容可能なものである。電槽は、電解液に対して耐性を有する材料で形成されており、通常、ポリエチレンやポリプロピレン、ＡＢＳ樹脂などの合成樹脂製である。蓋は、電槽の開口部を封口するものであり、電槽と同様に合成樹脂で形成することができる。 The electric tank is a container having an opening on the upper side, and can accommodate a group of plates and an electrolytic solution. The battery case is made of a material having resistance to an electrolytic solution, and is usually made of a synthetic resin such as polyethylene, polypropylene, or ABS resin. The lid seals the opening of the electric tank, and can be formed of a synthetic resin like the electric tank.
電槽は、極板群と電解液とが収容されたセルを複数有する構成であってもよい。蓋は、複数のセルの開口部を一括して封口するものを用いることができる。例えば、起電力２Ｖのセルを６個有する構成とすることで、１２Ｖのバッテリーとすることができる。 The battery case may have a configuration having a plurality of cells in which the electrode plate group and the electrolytic solution are housed. As the lid, a lid that collectively seals the openings of a plurality of cells can be used. For example, a 12V battery can be obtained by having six cells having an electromotive force of 2V.
鉛蓄電池は、化成を行った極板群と、電解液を電槽に収容し、蓋で封口する方法や、極板群と電解液を電槽に収容した後、電槽化成を行う方法で製造することができる。化成は公知の方法を用いることができる。
また、本発明の鉛蓄電池の電解液は、例えば、本発明の添加剤と希硫酸とを混合することで調製することができる。本発明の添加剤と希硫酸との混合は、化成前であっても化成後であってもよいが、化成後に本発明の添加剤と希硫酸とを混合する方が、化成に対する本発明の添加剤の影響を少なくすることができる。
また、市販の鉛蓄電池の電解液に本発明の添加剤を投入することで、本発明の鉛蓄電池とすることもできる。
例えば、本発明の鉛蓄電池は、化成処理された正極、化成処理された負極、セパレーター、および希硫酸を含む電解液を収容した電槽に、本発明の添加剤を加えて、本発明の添加剤と希硫酸とを混合する工程と、本発明の添加剤を混合した後、電槽を蓋で封口する工程とを有する製造方法で製造することができる。
Lead-acid batteries can be prepared by storing the chemically formed electrode plate group and the electrolytic solution in an electric tank and sealing them with a lid, or by storing the electrode plate group and the electrolytic solution in the electric tank and then performing the electric tank chemical conversion. Can be manufactured. A known method can be used for chemical conversion.
Further, the electrolytic solution of the lead storage battery of the present invention can be prepared, for example, by mixing the additive of the present invention and dilute sulfuric acid. The additive of the present invention and dilute sulfuric acid may be mixed before or after chemical conversion, but it is better to mix the additive of the present invention and dilute sulfuric acid after chemical conversion according to the present invention for chemical conversion. The influence of additives can be reduced.
Further, the lead storage battery of the present invention can be obtained by adding the additive of the present invention to the electrolytic solution of a commercially available lead storage battery.
For example, in the lead-acid battery of the present invention, the additive of the present invention is added to an electric tank containing an electrolytic solution containing a chemical-treated positive electrode, a chemical-treated negative electrode, a separator, and dilute sulfuric acid. It can be produced by a production method including a step of mixing the agent and dilute sulfuric acid and a step of mixing the additive of the present invention and then sealing the battery case with a lid.
