JP2612006B2 - Method for producing hydrogen storage alloy material for battery electrode - Google Patents
Method for producing hydrogen storage alloy material for battery electrodeInfo
- Publication number
- JP2612006B2 JP2612006B2 JP62255480A JP25548087A JP2612006B2 JP 2612006 B2 JP2612006 B2 JP 2612006B2 JP 62255480 A JP62255480 A JP 62255480A JP 25548087 A JP25548087 A JP 25548087A JP 2612006 B2 JP2612006 B2 JP 2612006B2
- Authority
- JP
- Japan
- Prior art keywords
- storage alloy
- hydrogen storage
- hydrogen
- alloy material
- battery electrode
- 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 - Fee Related
Links
- 239000001257 hydrogen Substances 0.000 title claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 59
- 239000000956 alloy Substances 0.000 title claims description 48
- 238000003860 storage Methods 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 229910010380 TiNi Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- 229910008340 ZrNi Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alicyclic hydrocarbons Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000008016 vaporization Effects 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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、水素の吸収・放出を行う水素吸蔵合金材
料、特に表面に炭素体が被覆されてなる電池電極用水素
吸蔵合金材料の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a hydrogen storage alloy material for absorbing and releasing hydrogen, in particular, a hydrogen storage alloy material for a battery electrode having a surface coated with a carbon body. About.
（従来の技術） 近年、水素吸蔵合金材料の研究、開発が盛んに行わ
れ、様々な分野において該材料がもつ種々の特性を生か
した利用が図られている。(Prior Art) In recent years, research and development of a hydrogen storage alloy material have been actively carried out, and utilization in various fields utilizing various characteristics of the material has been attempted.
例えば、水素吸蔵合金材料がもつ水素の吸収・放出と
いった主たる特性を生かして水素の貯蔵および輸送への
利用が考えられている。従来は水素を耐圧性のある容器
に高圧に圧縮して保存しているが、それには温度の上昇
に伴い容器の臨界圧に近づくようなことがないよう非常
に頑丈な容器が必要とされていた。しかし、水素吸蔵合
金材料を用いることにより、通常の容器より低い圧力で
安全に貯蔵、輸送ができるため、容器を簡便にすること
ができるといった利点がある。For example, utilization of hydrogen in storage and transport has been considered by taking advantage of the main characteristics of the hydrogen storage alloy material such as absorption and release of hydrogen. Conventionally, hydrogen is compressed and stored in a pressure-resistant container at high pressure, but this requires a very sturdy container so that the temperature does not approach the critical pressure of the container. Was. However, the use of the hydrogen storage alloy material has the advantage that the container can be stored and transported safely at a lower pressure than that of a normal container, so that the container can be simplified.
また、水素吸蔵合金材料は、水素のみを吸収するとい
った特性があることから、該材料により水素の吸収・放
出を繰り返し行い、これによって水素の精製を行うこと
も可能である。Further, since the hydrogen storage alloy material has a characteristic of absorbing only hydrogen, it is possible to repeatedly absorb and release hydrogen with the material, thereby purifying the hydrogen.
さらに、水素吸蔵合金材料は、水素の吸収・放出の際
に活性な原子状水素を生成することから、燃料電池の水
素極、アルカリ電池の水素極としての応用も可能であ
る。Further, the hydrogen storage alloy material generates active atomic hydrogen upon absorption and release of hydrogen, so that it can be applied as a hydrogen electrode of a fuel cell or a hydrogen electrode of an alkaline battery.
（発明が解決しようとする問題点） ところで、この水素吸蔵合金材料は比較的高価である
ため、上述したいずれの分野でも繰り返し使用できるこ
とが望まれる。(Problems to be Solved by the Invention) Incidentally, since this hydrogen storage alloy material is relatively expensive, it is desired that it can be repeatedly used in any of the fields described above.
しかしながら、従来の水素吸蔵合金材料にあっては、
雰囲気からの表面への汚染による水素吸収・放出能力の
低下、および水素吸収・放出の繰り返しによる格子膨脹
・収縮からくる微粉化によって、周辺機器の機能を麻痺
させてしまうといった問題があった。However, in the conventional hydrogen storage alloy material,
There has been a problem that the functions of peripheral devices are paralyzed by reduction of the ability of absorbing and releasing hydrogen due to contamination of the surface from the atmosphere and pulverization caused by lattice expansion and contraction due to repeated absorption and release of hydrogen.
