JP5138429B2 - Hydrogen storage alloy for secondary battery - Google Patents
Hydrogen storage alloy for secondary battery Download PDFInfo
- Publication number
- JP5138429B2 JP5138429B2 JP2008059341A JP2008059341A JP5138429B2 JP 5138429 B2 JP5138429 B2 JP 5138429B2 JP 2008059341 A JP2008059341 A JP 2008059341A JP 2008059341 A JP2008059341 A JP 2008059341A JP 5138429 B2 JP5138429 B2 JP 5138429B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen storage
- storage alloy
- amount
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910045601 alloy Inorganic materials 0.000 title claims description 50
- 239000000956 alloy Substances 0.000 title claims description 50
- 239000001257 hydrogen Substances 0.000 title claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910020794 La-Ni Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 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
Landscapes
- Powder Metallurgy (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本発明は、二次電池用水素吸蔵合金に関し、特にサイクル寿命が長くかつ高容量の二次電池用水素吸蔵合金について提案する。 The present invention relates to a hydrogen storage alloy for a secondary battery, and particularly proposes a hydrogen storage alloy for a secondary battery having a long cycle life and a high capacity.
現在、二次電池用の負極として用いられている水素吸蔵合金は、ミッシュメタルのようなＬａ、Ｃｅ、Ｎｄ、Ｐｒ等の希土類金属にニッケルを配合した希土類−ニッケル合金に、ＡｌやＭｎ、Ｃｏ等の金属を固溶した、いわゆるＡＢ５系の合金が主体である。二次電池用水素吸蔵合金として、Ｌａ、Ｃｅ等を含有する混合希土類金属を配合した希土類−ニッケル系のＡＢ５系の合金が賞用される理由は、Ｔｉ−Ｚｒ系のいわゆるＡＢ２系合金に比べると、サイクル寿命が永いという特性を有するためである。 Currently, hydrogen storage alloys used as negative electrodes for secondary batteries are rare earth-nickel alloys in which nickel is mixed with rare earth metals such as La, Ce, Nd, Pr such as Misch metal, Al, Mn, Co metal etc. and solid solution, so-called AB 5 type alloy is mainly. The reason why a rare earth-nickel AB 5 alloy containing a mixed rare earth metal containing La, Ce, etc. is used as a hydrogen storage alloy for a secondary battery is because of a so-called AB 2 alloy of Ti—Zr This is because the cycle life is longer than that of.
このような希土混合系合金において、Ｌａは、電池容量を高めるという特性を有する。従って、混合希土類金属中には、Ｌａ量を多めに配合することが好ましいが、あまり多いと、電池のサイクル寿命、すなわち繰り返し充放電回数が少なくなってしまうという欠点があった。このことから、従来はＣｅリッチの合金が用いられたり、Ｌａ主体の合金であっても、Ｌａ量：６０％以下の合金が用いられてきた。 In such a rare earth mixed alloy, La has a characteristic of increasing the battery capacity. Therefore, it is preferable to mix a large amount of La in the mixed rare earth metal. However, if the amount is too large, there is a disadvantage that the cycle life of the battery, that is, the number of repeated charging and discharging is reduced. For this reason, a Ce-rich alloy has been conventionally used, and an alloy having an La content of 60% or less has been used even if the alloy is mainly La.
また、上記希土類元素含有水素吸蔵合金には、その他電池容量およびサイクル寿命を高めるためにＡｌ、Ｍｎ、Ｃｏのような金属を固溶・添加していた。例えば、Ｃｏは、サイクル寿命をさらに長くする目的で、原子比で０．６〜１．５程度添加していた。また、Ｍｎについては、Ｌａ量を抑制したために低下する容量を補う効果があり、原子比で０．２〜０．６程度を添加していた。 In addition, other metals such as Al, Mn, and Co have been added to the rare earth element-containing hydrogen storage alloy in order to increase battery capacity and cycle life. For example, Co was added in an atomic ratio of about 0.6 to 1.5 for the purpose of further extending the cycle life. Moreover, about Mn, it has the effect of supplementing the capacity | capacitance which falls because the amount of La was suppressed, About 0.2-0.6 was added by atomic ratio.