＜鉛蓄電池の再生方法＞
また、本発明は、正極、負極、セパレーター、および電解液が収容された電槽と、蓋とを備えた鉛蓄電池の再生方法であって、前記電解液と、本発明の添加剤とを混合し、電圧を印加する工程Ａを有する、再生方法（以下、「本発明の再生方法」と記載する場合がある。）に関するものとすることができる。
本発明の再生方法に用いられる鉛蓄電池は、使用中または使用済みの鉛蓄電池である。使用中または使用済みの鉛蓄電池の電槽に収容された電解液に、本発明の添加剤を投入し、所定の時間、電圧を印加することで、電気性能を回復させることができる。また、電槽から電解液を取出し、これと本発明の添加剤とを混合し、調製した混合液を電槽内に加えた後、電圧印加を行ってもよい。印加する電圧は、使用時よりも高い電圧が設定される。
また、工程Ａにおいて、鉛蓄電池の電気容量に対する本発明の添加剤の質量が、１／１８０［ｇ／Ａｈ］〜１／２２０［ｇ／Ａｈ］となるように、本発明の添加剤と電解液とを混合することが好ましい。
<How to recycle lead-acid batteries>
Further, the present invention is a method for regenerating a lead-acid battery provided with a battery case containing a positive electrode, a negative electrode, a separator, and an electrolytic solution, and a lid, wherein the electrolytic solution and the additive of the present invention are mixed. However, it can be related to a regeneration method (hereinafter, may be referred to as "regeneration method of the present invention") having a step A of applying a voltage.
The lead-acid battery used in the regeneration method of the present invention is a used or used lead-acid battery. The electrical performance can be restored by adding the additive of the present invention to the electrolytic solution housed in the battery case of the used or used lead-acid battery and applying a voltage for a predetermined time. Further, the electrolytic solution may be taken out from the electric tank, mixed with the additive of the present invention, the prepared mixed liquid may be added to the electric tank, and then a voltage may be applied. The voltage to be applied is set higher than that at the time of use.
Further, in step A, the additive and electrolysis of the present invention are made so that the mass of the additive of the present invention with respect to the electric capacity of the lead storage battery is 1/180 [g / Ah] to 1/220 [g / Ah]. It is preferable to mix with the liquid.
以下、実施例により本発明を更に詳細に説明するが、本発明は、その要旨を変更しない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is changed.
（添加剤）
表１に示す６種のポリビニルアルコールを用いて、実施例１〜実施例３を行った。
それぞれの５質量％水溶液の粘度は、純水に添加剤を投入して５質量％水溶液を作製し、良く撹拌させた後、株式会社エーアンドデイ製の粘度計（ＳＶ−１Ａ）を用いて温度が２５〜３０℃の範囲内である状態で、５回測定を行い、その平均値を計算することで算出した。
(Additive)
Examples 1 to 3 were carried out using 6 kinds of polyvinyl alcohols shown in Table 1.
The viscosity of each 5% by mass aqueous solution is adjusted by adding an additive to pure water to prepare a 5% by mass aqueous solution, stirring well, and then using a viscometer (SV-1A) manufactured by A & D Co., Ltd. It was calculated by measuring 5 times in a state of being within the range of 25 to 30 ° C. and calculating the average value thereof.
実施例１：交流インピーダンス法による電解液抵抗の測定
（実施例１−１）
０．５ｍｏｌ／Ｌの希硫酸（和光純薬工業株式会社製）に、添加剤１を０．１ｍｇ（電解質質量に対して０．０２質量％）投入し、電解液を調製した。
調製した電解液を用いて、以下の測定条件で、北斗電工株式会社のオートマチックポラリゼーションシステム（ＨＳＶ−１１０）を用いてＣＶ測定を行った。サイクル数が、１００、２００、４００、５００サイクル目に、エヌエフ回路設計ブロック製の周波数特性分析器（ＦＲＡ５０２２）によりＡＣインピーダンス測定（測定条件：ＡＣ振幅１０ｍＶ、測定周波数１０ｍＨｚ〜２０ｋＨｚ）を行った。
Example 1: Measurement of electrolyte resistance by AC impedance method (Example 1-1)
An electrolyte solution was prepared by adding 0.1 mg (0.02% by mass) of Additive 1 to 0.5 mol / L dilute sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.).
Using the prepared electrolytic solution, CV measurement was performed using an automatic polarization system (HSV-110) manufactured by Hokuto Denko Co., Ltd. under the following measurement conditions. At the 100th, 200th, 400th, and 500th cycles, AC impedance measurement (measurement conditions: AC amplitude 10 mV, measurement frequency 10 MHz to 20 kHz) was performed by a frequency characteristic analyzer (FRA5022) manufactured by NF Circuit Design Block.
