JP2015046335A - Zinc secondary battery suppressed in generation of dendrite - Google Patents
Zinc secondary battery suppressed in generation of dendrite Download PDFInfo
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- JP2015046335A JP2015046335A JP2013177590A JP2013177590A JP2015046335A JP 2015046335 A JP2015046335 A JP 2015046335A JP 2013177590 A JP2013177590 A JP 2013177590A JP 2013177590 A JP2013177590 A JP 2013177590A JP 2015046335 A JP2015046335 A JP 2015046335A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011701 zinc Substances 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 34
- 210000001787 dendrite Anatomy 0.000 title abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 240000000560 Citrus x paradisi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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)
- Secondary Cells (AREA)
Abstract
Description
この発明は亜鉛二次電池、特にそのデンドライトの生成を抑制する技術に関する。 The present invention relates to a zinc secondary battery, and more particularly to a technique for suppressing the formation of dendrite.
金属亜鉛は、安価かつ安全なエネルギー密度が高いことから、古くより一次電池の負極材料として利用されてきた。亜鉛は、二次電池の負極としても魅力的な材料であり、多くの研究者によって二次電池負極材料としての可能性が検討されてきた。 Metallic zinc has long been used as a negative electrode material for primary batteries because it is inexpensive and has a high safe energy density. Zinc is an attractive material as a negative electrode for a secondary battery, and many researchers have examined its possibility as a negative electrode material for a secondary battery.
亜鉛を負極に用いる場合、電解液は中性またはアルカリ性のものを用いる。電解液を酸性にすると、水素が発生して好ましくないからである。一次電池においては、電解液としてKOHが用いられることが多い。 When zinc is used for the negative electrode, a neutral or alkaline electrolyte is used. This is because if the electrolyte is made acidic, hydrogen is generated, which is not preferable. In primary batteries, KOH is often used as the electrolyte.
しかしながら、亜鉛電極を負極とし、電解液としてKOHを用いた二次電池では、次のような問題があった。すなわち、充電の際に、負極から溶け出した亜鉛が、再び負極に戻り針状となって析出する。これは、デンドライトと呼ばれる。充電を繰り返すと、デンドライトが成長し、負極と正極を短絡する可能性があり危険であった。また、充電効率が低いという問題もあった。 However, a secondary battery using a zinc electrode as a negative electrode and KOH as an electrolyte has the following problems. That is, at the time of charging, zinc dissolved from the negative electrode returns to the negative electrode and precipitates in a needle shape. This is called a dendrite. When charging was repeated, dendrites grew and there was a possibility that the negative electrode and the positive electrode could be short-circuited, which was dangerous. There is also a problem that charging efficiency is low.
これは、電解液である濃厚水酸化アルカリ中での亜鉛の高い溶解性に起因するところが大きいと考えられる。これまでの試みの多くは、亜鉛負極や電解質への添加剤導入による改善が主体であったが、いずれも実用化には至っていない。たとえば、特許文献１には、銀で亜鉛粒子の表面を被覆した粉末を、負極活物質として用いることでデンドライトの発生を抑制することが記載されているが、製造コストなどの問題から実用化されていない。 This is thought to be largely due to the high solubility of zinc in the concentrated alkali hydroxide that is the electrolytic solution. Many of the attempts so far have mainly been improvements by introducing additives into the zinc negative electrode and the electrolyte, but none has been put into practical use. For example, Patent Document 1 describes that generation of dendrites is suppressed by using a powder in which the surface of zinc particles is coated with silver as a negative electrode active material. Not.
この発明は、デンドライトの生成を抑えることのできる亜鉛電極二次電池を提供することを目的とする。 An object of this invention is to provide the zinc electrode secondary battery which can suppress the production | generation of a dendrite.
(1)この発明に係る亜鉛二次電池は、亜鉛を主成分とする負極と、当該負極に接し、K2CO3を主成分とする電解液とを備えている。これにより、負極におけるデンドライトの生成を抑制することができる。 (1) A zinc secondary battery according to the present invention includes a negative electrode containing zinc as a main component and an electrolyte solution which is in contact with the negative electrode and contains K 2 CO 3 as a main component. Thereby, the production | generation of the dendrite in a negative electrode can be suppressed.
(2)この発明に係る亜鉛二次電池は、電解液が、KOHをさらに含むことを特徴としている。これにより、負極におけるデンドライトの生成を抑制することができる。 (2) The zinc secondary battery according to the present invention is characterized in that the electrolytic solution further contains KOH. Thereby, the production | generation of the dendrite in a negative electrode can be suppressed.