なお、これらの添加元素は、ＡＢ５系合金のうちのＢサイト（Ｎｉサイト）に添加されるものがほとんどである。一方、Ａサイト（ＬａまたはＬａを含む混合希土類金属サイト）に添加する元素としては、特許文献１や特許文献２に記載されたＺｒ、Ｍｏ等の元素が知られている。 Most of these additive elements are added to the B site (Ni site) of the AB 5 alloy. On the other hand, as elements added to the A site (La or La-containing mixed rare earth metal site), elements such as Zr and Mo described in Patent Literature 1 and Patent Literature 2 are known.
上記特許文献１に記載された技術は、ＺｒをＬａに対し、原子比で０．２〜０．３を添加することによって、水素を吸蔵しないＮｉ−Ｚｒの網目状の析出相を合金中に析出させ、該析出相によって、水素吸蔵・放出時に起こるクラックの拡大を阻止するという技術である。また、上記特許文献２に記載された技術は、Ｌａを７０％以上含有する水素吸蔵合金に、ＺｒまたはＭｏを原子比で０．０２〜０．０３添加した合金であり、この合金溶製後に急冷凝固させることで、Ｚｒ−Ｃｏ−Ｎｉ−Ａｌのような金属間化合物を析出させ、合金の偏析を防止し、耐食性を向上させることによって、容量が大きいままで長サイクル寿命の合金を得ようとする技術である。
上述した各従来技術（特許文献１，特許文献２）のうち、例えば、Ｌａサイトに元素を添加して容量とサイクル寿命を高めるという技術は、同公報に記載されているように添加元素が第２相として析出相を形成し、この析出相がアルカリによる腐食を受け、電池性能が劣化する、という課題を残していた。 Among the above-described conventional techniques (Patent Document 1 and Patent Document 2), for example, the technique of increasing the capacity and cycle life by adding an element to the La site has the additive element as described in the same publication. There was a problem that a precipitated phase was formed as two phases, and this precipitated phase was corroded by alkali to deteriorate the battery performance.
本発明の主たる目的は、サイクル寿命が永くかつ高放電容量の二次電池用水素吸蔵合金を提供することにある。また、本発明の他の目的は、水素吸蔵・放出時の割れが少なく、かつ耐アルカリ性に優れる二次電池用水素吸蔵合金を提供することにある。 A main object of the present invention is to provide a hydrogen storage alloy for a secondary battery having a long cycle life and a high discharge capacity. Another object of the present invention is to provide a hydrogen storage alloy for a secondary battery that has few cracks during storage and release of hydrogen and is excellent in alkali resistance.
上記の目的の実現に向けて鋭意研究の結果、発明者らは、合金組成の最適バランスと、第２相を形成しない適切な添加元素の配合という合金設計を見いだし、本発明を完成した。
すなわち、本発明は、一般式がＡＢ ５ 系で表される水素吸蔵合金であって、Ａは（Ｒ ｘ Ｍ ｙ ）、Ｂ ５ は（Ｎｉ ａ Ｃｏ ｂ Ｍｎ ｃ Ａｌ ｄ ）（ただし、Ｒは、Ｌａを７５％以上含有する希土類混合金属、Ｍは、Ｔｉ、Ｚｒ、Ｈｆから選ばれる何れか一種の金属、ｘ＋ｙ＝１、０．００２≦ｙ＜０．０１、３．５＜ａ＜４．５、０．６≦ｂ＜１．０、ｃ≦０．２、０．２≦ｄ≦０．４）であり、マイクロビッカース硬度が、４００以上であることを特徴とする二次電池用水素吸蔵合金である。
なお、本発明にかかる水素吸蔵合金は、マイクロビッカース硬度を、４００以上にすることにより、水素吸蔵・放出時の割れが少なく、アルカリに対する腐食の小さいものが得られる。
As a result of diligent research toward the realization of the above object, the inventors have found an alloy design of an optimal balance of alloy composition and an appropriate additive element that does not form the second phase, and completed the present invention.