＜測定条件＞
電解セル：コンパクト分析セル（株式会社イーシーフロンティア製、ＶＢ２Ａ）
作用極：鉛プレート（株式会社ニラコ製、０．２０×１０×２０ｍｍ）
対極：白金ワイヤー（株式会社イーシーフロンティア製）
参照極：Ｈｇ／ＨｇＳＯ４（インターケミ株式会社製）
電解液：０．５ｍｏｌ／Ｌ硫酸＋添加剤１
掃引速度：２０ｍＶ／ｓ
電位幅：−２Ｖから０Ｖ
サイクル数：５００回
<Measurement conditions>
Electrolytic cell: Compact analysis cell (manufactured by EC Frontier Co., Ltd., VB2A)
Working electrode: Lead plate (manufactured by Nirako Co., Ltd., 0.20 x 10 x 20 mm)
Opposite: Platinum wire (manufactured by EC Frontier Co., Ltd.)
Reference pole: Hg / HgSO4 (manufactured by Interchemi Co., Ltd.)
Electrolyte: 0.5 mol / L sulfuric acid + additive 1
Sweep speed: 20 mV / s
Potential width: -2V to 0V
Number of cycles: 500 times
（実施例１−２、比較例１−１〜比較例１−４）
添加剤１に変えて、表２に示す添加剤とした以外は、実施例１−１と同様に評価した。
(Example 1-2, Comparative Example 1-1-1 to Comparative Example 1-4)
The evaluation was carried out in the same manner as in Example 1-1 except that the additive 1 was changed to the additive shown in Table 2.
表２に、実施例１−１、実施例１−２、比較例１−１〜比較例１−４における、電解液抵抗（Ｒｓｏｌ）の値を示す。 Table 2 shows the values of the electrolyte resistance (Rsol) in Example 1-1, Example 1-2, and Comparative Examples 1-1 to 1-4.
ここで、図１に得られたインピーダンススペクトルの一例（比較例１−２）を示す。電極と電解液との界面では、直列接続された電荷移動抵抗（Ｒct）とワールブルグインピーダンス（ＺＷ）が二重層容量（Ｃdl）に並列接続され、電解液抵抗（Ｒsol）が直列接続された等価回路が考えられる。この等価回路の入力周波数変化に対するインピーダンスを描くことによって、界面状態を知ることができる。Ｒsolは高周波数域における実軸と接する点と原点間の大きさであり、Ｒctは低周波数から中間周波数部分の円弧の半径を示している。ただし、交流の印加において細かい充放電が繰り返されることで、極板の状態が変化するおそれがあることが知られており、実際に電荷移動抵抗Ｒctを測定してみるサイクルごとにオーダーが変化した。そのため、実施例１では、電解液抵抗Ｒsolを評価した。 Here, an example of the impedance spectrum obtained in FIG. 1 (Comparative Example 1-2) is shown. At the interface between the electrode and the electrolyte, the charge transfer resistor (R ct ) and the Warburg impedance (ZW) connected in series are connected in parallel to the double layer capacitance (C dl ), and the electrolyte resistor (R sol ) is connected in series. An equivalent circuit can be considered. The interface state can be known by drawing the impedance with respect to the input frequency change of this equivalent circuit. R sol is the size between the point tangent to the real axis and the origin in the high frequency range, and R ct is the radius of the arc from the low frequency to the intermediate frequency. However, it is known that the state of the electrode plate may change due to repeated fine charging and discharging when alternating current is applied, and the order changes with each cycle in which the charge transfer resistance R ct is actually measured. did. Therefore, in Example 1, the electrolyte resistance R sol was evaluated.
実施例２：ＣＶ法による電位変化に対する電流の評価
実施例１で得られた４００サイクル目および５００サイクル目のサイクリックボルタモグラムにおける、還元反応から酸化反応に転じた直後の酸化反応において、電位幅−０．９５Ｖ〜−０．８５Ｖ（ｄＶ）における電流変化（ｄＩ）の割合（ｄＩ／ｄＶ）を求めた。
Example 2: Evaluation of current for potential change by CV method In the cyclic voltammetry at the 400th cycle and the 500th cycle obtained in Example 1, the potential width-in the oxidation reaction immediately after the reduction reaction was changed to the oxidation reaction. The ratio (dI / dV) of the current change (dI) from 0.95 V to −0.85 V (dV) was determined.