（発明の目的） 本発明は、上記従来の問題に鑑みなされたものであっ
て、炭素体を水素吸蔵合金粉末の表面に被覆することに
より、微粉化が起こり難く、熱伝導性に優れ、しかも雰
囲気による表面の汚染を受け難い電池電極用水素吸蔵合
金材料の製造方法を提供することを目的としている。(Object of the Invention) The present invention has been made in view of the above-mentioned conventional problems. By coating a surface of a hydrogen-absorbing alloy powder with a carbon body, pulverization hardly occurs, and excellent heat conductivity is obtained. An object of the present invention is to provide a method for producing a hydrogen storage alloy material for a battery electrode which is less susceptible to surface contamination by an atmosphere.
（発明の構成） 本発明に係る電池電極用水素吸蔵合金材料の製造方法
は、水素吸蔵合金粉末の表面に、1500℃以下の低温熱分
解による気相堆積法により炭素堆積物として形成される
炭素体を堆積させることを特徴とするものである。(Constitution of the Invention) The method for producing a hydrogen storage alloy material for a battery electrode according to the present invention is a method of forming carbon deposits on a surface of a hydrogen storage alloy powder by vapor phase deposition by low-temperature pyrolysis at 1500 ° C or lower. It is characterized by depositing the body.
より詳しくは、出発原料として炭化水素類を用い、こ
の炭化水素類を気化し、反応系内において1000℃程度の
低温で気相熱分解して得られる炭素体を、1000℃程度の
温度で気化乃至融解、溶解、凝集を起こさない水素吸蔵
合金粉末の表面に直接気相堆積させることを特徴とする
ものである。More specifically, using hydrocarbons as starting materials, the hydrocarbons are vaporized, and a carbon body obtained by gas phase pyrolysis at a low temperature of about 1000 ° C in the reaction system is vaporized at a temperature of about 1000 ° C. In addition, the present invention is characterized in that gas phase deposition is performed directly on the surface of a hydrogen storage alloy powder that does not cause melting, melting, or aggregation.
ここでの水素吸蔵合金粉末とは、粒径が75μｍ以下の
ものであり、TiNi系、VNi系、ZrNi系、TiCu系等の1000
℃程度の温度でも気化、融解、溶解、および凝集を起こ
さない組成の合金であり、特に、Ti2-xNix（0.6≦ｘ≦
1.2）で示される合金が望ましい。Here, the hydrogen storage alloy powder has a particle size of 75 μm or less, and may be a TiNi-based, VNi-based, ZrNi-based, TiCu-based
An alloy with a composition that does not vaporize, melt, dissolve, or agglomerate even at temperatures of about ℃, especially Ti 2-x Ni x (0.6 ≦ x ≦
The alloy shown in 1.2) is desirable.
本発明における炭化水素類とは、脂肪族炭化水素（特
に不飽和炭化水素）、芳香族炭化水素、脂環式炭化水素
およびそれらの誘導体のことであり、具体例としては、
例えば、ベンゼンナフタレン、アントラセン、ヘキサメ
チルベンゼン、２−ブチン、アセチレン、ビフェニル、
ジフェニルアセチレン、シクロヘキサン等が挙げられ、
特にベンゼン等の芳香族炭化水素類が好ましい。The hydrocarbons in the present invention are aliphatic hydrocarbons (especially unsaturated hydrocarbons), aromatic hydrocarbons, alicyclic hydrocarbons and derivatives thereof, and specific examples thereof include:
For example, benzene naphthalene, anthracene, hexamethylbenzene, 2-butyne, acetylene, biphenyl,
Diphenylacetylene, cyclohexane and the like,
Particularly, aromatic hydrocarbons such as benzene are preferred.
上記炭化水素類を低温熱分解する際の濃度、温度は、
出発原料となる有機材料により異なるが、数ミリモルパ
ーセントの濃度、1000℃程度以下の温度に制御され、炭
素体の堆積量は数μｍ以下に制御される。The concentration and temperature at which the hydrocarbons are pyrolyzed at low temperature are as follows:
Although it depends on the organic material used as the starting material, the concentration is controlled to several millimoles, the temperature is controlled to about 1000 ° C. or less, and the deposition amount of the carbon body is controlled to several μm or less.