That is, the present invention is a hydrogen storage alloy whose general formula is represented by the AB 5 system, where A is (R x M y ), B 5 is (Ni a Co b Mn c Al d ) (where R is , La is a rare earth mixed metal containing 75% or more, M is any one metal selected from Ti, Zr and Hf, x + y = 1, 0.002 ≦ y <0.01, 3.5 <a <4 0.5, 0.6 ≦ b <1.0, c ≦ 0.2, 0.2 ≦ d ≦ 0.4 ), and the micro Vickers hardness is 400 or more . It is a hydrogen storage alloy.
In addition, the hydrogen storage alloy concerning this invention can obtain the thing with few cracks at the time of hydrogen storage and discharge | release, and little corrosion with respect to alkali by making micro Vickers hardness 400 or more.
本発明の水素吸蔵合金は、放電容量が大きく、かつサイクル寿命が永く、二次電池用負極として好適である。 The hydrogen storage alloy of the present invention has a large discharge capacity and a long cycle life, and is suitable as a negative electrode for a secondary battery.
本発明の水素吸蔵合金設計思想の特徴は、第１に、該合金中のＬａ配合比率を高めることにより、高容量化を実現することにある。第２は、Ｌａサイトに添加固溶させるＴｉ、Ｚｒ、Ｈｆのいずれか１種の添加元素の作用により、合金の硬度を向上させてサイクル寿命を高めることにある。本発明は、このような考え方に立脚して開発したものであり、前者の考え方に対しては、Ｌａ量を混合希土類金属（Ｒ）中に占めるＬａの量にして７５％以上とする。これによって、放電容量を可能な限り高め、Ｌａ−Ｎｉ系の合金の理論放電容量に限りなく近づけることができる。 The feature of the design concept of the hydrogen storage alloy of the present invention is firstly to realize a high capacity by increasing the La mixture ratio in the alloy. The second is to improve the hardness of the alloy and increase the cycle life by the action of any one of the additive elements Ti, Zr, and Hf added and dissolved in the La site. The present invention has been developed based on such a concept. For the former concept, the amount of La is 75% or more in terms of the amount of La in the mixed rare earth metal (R). As a result, the discharge capacity can be increased as much as possible and can approach the theoretical discharge capacity of the La-Ni alloy as much as possible.
一方、後者の考え方に立脚する構成として、上記のＬａサイトに添加する元素Ｍ（Ｔｉ、Ｚｒ、Ｈｆの何れか１種）の量ｙは、Ｌａと固溶することを前提とし、かつ第２相を析出させない量、即ち、原子比で０．００２以上０．０１未満の極微量とした。なお、Ｍの添加量ｙを、原子比で０．００２以上０．０１未満とした理由は、０．００２未満では、この合金のマイクロビッカース硬度を４００以上とすることができず、そのために水素吸蔵・放出時、すなわち、充放電時に合金が割れやすくなり、サイクル寿命が低下するからであり、一方、０．０１以上では、Ｍ元素が、合金中に第２相として析出し、該第２相がアルカリによる腐食を受けるため、耐食性の低下を招いてサイクル寿命の低下につながるからである。 On the other hand, as a configuration based on the latter concept, the amount y of the element M (any one of Ti, Zr, and Hf) added to the La site is premised on being dissolved in La, and the second The amount that does not precipitate the phase, that is, a very small amount of 0.002 or more and less than 0.01 by atomic ratio. The reason why the addition amount y of M is set to 0.002 or more and less than 0.01 in atomic ratio is that if it is less than 0.002, the micro Vickers hardness of this alloy cannot be set to 400 or more. This is because the alloy is easily cracked at the time of occlusion / release, that is, at the time of charge / discharge, and the cycle life is reduced. On the other hand, at 0.01 or more, the M element is precipitated as a second phase in the alloy. This is because the phase is corroded by alkali, leading to a decrease in corrosion resistance and a decrease in cycle life.