(3)この発明に係る亜鉛二次電池は、負極が、多孔質、表面粗化、球状体の集合のいずれかであることを特徴としている。これにより、充電電流、放電電流を増加させることができる。 (3) The zinc secondary battery according to the present invention is characterized in that the negative electrode is any one of porous, surface roughened, and spherical aggregates. Thereby, a charging current and a discharging current can be increased.
この発明の一実施形態による亜鉛電極二次電池は、電解液としてK2CO3を主成分としている。これにより、電極におけるデンドライトの生成が抑制された。その原因は定かではないが、電解液としてK2CO3を用いることで、負極の亜鉛表面自体に、亜鉛の溶解を阻害する非常に薄い（数１０nm程度）膜が形成されたか、あるいは、負極を取り囲む電解液に亜鉛の溶解を阻害する非常に薄い層が形成されたか、またはその双方が形成されたためではないかと推測される。 The zinc electrode secondary battery according to one embodiment of the present invention contains K 2 CO 3 as a main component as an electrolytic solution. Thereby, the production | generation of the dendrite in an electrode was suppressed. The cause is not clear, but by using K 2 CO 3 as the electrolyte, a very thin film (about several tens of nanometers) that inhibits zinc dissolution was formed on the zinc surface of the negative electrode itself, or the negative electrode It is speculated that a very thin layer that inhibits dissolution of zinc was formed in the electrolyte solution surrounding the substrate, or that both were formed.
なお、K2CO3を用いると、デンドライトが抑制される一方で電流が小さくなるため、負極の表面積を大きくすることが好ましい。負極を多孔質にする、表面を粗くする、球状にすることなどが可能である。たとえば、図９に示すようなブドウの実のような形状にすることで、表面積を大きくすることができる。 Note that when K 2 CO 3 is used, the surface area of the negative electrode is preferably increased because the current is reduced while dendrite is suppressed. It is possible to make the negative electrode porous, roughen the surface, or make it spherical. For example, the surface area can be increased by making the shape like a grape fruit as shown in FIG.
また、K2CO3にKOHを混合することにより、二次電池としての特性向上がみられた。 Further, by mixing KOH in K 2 CO 3, characteristic improvement of the secondary battery was observed.
図１に、この発明の一実施形態による空気亜鉛二次電池の構造を示す。筐体２の内部に、亜鉛負極８が収納されている。亜鉛負極８を覆うように負極端子６が設けられている。亜鉛負極８の下部には、セパレータ１０が設けられている。さらにその下には、正極である空気極１２が設けられている。その下部に、撥水膜１４、拡散紙１６が設けられている。なお、空気孔１８を介して、正極である空気が供給される。最下層には、シール紙２０が設けられている。この実施形態では、セパレータ１０に電解液としてのK2CO3を含浸させている。 FIG. 1 shows the structure of a zinc-air secondary battery according to an embodiment of the present invention. A zinc negative electrode 8 is housed inside the housing 2. A negative electrode terminal 6 is provided so as to cover the zinc negative electrode 8. A separator 10 is provided below the zinc negative electrode 8. Further below that, an air electrode 12 as a positive electrode is provided. A water repellent film 14 and a diffusion paper 16 are provided at the lower part. Note that air as a positive electrode is supplied through the air hole 18. A sticker paper 20 is provided in the lowermost layer. In this embodiment, the separator 10 is impregnated with K 2 CO 3 as an electrolytic solution.
本発明の一実施形態によるK2CO3電解液の効果を確認するため、図２のような装置にて、サイクリックボルタンメトリーを行った。作用極ＷＥは亜鉛、対極ＣＥはNiOH2、参照極ＲＥはHg/HgOとした。ポテンショ／ガルバノスタット３０により電流を制御するようにしている。電解液３２としては、K2CO3、KOH、両者の混合液を、濃度を変化させて用いた。 In order to confirm the effect of the K 2 CO 3 electrolyte according to one embodiment of the present invention, cyclic voltammetry was performed using an apparatus as shown in FIG. The working electrode WE was zinc, the counter electrode CE was NiOH 2 , and the reference electrode RE was Hg / HgO. The current is controlled by the potentio / galvanostat 30. As the electrolytic solution 32, K 2 CO 3 , KOH, and a mixture of both were used with varying concentrations.
図３Ａに、K2CO3、KOHを、それぞれ単独で電解液として用い、濃度を７Mまで変化させた場合の、電解液の伝導度の変化を示す。KOHと比べて、K2CO3の伝導度が高いことが分かる。 FIG. 3A shows the change in conductivity of the electrolytic solution when K 2 CO 3 and KOH are each used alone as the electrolytic solution and the concentration is changed to 7M. It can be seen that the conductivity of K 2 CO 3 is higher than that of KOH.