また炭化水素類を気化する方法としては、アルゴンガ
スをキャリアガスとするバブラ法が通常であるが、水素
吸蔵合金および出発原料となる有機材料によっては水素
とアルゴンの混合ガスまたは水素ガスをキャリアガスと
するバブラ法、あるいは蒸発法、昇華法等によって行う
ことができる。As a method for vaporizing hydrocarbons, a bubbler method using argon gas as a carrier gas is usually used, but depending on the hydrogen storage alloy and the organic material used as a starting material, a mixed gas of hydrogen and argon or a hydrogen gas is used as a carrier gas. Or an evaporation method, a sublimation method, or the like.
（発明の効果） 本発明によれば、微粉化が起こり難く、また熱乃至電
気伝導性に優れ、しかも雰囲気からの被毒による特性劣
化を起こさないといった利点を有し、長期間にわたる使
用においても安定した特性を示す電池電極用水素吸蔵合
金材料を提供することができる。(Effects of the Invention) According to the present invention, there is an advantage that pulverization hardly occurs, heat and electric conductivity are excellent, and characteristics are not deteriorated by poisoning from an atmosphere. A hydrogen storage alloy material for a battery electrode exhibiting stable characteristics can be provided.
（実施例） 以下、本発明の実施例を示すが、本発明はこれに限定
されるものではない。(Example) Hereinafter, an example of the present invention will be described, but the present invention is not limited thereto.
本例では、水素吸蔵合金にTiNiを、またTiNi粉末の表
面上に堆積させる炭素体作製のための出発物質としてベ
ンゼンを用いた。In this example, TiNi was used as the hydrogen storage alloy, and benzene was used as a starting material for producing a carbon body to be deposited on the surface of the TiNi powder.
まず、TiとNiを化学量論比で1:1となるようにTi粉末
とNi粉末を秤量し、アルミナ製乳鉢を用いて均一に混合
した。この混合粉末を錠剤成形器を用いて直径15mm、厚
さ5mmのペレットに作製した。このペレットをアルゴン
アーク溶解炉内でアーク溶解し、均一なTiNi合金を作製
した後、粉砕し、最大粒径75μｍ、平均粒径40μｍの水
素吸蔵合金粉末を得た。First, Ti powder and Ni powder were weighed so that the stoichiometric ratio of Ti and Ni was 1: 1 and uniformly mixed using an alumina mortar. This mixed powder was formed into a pellet having a diameter of 15 mm and a thickness of 5 mm using a tableting machine. The pellets were arc-melted in an argon arc melting furnace to produce a uniform TiNi alloy and then pulverized to obtain a hydrogen storage alloy powder having a maximum particle size of 75 μm and an average particle size of 40 μm.
このようにして得られた水素吸蔵合金粉末を第１図に
示した炭素体堆積用装置内の試料ホルダー７に載せ、以
下の手順により水素吸蔵合金の表面上に炭素体を堆積さ
せた。The hydrogen storage alloy powder thus obtained was placed on the sample holder 7 in the carbon body deposition apparatus shown in FIG. 1, and a carbon body was deposited on the surface of the hydrogen storage alloy by the following procedure.
まず、一旦脱水処理を施しさらに真空移送による蒸留
精製操作を行ったベンゼンが収納された容器１内に、ア
ルゴン供給器２よりアルゴンガスを供給してベンゼンの
バブルを行い、このベンゼンをパイレックス製ガラス管
３を介して石英製反応管４へ給送した。その際、容器１
をベンゼンの蒸発による吸熱分だけ加熱することにより
温度を一定に保ち、またニードル弁5,6を適宜操作して
ベンゼン量を最適化した。First, argon gas is supplied from an argon supply unit 2 into a container 1 in which benzene that has been subjected to a dehydration treatment and further subjected to a distillation purification operation by vacuum transfer is bubbled with benzene, and the benzene is made of Pyrex glass. It was fed through a tube 3 to a quartz reaction tube 4. At that time, container 1
Was heated by the amount of heat absorbed by the evaporation of benzene to keep the temperature constant, and the amount of benzene was optimized by appropriately operating the needle valves 5 and 6.
一方、反応管４に設置された試料ホルダー７上には、
水素吸蔵合金粉末が載置されており、また反応管４の外
周囲には加熱炉８が周設されている。この加熱炉８によ
り試料ホルダー７および水素吸蔵合金を約800℃の温度
に維持し、パイレックス製ガラス管３から供給されるベ
ンゼンを熱分解し、水素吸蔵合金の粉末表面に炭素体を
堆積させた。なお、熱分解反応後の反応管４内に残留す
るガスは排気設備9,10により排気し除去した。On the other hand, on the sample holder 7 installed in the reaction tube 4,
A hydrogen storage alloy powder is placed, and a heating furnace 8 is provided around the outer periphery of the reaction tube 4. The heating furnace 8 kept the sample holder 7 and the hydrogen storage alloy at a temperature of about 800 ° C., thermally decomposed benzene supplied from the Pyrex glass tube 3, and deposited carbon bodies on the surface of the powder of the hydrogen storage alloy. . The gas remaining in the reaction tube 4 after the thermal decomposition reaction was exhausted and removed by exhaust equipments 9 and 10.
このようにして得られた電池電極用水素吸蔵合金材料
についてCoKα線を光源とするＸ線回折を行った。その
結果を第２図Ａに示す。また、アーク溶解炉により得ら
れたTiNiを粉砕して得られた粉末、すなわち炭素体を堆
積させる以前の水素吸蔵合金粉末についても上記と同様
のＸ線回折を行った。その結果を第２図Ｂに示す。The thus obtained hydrogen storage alloy material for a battery electrode was subjected to X-ray diffraction using CoKα radiation as a light source. The result is shown in FIG. 2A. The same X-ray diffraction as described above was also performed on powder obtained by pulverizing TiNi obtained by an arc melting furnace, that is, on a hydrogen storage alloy powder before depositing a carbon body. The result is shown in FIG. 2B.
これらの結果より、本発明による方法によって得られ
る電池電極用水素吸蔵合金材料は著しい組成変化を受け
てないことがわかる。From these results, it can be seen that the hydrogen storage alloy material for a battery electrode obtained by the method according to the present invention has not undergone a significant change in composition.
第３図は、水素吸蔵合金材料の粒径分布を示し、同図
Ａはアーク溶解炉により得られたTiNiを粉砕して得られ
た粉末の粒径分布を、同図Ｂは炭素体を堆積させた水素
吸蔵合金材料について100回の水素吸収・放出の繰り返
しを行った後の粒径分布を、また同図Ｃは炭素体を堆積
させない水素吸蔵合金材料について100回の水素吸収・
放出の繰り返しを行った後の粒径分布を示す。Fig. 3 shows the particle size distribution of the hydrogen storage alloy material, Fig. A shows the particle size distribution of the powder obtained by pulverizing TiNi obtained by an arc melting furnace, and Fig. B shows the deposition of carbon bodies. The particle size distribution of the hydrogen-absorbing alloy material subjected to 100 repetitions of hydrogen absorption and desorption is shown in FIG.
3 shows the particle size distribution after repeated release.
これらの結果から、炭素体を堆積させることにより水
素吸蔵合金材料は水素の吸収・放出を繰り返すことによ
る微粉化が起こり難くなることがわかる。From these results, it can be seen that the deposition of the carbon body makes it difficult for the hydrogen storage alloy material to be pulverized due to repeated absorption and release of hydrogen.
また、水分を５％含んだ水素ガスを用い、炭素体を堆
積させた水素吸蔵合金材料Ａおよび炭素体を堆積させな
い水素吸蔵合金材料Ｂにそれぞれ水素の吸収・放出の繰
り返しを行わせ、各材料A,Bの水素吸収・放出可能な量
について調べた。その結果を第４図に示す。Further, using hydrogen gas containing 5% of moisture, the hydrogen storage alloy material A on which the carbon body is deposited and the hydrogen storage alloy material B on which the carbon body is not deposited are repeatedly subjected to absorption and release of hydrogen, respectively. The amount of A and B that can absorb and release hydrogen was investigated. The result is shown in FIG.
これらの結果から、炭素体を堆積させることにより雰
囲気による表面汚染が起こり難いことがわかる。From these results, it can be understood that the surface contamination due to the atmosphere hardly occurs by depositing the carbon body.
以上の事柄より、本発明に係る製造方法により得られ
た電池電極用水素吸蔵合金材料は、微粉化が起こり難
く、雰囲気による特性劣化の起こり難い材料であり、長
時間の使用においても安定した特性を供給できるもので
あることがわかる。From the above, the hydrogen-absorbing alloy material for a battery electrode obtained by the production method according to the present invention is a material that hardly causes pulverization and does not easily deteriorate in characteristics due to the atmosphere, and has stable characteristics even when used for a long time. Can be supplied.
第１図は本発明に係る電池電極用水素蔵吸蔵合金材料の
製造に用いる炭素体堆積装置の一例を示す概略図、第２
図は水素吸蔵合金材料のCoKα線による粉末Ｘ線回折図
であり、同図Ａは本発明方法によって得られた電池電極
用水素吸蔵合金材料についてのＸ線回折図、同図Ｂは炭
素体が被覆されていない水素吸蔵合金材料についてのＸ
線回折図、第３図は水素吸蔵合金材料の水素吸収・放出
の繰り返し過程を実施する前後の粒径分布の比較図であ
り、同図Ａはアーク溶解炉により得られたTiNiを粉砕し
て得られた粉末の粒径分布を示す図、同図Ｂは炭素体を
堆積させた水素吸蔵合金材料について100回の水素吸収
・放出の繰り返しを行った後の粒径分布を示す図、同図
Ｃは炭素体を堆積させない水素吸蔵合金材料について10
0回の水素吸収・放出の繰り返しを行った後の粒径分布
を示す図、第４図は本発明に係る水素吸蔵合金材料と、
炭素体が被覆されていない水素吸蔵合金材料についての
水素吸収・放出可能な量の吸収・放出繰り返しによる変
化を示す特性図である。 １……容器 ２……アルゴン供給器 ３……パイレックス製ガラス管 ４……石英製反応管 5,6……ニードル弁 ７……試料ホルダー、８……加熱炉 9,10……排気設備FIG. 1 is a schematic view showing an example of a carbon body deposition apparatus used for producing a hydrogen storage alloy material for a battery electrode according to the present invention.
The figure is a powder X-ray diffraction diagram of the hydrogen storage alloy material by CoKα radiation, FIG. A shows an X-ray diffraction diagram of the hydrogen storage alloy material for a battery electrode obtained by the method of the present invention, and FIG. X for uncoated hydrogen storage alloy material
X-ray diffraction diagram, FIG. 3 is a comparison diagram of the particle size distribution before and after the repetition process of hydrogen absorption / release of the hydrogen storage alloy material, and FIG. A shows the pulverized TiNi obtained by the arc melting furnace. FIG. B shows the particle size distribution of the obtained powder, and FIG. B shows the particle size distribution of the hydrogen-absorbing alloy material on which the carbon body is deposited after repeating 100 times of absorption and release of hydrogen. C is 10% for hydrogen storage alloy materials that do not deposit carbon bodies.
FIG. 4 is a diagram showing a particle size distribution after performing hydrogen absorption / release repeatedly 0 times, FIG. 4 shows a hydrogen storage alloy material according to the present invention,
FIG. 9 is a characteristic diagram showing a change in the amount of hydrogen that can be absorbed and released due to repeated absorption and release of a hydrogen storage alloy material that is not coated with a carbon body. DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Argon supply device 3 ... Pyrex glass tube 4 ... Quartz reaction tube 5, 6 ... Needle valve 7 ... Sample holder, 8 ... Heating furnace 9, 10 ... Exhaust equipment
Claims (1)
低温熱分解による気相堆積法により炭素堆積物として形
成される炭素体を堆積させることを特徴とする電池電極
用水素吸蔵合金材料の製造方法。1. A hydrogen storage alloy material for a battery electrode, wherein a carbon body formed as a carbon deposit is deposited on a surface of a hydrogen storage alloy powder by a vapor phase deposition method at a low temperature of 1500 ° C. or lower by thermal decomposition. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62255480A JP2612006B2 (en) | 1987-10-08 | 1987-10-08 | Method for producing hydrogen storage alloy material for battery electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62255480A JP2612006B2 (en) | 1987-10-08 | 1987-10-08 | Method for producing hydrogen storage alloy material for battery electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0196301A JPH0196301A (en) | 1989-04-14 |
| JP2612006B2 true JP2612006B2 (en) | 1997-05-21 |
Family
ID=17279347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62255480A Expired - Fee Related JP2612006B2 (en) | 1987-10-08 | 1987-10-08 | Method for producing hydrogen storage alloy material for battery electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2612006B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2514274B2 (en) * | 1990-12-28 | 1996-07-10 | シャープ株式会社 | Method for manufacturing hydrogen storage alloy material |
| CN110482488B (en) * | 2019-09-11 | 2021-12-14 | 广东省稀有金属研究所 | Composite hydrogen storage material, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581032A (en) * | 1981-06-27 | 1983-01-06 | Nippon Steel Corp | Production of hydrogen absorbing metallic material |
-
1987
- 1987-10-08 JP JP62255480A patent/JP2612006B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0196301A (en) | 1989-04-14 |
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