また、本発明のＮｉサイトに添加する元素は、Ｌａサイトに添加する上記元素Ｍとのバランスを考慮して、Ａｌ、Ｍｎ、Ｃｏの３元素とした。特に、Ｍｎの量ｃは、この組み合わせの合金では、このＭｎが多すぎると、容量が大きくなる反面、耐食性の低下を招くので、原子比で０．２以下とした。Ｃｏの量ｂについては、添加量が多ければ多いほど電池寿命、すなわち、サイクル寿命を長くできるが、本発明の合金系では、原子比で１以上添加・配合してもそれほどの向上がみられず、また、０．６以下では寿命が短くなるので、０．６以上で、かつ１．０未満とした。また、Ａｌの量ｄについては、本発明の合金の耐食性を改善しサイクル寿命を高める効果があるが、添加元素Ｍとの関係で、添加量が多すぎるとＭ元素との第２相を作りやすくなり、また、少なすぎると耐食性改善に効果がないので、原子比で０．２以上で、かつ、０．４以下とした。また、Ｎｉの量ａは、原子比で３．５超え４．５未満とする。 Further, considering the balance with the element M added to the La site, the elements added to the Ni site of the present invention are three elements of Al, Mn, and Co. In particular, the amount c of Mn is set to 0.2 or less in terms of atomic ratio, because in this alloy combination, if the amount of Mn is too large, the capacity increases, but the corrosion resistance is lowered. Regarding the amount of Co b, the more the amount added, the longer the battery life, that is, the cycle life. However, in the alloy system of the present invention, even if it is added and blended in an atomic ratio of 1 or more, so much improvement is seen. In addition, since the life is shortened at 0.6 or less, it is set at 0.6 or more and less than 1.0. Further, the Al amount d has the effect of improving the corrosion resistance of the alloy of the present invention and increasing the cycle life. However, in relation to the additive element M, if the additive amount is too large, a second phase with the M element is formed. If the amount is too small, there is no effect in improving the corrosion resistance. Therefore, the atomic ratio is set to 0.2 or more and 0.4 or less. The amount a of Ni is set to be more than 3.5 and less than 4.5 in atomic ratio .
次に、本発明の合金においては、マイクロビッカース硬度が４００以上を示す特性が要求される。この理由は、水素吸蔵・放出時の割れを減少して、サイクル寿命を長くするために必要である。 Next, the alloy of the present invention is required to have a characteristic that the micro Vickers hardness is 400 or more. The reason for this is necessary to reduce the cracks at the time of hydrogen storage / release and to prolong the cycle life.
なお、本発明の合金を溶製後は、鋳込み時に第２相を形成しないような鋳込み方法または、焼鈍処理を行うことが好ましい。 In addition, after melting the alloy of the present invention, it is preferable to perform a casting method or an annealing process so as not to form the second phase during casting.
Ｒとして、ランタンリッチミッシュメタルと純ランタンメタル（Ｌａ １００％）を用い、これに金属Ｈｆ、金属Ｚｒ或いは金属Ｔｉの内の一種の金属と、金属Ｎｉ、金属Ｃｏ、金属Ｍｎ、金属Ａｌの所定量を高周波溶解炉で、アルゴン雰囲気下で加熱溶解して表１に示す組成の合金を作製し、得られた合金を、１０００℃×１０時間で熱処理を行い、不活性ガス中で １００ミクロン以下に粉砕した。こうして得られた合金粉末０．５ｇと金属Ｎｉ粉末０．１２ｇおよびＰＴＦＥ ０．０３ｇを混合し、加圧成形して試験用の負極を得た。 As R, lanthanum-rich misch metal and pure lanthanum metal (La 100%) are used, and this is a kind of metal Hf, metal Zr or metal Ti, metal Ni, metal Co, metal Mn, and metal Al. A fixed quantity was heated and melted in an argon atmosphere in an high-frequency melting furnace to produce an alloy having the composition shown in Table 1, and the obtained alloy was heat-treated at 1000 ° C. for 10 hours to be 100 microns or less in an inert gas. To grind. 0.5 g of the alloy powder thus obtained, 0.12 g of metallic Ni powder and 0.03 g of PTFE were mixed and pressure-molded to obtain a negative electrode for testing.