表３に、実施例２−１、実施例２−２、比較例２−１〜比較例２−４における、ｄＩ／ｄＶ値を示す。
酸化反応において、添加剤１、添加剤２は、添加剤４と比べて粘度が小さいため、イオンが移動しやすく化学反応が起こりやすいことが推察できる。また、添加剤１、添加剤２は、ポリビニルアルコールの酢酸基部分の効果により導電性が向上したと考えられる。
Table 3 shows the dI / dV values in Example 2-1 and Example 2-2 and Comparative Examples 2-1 to 2-4.
In the oxidation reaction, since the additives 1 and 2 have lower viscosities than the additive 4, it can be inferred that ions are easily transferred and a chemical reaction is likely to occur. Further, it is considered that the conductivity of Additive 1 and Additive 2 was improved by the effect of the acetic acid group portion of polyvinyl alcohol.
実施例３：鉛負電極のＦＥ−ＳＥＭによる表面観察およびＥＤＸによる元素分析
（鉛負電極のFE−ＳＥＭによる表面観察）
添加剤１、添加剤３〜６を用いて実施例１と同様にして、ＣＶ測定を５００サイクル行った。また、添加剤なしの系もあわせて測定を行った。５００サイクルのＣＶ測定終了後（充放電サイクル試験後）の鉛電極の表面を、ＦＥ−ＳＥＭにより観察した。
Example 3: Surface observation of lead-negative electrode by FE-SEM and elemental analysis by EDX (surface observation of lead-negative electrode by FE-SEM)
CV measurement was carried out for 500 cycles in the same manner as in Example 1 using Additive 1 and Additives 3 to 6. In addition, the system without additives was also measured. The surface of the lead electrode after the completion of the CV measurement of 500 cycles (after the charge / discharge cycle test) was observed by FE-SEM.
図２に、測定前の鉛負電極の表面状態と、実施例３−１（添加剤１投入）、実施例３−２（添加剤３投入）、比較例３−１（添加剤なし）、比較例３−２（添加剤４投入）、比較例３−３（添加剤５投入）、比較例３−４（添加剤６投入）のＣＶ測定終了後の鉛電極の表面の状態を示す。図２に示すように、ＣＶ測定後の各電極の表面には、何らかの物質が形成されていることがわかった。実施例３−１のＣＶ測定終了後の電極表面は、繊維状のネットワークの形成が観察され、細かい電気の通り道ができていると考えられる。実施例３−２のＣＶ測定終了後の電極表には細かい粒子が付着しており、硫酸鉛が電子伝導に及ぼす影響が小さく、導電性が高まると考えられる。 FIG. 2 shows the surface state of the lead-negative electrode before measurement, Example 3-1 (additive 1 added), Example 3-2 (additive 3 added), Comparative Example 3-1 (no additive), and FIG. The state of the surface of the lead electrode after the completion of the CV measurement of Comparative Example 3-2 (additive 4 added), Comparative Example 3-3 (additive 5 added), and Comparative Example 3-4 (additive 6 added) is shown. As shown in FIG. 2, it was found that some substance was formed on the surface of each electrode after the CV measurement. It is considered that the formation of a fibrous network is observed on the electrode surface after the completion of the CV measurement of Example 3-1 and a fine electrical path is formed. It is considered that fine particles are attached to the electrode table after the completion of the CV measurement in Example 3-2, the influence of lead sulfate on electron conduction is small, and the conductivity is enhanced.
（鉛負電極のＥＤＸによる元素分析）
ＦＥ−ＳＥＭで示している画像上の元素分析をＥＤＸにより行った。
質量％濃度による鉛（Ｐｂ）元素に対する硫黄（Ｓ）元素の割合としてＳ／Ｐｂ、および鉛（Ｐｂ）元素に対する酸素（Ｏ）元素の割合としてＯ／Ｐｂを計算した結果を示す。新品鉛にはＳ元素の付着は実質的にないといえる。鉛電極表面に発生する物質が硫酸鉛（ＰｂＳＯ4）であるために、硫酸鉛が生成されればＳ原子、Ｏ原子共に増える。そのため、Ｓ／ＰｂおよびＯ／Ｐｂを求めると鉛電極表面にどれくらいの硫酸鉛の付着があるのか確かめる一つの指標とすることができる。
(Elemental analysis of lead-negative electrodes by EDX)
Elemental analysis on the image shown by FE-SEM was performed by EDX.
The results of calculating S / Pb as the ratio of sulfur (S) element to lead (Pb) element and O / Pb as the ratio of oxygen (O) element to lead (Pb) element by mass% concentration are shown. It can be said that there is virtually no adhesion of element S to new lead. Since the substance generated on the surface of the lead electrode is lead sulfate (PbSO 4 ), if lead sulfate is generated, both S and O atoms increase. Therefore, when S / Pb and O / Pb are obtained, it can be used as an index for confirming how much lead sulfate is attached to the surface of the lead electrode.
表４に、実施例３−１、実施例３−２、比較例３−１〜比較例３−４における、Ｓ／Ｐｂ値とＯ／Ｐｂ値を示す。
表４に示すように、実施例３−１、実施例３−２は、Ｓ／ＰｂおよびＯ／Ｐｂが小さいことから、硫酸鉛の生成が抑制されており、サルフェーションの発生を抑制しているといえる。
Table 4 shows the S / Pb value and the O / Pb value in Example 3-1, Example 3-2, and Comparative Example 3-1 to Comparative Example 3-4.
As shown in Table 4, in Examples 3-1 and 3-2, since S / Pb and O / Pb are small, the production of lead sulfate is suppressed and the occurrence of sulfation is suppressed. It can be said that.
また、実施例２と実施例３の結果を用いて、Ｓ／Ｐｂ値に対するｄＩ／ｄＶ値をプロットすると、Ｓ／Ｐｂ値の増加と共にｄＩ／ｄＶ値は減少しており、相関する傾向にあることが分かる。
特に、添加剤１を投入した系では、ｄＩ／ｄＶ値が大きく、Ｓ／Ｐｂ、Ｏ／Ｐｂの値が小さいことから、放電反応が促進されており、導電性が良いといえる。放電反応が促進されたということは、硫酸鉛を分解し、Ｐｂ2+を比較例に比べて良く供給していたと考えることができる。
Further, when the dI / dV value with respect to the S / Pb value is plotted using the results of Examples 2 and 3, the dI / dV value decreases as the S / Pb value increases, and tends to correlate with each other. You can see that.
In particular, in the system in which the additive 1 is added, the dI / dV value is large and the S / Pb and O / Pb values are small, so that the discharge reaction is promoted and the conductivity is good. The fact that the discharge reaction was promoted can be considered to indicate that lead sulfate was decomposed and Pb 2+ was supplied better than in the comparative example.
実施例４：実電池を用いた試験
（実施例４−１）
市販の鉛蓄電池（Ｓｕｎｇｗｏｏ Ａｕｔｏｍｏｔｉｖｅ社製、Ｅｕｒｏｐｏｗｅｒ、３０Ａ１９Ｌ）、定格電圧１２Ｖ、５時間率容量２４Ａｈを用い、添加剤１を電池容量（Ａｈ）に対して１／２００ｇ（０．１８ｇ）の割合でセル内に投入後、添加剤１が分散するように撹拌した。添加剤１の分散が終わった鉛蓄電池を８Ａで５時間充電し、満充電後８０Ａで放電し、１０．５Ｖに到達するまでのサイクルを３０サイクル行い、その時の放電時間の変化及び放電容量を評価した。
Example 4: Test using an actual battery (Example 4-1)
Using a commercially available lead-acid battery (Sungwo Automotive, Europower, 30A19L), rated voltage 12V, 5-hour rate capacity 24Ah, additive 1 is added at a ratio of 1/200g (0.18g) to the battery capacity (Ah). After being charged into the cell, the mixture was stirred so that the additive 1 was dispersed. The lead-acid battery in which the additive 1 has been dispersed is charged at 8 A for 5 hours, discharged at 80 A after being fully charged, and 30 cycles are performed until it reaches 10.5 V, and the change in discharge time and the discharge capacity at that time are measured. evaluated.
（比較例４−１、比較例４−２）
添加剤を投入せずに、実施例４−１と同様に評価したものを比較例４−１とした。また、添加剤１に変えて添加剤４を用いた以外は、実施例４−１と同様に評価したものを比較例４−２とした。
(Comparative Example 4-1 and Comparative Example 4-2)
Comparative Example 4-1 was evaluated in the same manner as in Example 4-1 without adding an additive. Further, those evaluated in the same manner as in Example 4-1 except that the additive 4 was used instead of the additive 1 were designated as Comparative Example 4-2.
図３に、サイクル数に対する放電時間の変化を示す。全ての場合において、初期サイクル（１〜３サイクル）で放電時間の減少が見られ、それ以降ではサイクル数の増加と共に、放電時間は徐々に減少し、２２サイクル以降はほぼ一定値で推移していることが分かる。比較例４−１（添加剤なし）と比較して、実施例４−１（添加剤１投入）は、サイクル数に対する放電時間が長いことが確認できた。 FIG. 3 shows the change in discharge time with respect to the number of cycles. In all cases, the discharge time decreased in the initial cycle (1 to 3 cycles), and after that, the discharge time gradually decreased as the number of cycles increased, and remained almost constant after 22 cycles. You can see that there is. It was confirmed that the discharge time of Example 4-1 (additive 1 added) was longer than that of Comparative Example 4-1 (without additive).
表５に、３０サイクルまでの実施例４−１、比較例４−１、比較例４−２の放電容量を示す。実施例４−１は、比較例４−１と比較して約１５％高いことが分かる。これは、電極表面の導電状態を高く維持しつつ、サルフェーションを抑制していたものと推察される。 Table 5 shows the discharge capacities of Example 4-1 and Comparative Example 4-1 and Comparative Example 4-2 up to 30 cycles. It can be seen that Example 4-1 is about 15% higher than Comparative Example 4-1. It is presumed that this was because sulfation was suppressed while maintaining a high conductive state on the electrode surface.
本発明によれば、電池性能が劣化しにくい鉛蓄電池が得られるため、自動車、非常用電源、電力貯蔵、太陽光発電システムなど多くの用途にさらに利用しやすいものとなる。さらに、廃棄される鉛蓄電池の量を削減することができ、環境的にも負荷を軽減できる。 According to the present invention, since a lead-acid battery whose battery performance does not easily deteriorate can be obtained, it becomes easier to use in many applications such as automobiles, emergency power sources, electric power storage, and photovoltaic power generation systems. Furthermore, the amount of lead-acid batteries that are discarded can be reduced, and the environmental load can be reduced.
Claims (7)
前記ポリビニルアルコールの５質量%水溶液の粘度が、１〜３０ｍＰａ・ｓである鉛蓄電池用の添加剤。 An additive for lead-acid batteries containing polyvinyl alcohol.
An additive for a lead storage battery having a viscosity of a 5% by mass aqueous solution of polyvinyl alcohol of 1 to 30 mPa · s.
前記電解液が、請求項１から３のいずれかに記載の添加剤と、硫酸とを含む水溶液である、鉛蓄電池。 A lead-acid battery including a battery case containing a positive electrode, a negative electrode, a separator, and an electrolytic solution, and a lid.
A lead-acid battery in which the electrolytic solution is an aqueous solution containing the additive according to any one of claims 1 to 3 and sulfuric acid.
前記電解液と、請求項１から３のいずれかに記載の添加剤とを混合した後に、電圧を印加する工程Ａを有する、再生方法。 A method for regenerating a lead-acid battery having a lid and an electric tank containing a positive electrode, a negative electrode, a separator, and an electrolytic solution.
A regeneration method comprising a step A in which a voltage is applied after mixing the electrolytic solution with the additive according to any one of claims 1 to 3.
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