図３Ｂに、K2CO3とKOHを混合した電解液において、K2CO3の濃度を５Mに固定し、KOHの濃度を変化させた場合の、電解液の伝導度の変化を示す。KOHの濃度変化にもかかわらず、安定した伝導度が示されている。 FIG. 3B shows the change in conductivity of the electrolytic solution when the concentration of K 2 CO 3 is fixed at 5 M and the concentration of KOH is changed in the electrolytic solution in which K 2 CO 3 and KOH are mixed. Despite the change in KOH concentration, stable conductivity is shown.
作用極ＷＥの電位を徐々に増加させ、所定電位まで到達したら徐々に減少させ、その際の、両電極間の電流の変化を測定した。K2CO3の濃度を、０．５M〜５．０Mに変化させて測定した。図４ＡにK2CO3の濃度を０．５M〜３．０Mに変化させた場合、図４ＢにK2CO3の濃度を０．５M〜５．０Mに変化させた場合の電流の変化を示す。このグラフより、２．０Mより濃度が高くなれば、十分な電流が得られることがわかる。なお、３．０Mより高い濃度であることが好ましい。 The potential of the working electrode WE was gradually increased, and when the potential reached a predetermined potential, the potential was gradually decreased, and the change in current between the electrodes at that time was measured. The concentration of K 2 CO 3 was measured while changing from 0.5M to 5.0M. 4A shows the change in current when the concentration of K 2 CO 3 is changed from 0.5M to 3.0M, and FIG. 4B shows the change in current when the concentration of K 2 CO 3 is changed from 0.5M to 5.0M. Show. From this graph, it can be seen that if the concentration is higher than 2.0M, a sufficient current can be obtained. It is preferable that the concentration is higher than 3.0M.
なお、K2CO3の濃度が電流増加に寄与しているのか、単に電解液のPH値が寄与しているのかを明らかにするため、５．０MのK2CO3と同じPHとなるように、１MのK2CO3に０．１MのKOHを混ぜた溶液にて、電流値を測定した。その結果を、図５に示す。この図から明らかなように、１MのK2CO3に０．１MのKOHを混ぜた溶液では、十分な電流値を得ることはできなかった。このように、K2CO3の濃度が高い方が好ましいことが明らかとなった。 In order to clarify whether the concentration of K 2 CO 3 contributes to the current increase or simply the PH value of the electrolyte solution, the PH is the same as 5.0 M K 2 CO 3. In addition, the current value was measured in a solution in which 0.1 M KOH was mixed with 1 M K 2 CO 3 . The result is shown in FIG. As is apparent from this figure, a sufficient current value could not be obtained with a solution in which 0.1 M KOH was mixed with 1 M K 2 CO 3 . Thus, it was revealed that a higher concentration of K 2 CO 3 is preferable.
次に、電解液として５MのK2CO3にKOHを混合し、KOHの濃度を変化させて実験を行った。ここでは、KOHの濃度を、０．０５M〜限界濃度まで変化させた。図６Ａに、０．０５M、０．１M、０．２M、０．５Mと変化させた場合の電流値を示す。 Next, an experiment was performed by mixing KOH with 5M K 2 CO 3 as an electrolyte and changing the concentration of KOH. Here, the concentration of KOH was varied from 0.05M to the limit concentration. FIG. 6A shows current values when changed to 0.05M, 0.1M, 0.2M, and 0.5M.
KOHの濃度が０．２Mを超えたところから電流が大きく流れ始めている。また、充電と放電のバランス（プラスの側の電流波形面積が放電量、マイナスの側の電流波形面積が充電量を示す）が良いのは、０．５M近傍であることも明らかとなった。 A large current starts to flow when the KOH concentration exceeds 0.2M. It was also found that the balance between charging and discharging (the positive current waveform area indicates the amount of discharge and the negative current waveform area indicates the amount of charge) is around 0.5M.
次に、電解液として６MのKOH、５MのK2CO3、０．５MのKOHと５MのK2CO3の混合液を用いた場合の亜鉛電極におけるデンドライトの発生を調べた。それぞれの電解液について、2mA/cm2の電流を１１０分流したときの亜鉛電極の状況を調べた。亜鉛電極表面の拡大写真を、図７に示す。図７Ａは６MのKOHの電解液を用いた場合である。この写真から明らかなようにデンドライトの発生が確認できる。図７Ｂは５MのK2CO3の電解液を用いた場合である。図７Ｃは０．５MのKOHと５MのK2CO3の混合液を用いた場合である。図７Ｂ、図７Ｃから明らかなように、これらの場合、デンドライトの発生は見られなかった。 Next, the generation of dendrites at the zinc electrode was investigated when 6 M KOH, 5 M K 2 CO 3 , 0.5 M KOH and 5 M K 2 CO 3 mixed solution was used as the electrolyte. About each electrolyte solution, the condition of the zinc electrode when a current of 2 mA / cm 2 was passed for 110 minutes was examined. An enlarged photograph of the zinc electrode surface is shown in FIG. FIG. 7A shows the case of using an electrolyte solution of 6M KOH. As is apparent from this photograph, the occurrence of dendrites can be confirmed. FIG. 7B shows the case where 5M K 2 CO 3 electrolyte is used. FIG. 7C shows the case where a mixed solution of 0.5 M KOH and 5 M K 2 CO 3 is used. As is apparent from FIGS. 7B and 7C, no dendrite was observed in these cases.
図８に、2mA/cm2の電流を１１０分流したとき、5mA/cm2の電流を４４分流したとき、10mA/cm2の電流を２２分流したとき、22mA/cm2の電流を１０分流したときのデンドライトの発生状況を調べた結果を示す。丸印はデンドライトが発生したこと、バツ印はデンドライトが発生しなかったことを表している。電流値にかかわらず、６MのKOHの場合にはデンドライトが発生し、５MのK2CO3、０．５MのKOHと５MのK2CO3の混合液の場合にはデンドライトの発生は見られなかった。 8, when a current of 2 mA / cm 2 and 110 shunt, when a current of 5 mA / cm 2 44 diverted, when a current of 10 mA / cm 2 22 shunting and 10 shunting a current of 22mA / cm 2 The result of investigating the state of occurrence of dendrites is shown. A circle indicates that dendrite has occurred, and a cross indicates that no dendrite has occurred. Regardless of the current value, dendrites are generated in the case of 6M KOH, and dendrites are generated in the case of a mixture of 5M K 2 CO 3 , 0.5M KOH and 5M K 2 CO 3. There wasn't.
Claims (3)
当該負極に接し、K2CO3を主成分とする電解液と、
を備えた亜鉛二次電池。 A negative electrode mainly composed of zinc;
An electrolyte in contact with the negative electrode and containing K 2 CO 3 as a main component;
A zinc secondary battery comprising:
前記電解液は、KOHをさらに含むことを特徴とする亜鉛二次電池。 The secondary battery according to claim 1,
The zinc secondary battery, wherein the electrolytic solution further contains KOH.
前記負極は、多孔質、表面粗化、球状体の集合のいずれかであることを特徴とする亜鉛二次電池。
The zinc secondary battery according to claim 1 or 2,
The zinc secondary battery is characterized in that the negative electrode is any one of porous, roughened surface, and spherical aggregate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023167330A1 (en) * | 2022-03-03 | 2023-09-07 | 国立大学法人千葉大学 | Secondary battery having zinc negative electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54164229A (en) * | 1977-12-08 | 1979-12-27 | Imatra Paristo Oy | Battery |
| JPS62262367A (en) * | 1986-05-06 | 1987-11-14 | Sanyo Electric Co Ltd | Alkaline zing storage battery |
| JPH03272563A (en) * | 1990-03-20 | 1991-12-04 | Sanyo Electric Co Ltd | Alkali zinc storage battery |
| JPH06124706A (en) * | 1992-10-07 | 1994-05-06 | Yuasa Corp | Sealed nickel-zinc storage battery |
| JP2014165099A (en) * | 2013-02-27 | 2014-09-08 | Sumitomo Chemical Co Ltd | Air secondary battery |
-
2013
- 2013-08-29 JP JP2013177590A patent/JP6195154B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54164229A (en) * | 1977-12-08 | 1979-12-27 | Imatra Paristo Oy | Battery |
| JPS62262367A (en) * | 1986-05-06 | 1987-11-14 | Sanyo Electric Co Ltd | Alkaline zing storage battery |
| JPH03272563A (en) * | 1990-03-20 | 1991-12-04 | Sanyo Electric Co Ltd | Alkali zinc storage battery |
| JPH06124706A (en) * | 1992-10-07 | 1994-05-06 | Yuasa Corp | Sealed nickel-zinc storage battery |
| JP2014165099A (en) * | 2013-02-27 | 2014-09-08 | Sumitomo Chemical Co Ltd | Air secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023167330A1 (en) * | 2022-03-03 | 2023-09-07 | 国立大学法人千葉大学 | Secondary battery having zinc negative electrode |
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