上記負極の性能試験を行うべく、該負極と市販の焼結式ニッケル極と組み合わせ、セパレータとしてポリイミド不織布を用いて、８ＮＫＯＨ電解液中で電池評価試験を行った。この試験は、２５℃で６０ｍＡ／ｇの電気量での６時間の充電と、６０ｍＡ／ｇの電流で端子電圧０．８Ｖまでの放電を繰り返す充・放電サイクルで行い、負極規制の放電容量の変化を調べたものである。得られた、飽和放電容量、サイクル特性（１０サイクル目の容量と３００サイクル目の容量の比）および合金の硬度を表１に示した。なお、同様の方法で作製した従来合金の電池特性試験の結果を比較例として表１に示した。 In order to perform a performance test of the negative electrode, a battery evaluation test was performed in an 8NKOH electrolyte using a combination of the negative electrode and a commercially available sintered nickel electrode and using a polyimide nonwoven fabric as a separator. This test was performed in a charge / discharge cycle in which charging was performed for 6 hours at 25 ° C. with an electric charge of 60 mA / g and discharging to a terminal voltage of 0.8 V with a current of 60 mA / g. It is what investigated change. Table 1 shows the saturation discharge capacity, cycle characteristics (ratio of the capacity at the 10th cycle to the capacity at the 300th cycle), and the hardness of the alloy. In addition, the result of the battery characteristic test of the conventional alloy produced by the same method is shown in Table 1 as a comparative example.
表１に示す結果から明らかなように、本発明の合金は、飽和容量が３００ｍＡｈ／ｇ以上で、容量維持率９０％と高いことが判った。従って、本発明の合金は、電池寿命が長く、かつ、サイクル特性に優れていることが判る。また、上記の結果から、本発明合金は従来合金と比較すると硬度が大きく、それはサイクル特性とも比例していて、両者の間には相関があることが判った。従って、本発明合金によれば、硬度を大きくすることにより、水素吸蔵・放出時の割れが少なくかつ添加元素の均一混合による耐アルカリ性の向上によるサイクル寿命の改善が図れることが認められた。 As is apparent from the results shown in Table 1, it was found that the alloy of the present invention had a saturation capacity of 300 mAh / g or more and a high capacity retention rate of 90%. Therefore, it can be seen that the alloy of the present invention has a long battery life and excellent cycle characteristics. Further, from the above results, it was found that the alloy of the present invention has higher hardness than the conventional alloy, which is proportional to the cycle characteristics, and there is a correlation between the two. Therefore, according to the alloy of the present invention, it was recognized that by increasing the hardness, the cracking at the time of hydrogen occlusion / release can be reduced and the cycle life can be improved by improving the alkali resistance by homogeneous mixing of the additive elements.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008059341A JP5138429B2 (en) | 2008-03-10 | 2008-03-10 | Hydrogen storage alloy for secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008059341A JP5138429B2 (en) | 2008-03-10 | 2008-03-10 | Hydrogen storage alloy for secondary battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9066822A Division JPH10261413A (en) | 1997-03-19 | 1997-03-19 | Hydrogen storage alloy for secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008210809A JP2008210809A (en) | 2008-09-11 |
| JP5138429B2 true JP5138429B2 (en) | 2013-02-06 |
Family
ID=39786900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008059341A Expired - Lifetime JP5138429B2 (en) | 2008-03-10 | 2008-03-10 | Hydrogen storage alloy for secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5138429B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740768B (en) * | 2008-11-27 | 2012-09-26 | 比亚迪股份有限公司 | Hydrogen storage alloy and preparation method thereof and cathode and battery using same |
| CN102828069B (en) * | 2012-09-26 | 2015-05-20 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2847874B2 (en) * | 1990-03-24 | 1999-01-20 | 日本電池株式会社 | Hydrogen storage electrode |
| JP3321818B2 (en) * | 1992-02-07 | 2002-09-09 | 住友金属工業株式会社 | Method for producing hydrogen storage alloy for Ni-hydrogen battery |
| JP3184609B2 (en) * | 1992-04-14 | 2001-07-09 | 東芝電池株式会社 | Metal oxide / hydrogen battery and manufacturing method thereof |
| JP3501382B2 (en) * | 1995-01-23 | 2004-03-02 | 信越化学工業株式会社 | Hydrogen storage alloy negative electrode and method for producing the same |
| JPH10261413A (en) * | 1997-03-19 | 1998-09-29 | Japan Metals & Chem Co Ltd | Hydrogen storage alloy for secondary battery |
| JPH1197003A (en) * | 1997-09-19 | 1999-04-09 | Toshiba Battery Co Ltd | Nickel hydrogen secondary cell |
-
2008
- 2008-03-10 JP JP2008059341A patent/JP5138429B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008210809A (en) | 2008-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5466015B2 (en) | Nickel metal hydride storage battery and method for producing hydrogen storage alloy | |
| KR20170131239A (en) | A material of negative electrode for lithium secondary battary | |
| JP3432873B2 (en) | Hydrogen storage alloy for alkaline storage batteries | |
| JP2012067357A (en) | Hydrogen storage alloy, and nickel hydrogen secondary battery | |
| JP5681729B2 (en) | Hydrogen storage alloy powder, negative electrode and nickel metal hydride secondary battery | |
| WO2021205749A1 (en) | Hydrogen storage alloy for alkaline storage battery | |
| JP5138429B2 (en) | Hydrogen storage alloy for secondary battery | |
| JP2001040442A (en) | Hydrogen storage alloy | |
| JP5825671B2 (en) | Hydrogen storage alloy and nickel metal hydride secondary battery using this hydrogen storage alloy | |
| JP3881823B2 (en) | Hydrogen storage alloy and method for producing the same | |
| JP3266980B2 (en) | Hydrogen storage alloy, method for producing the same, and hydrogen storage alloy electrode | |
| CN101417786A (en) | La15Fe77B8 type hydrogen storage alloy and use thereof | |
| JP2008218070A (en) | Hydrogen storage alloy for alkaline storage battery and alkaline storage battery | |
| JP5119551B2 (en) | Hydrogen storage alloy, method for producing the same, and secondary battery | |
| JP5716195B2 (en) | Hydrogen storage alloy and alkaline storage battery using this hydrogen storage alloy | |
| JP5850493B2 (en) | Hydrogen storage alloy and nickel metal hydride secondary battery using this hydrogen storage alloy | |
| JPWO2006085542A1 (en) | Low Co hydrogen storage alloy | |
| JP2001266864A (en) | Hydrogen storage alloy, alloy powder for nickel-hydrogen secondary battery negative electrode, and negative electrode for nickel-hydrogen secondary battery | |
| JP5573083B2 (en) | Hydrogen storage alloy electrode for alkaline storage battery | |
| JP6934097B1 (en) | Hydrogen storage alloy | |
| JPH10261413A (en) | Hydrogen storage alloy for secondary battery | |
| JP2005133193A (en) | Low Co hydrogen storage alloy | |
| JP2004285406A (en) | Hydrogen storage alloy and nickel-hydrogen battery electrode using the same | |
| JP2001294958A (en) | Hydrogen storage alloy for nickel-hydrogen secondary battery and method for producing the same | |
| JP3321818B2 (en) | Method for producing hydrogen storage alloy for Ni-hydrogen battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110614 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110810 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20120508 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120807 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20120807 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20121004 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121113 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121114 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151122 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |