Lub ntsiab lus ntawm hydrogen cia alloys
Sib txawv ntawm lub cev hydrogen cia txoj kev xws li lub tog raj kheej siab siab los yog qis kub liquefaction, hydrogen cia alloys tuaj yeem khaws cov hydrogen hauv cov hlau hydride los ntawm kev sib txuas nrog hydrogenation, thiab tuaj yeem tso tawm hydrogen nyob rau hauv qee yam mob. Siv hydrogen cia alloy los khaws cov hydrogen tsis tsuas yog muaj cov yam ntxwv ntawm cov hydrogen cia loj, kev siv hluav taws xob tsawg thiab siv tau yooj yim, tab sis kuj zam lub thawv loj loj thiab loj, uas ua rau kev cia thiab kev thauj mus los yooj yim dua thiab nyab xeeb.
Raws li cov khoom siv hydrogen cia, alloys muaj cov kev xav tau sib txawv raws li lawv cov kev siv sib txawv. Feem ntau hais lus, muaj ntau yam yuav tsum tau ua: ua ntej, lub peev xwm nqus hydrogen ib chav tsev loj thiab chav tsev ntim yuav tsum loj, uas txiav txim siab qhov muaj zog ntawm cov khoom siv; Qhov thib ob, qhov sib npaug siab rau kev tsim thiab decomposition ntawm hlau hydrides yuav tsum tsim nyog, uas yog, lawv tuaj yeem nqus tau thiab tso tawm ntau cov hydrogen nyob rau hauv qhov tsim nyog thiab ruaj khov hydrogen siab; Thib peb, qhov nqus hydrogen thiab desorption tus nqi nrawm thiab muaj qhov rov qab zoo; Plaub, nws muaj zog antioxidant, av noo, thiab impurity lom lom, thiab muaj lub neej voj voog siab. Qhov no zoo li kev ua pa lom, uas yuav tsum tau ua pa txaus, ua pa kom zoo thiab ua pa.
Txoj kev tshawb fawb ntawm hydrogen cia alloy pib hauv xyoo 1960. Ua ntej, Reilly thiab Wiswall ntawm Brooke-Haven National Laboratory hauv Tebchaws Meskas tau tshawb pom Mg hydrogen cia Ni alloy nrog mg / Ni piv ntawm 2: 1. Xyoo 1970, Phillips Laboratory hauv Netherlands tau tshawb pom LaNi5 alloy, uas muaj cov khoom siv hydrogen zoo ntawm chav tsev kub. Tom qab ntawd Reilly thiab Wiswall nrhiav tau FeTi intermetallic compounds. Txij thaum ntawd los, cov teb chaws thoob plaws ntiaj teb tsis tau tso tseg txoj kev tshawb fawb thiab kev tsim kho tshiab hydrogen cia alloys.
Daim duab 1 Schematic daim duab ntawm hydrogen absorption mechanism ntawm hydrogen cia alloys
Cov ntsiab lus hlau uas tuaj yeem cuam tshuam nrog hydrogen los ua hydrides feem ntau tuaj yeem muab faib ua ob pawg: ib qho yog A-sab hlau, xws li Ti, Zr, Ca, Mg, V, Nb, tsis tshua muaj ntiaj teb cov ntsiab lus, thiab lwm yam. Cov ntsiab lus hlau no yooj yim. kom hnov mob nrog hydrogen los tsim cov hydrides ruaj khov thiab tso tawm ntau cov cua sov, hu ua exothermic hlau; Lwm hom yog B-sab hlau, xws li Fe, Co, Ni, Cr, Cu, Al, thiab lwm yam. Cov hlau no muaj qhov tsis sib xws rau hydrogen thiab tsis yooj yim rau kev tsim hydrides. Thaum hydrogen dissolves nyob rau hauv lawv, nws yog ib qho endothermic cov tshuaj tiv thaiv, yog li cov hlau no hu ua endothermic hlau. Cov hydrogen cia alloys tam sim no nyob rau hauv kev tshawb fawb thiab kev loj hlob feem ntau yog tsim los ntawm A-chav kawm hlau thiab B-chav kawm hlau los npaj hydrogen cia alloys nrog reversible hydrogen nqus thiab desorption muaj peev xwm ntawm qhov tsim nyog kub. Cov hydrogen cia alloys tuaj yeem muab faib ua pawg hauv qab no: AB5 hom (tsis tshua muaj ntiaj teb series), AB ₂ hom (zirconium thiab titanium series), AB hom (hlau titanium series), A ₂ B hom (magnesium series) hydrogen cia alloys , lwm.
Tsev neeg loj ntawm hydrogen cia alloys
(1) AB5 yam tsawg lub ntiaj teb hydrogen cia alloy
Lub ntiaj teb tsis tshua muaj hydrogen cia alloy sawv cev los ntawm LaNi5 yog suav tias muaj daim ntawv thov kev ua tau zoo tshaj plaws ntawm tag nrho cov hydrogen cia alloys. Nws cov qauv siv lead ua tau pom nyob rau hauv daim duab 2. LaNi5 reacts nrog hydrogen ntawm ob peb atmospheric pressures ntawm chav tsev kub thiab tuaj yeem hydrogenated los tsim LaNi5H6. Lub peev xwm ntawm hydrogen yog li 1.4wt.%, qhov decomposition siab (hydrogen tso tawm qhov sib npaug siab) ntawm 25 degree yog hais txog 0.2MPa, hydrogen nqus thiab tso tawm tus nqi yog ceev, thiab nws yog heev haum rau siv nyob rau hauv chav kub ib puag ncig. Txawm li cas los xij, tom qab nqus dej hydrogen, chav tsev ntim ntawm tes nthuav dav (kwv yees li 23.5%), thiab thaum rov nqus hydrogen thiab tso tawm, cov hlau yuav raug pulverized hnyav heev. Tsis tshua muaj ntiaj teb AB5 hom LaNi5 thiab lwm yam derivative alloys tuaj yeem siv los ua cov khoom tsis zoo electrode rau cov roj teeb nickel-hlau hydride, thiab tam sim no tau ua lag luam hauv ntau lub teb chaws.
Nyob rau hauv xyoo tas los no, tsawg lub ntiaj teb hydrogen cia alloys tau tsim non-stoichiometric AB₃ thiab A2B7 hydrogen cia alloys. Lub peev xwm hydrogen cia ntawm cov hlau yog siab dua li ntawm AB5 alloy, thiab nws tuaj yeem nqus tau hydrogen ntawm chav tsev kub, xws li La0.7Mg0.3Ni2 Lub peev xwm rov qab hydrogen ntawm .8Co 0.3 tuaj yeem ncav cuag 1.8wt.%.
Daim duab 2 Crystal qauv ntawm LaNi5
(2) AB2 hom zirconium-based thiab titanium-based hydrogen cia alloys
AB₂ hom Laves theem hydrogen cia alloys muab faib ua ob pawg: titanium-based thiab zirconium-based. Zirconium-based AB₂-hom hydrogen cia alloys feem ntau suav nrog Zr-V series, Zr-Cr series, thiab Zr-Mn series. ZrMn₂ yog ib qho hlau uas muaj peev xwm nqus tau hydrogen loj (hydrogen cia muaj peev xwm 2.0wt.%, theoretical electrochemical peev 482mAh / g). Nyob rau xyoo 1980s, txhawm rau hloov kho cov khoom siv hluav taws xob, cov khoom siv electrode tau tsim los ntawm ZrMn alloy. Cov khoom siv no muaj qhov zoo ntawm qhov muaj peev xwm tawm tau zoo thiab kev ua haujlwm zoo, yog li nws muaj qhov zoo ntawm daim ntawv thov. Titanium-based AB₂-hom hydrogen cia alloys feem ntau suav nrog ob pawg: TiMn-based thiab TiCr-based. Thaum optimizing Ti-Mn muaj pes tsawg leeg, Panasonic Corporation ntawm Nyiv tau pom tias cov hlau alloy nrog Mn/Ti=1.5 muaj qhov loj tshaj plaws hydrogen cia peev nyob rau hauv chav tsev kub, uas muaj peev xwm ncav cuag TiMn1.5H2 .5 (hydrogen ntsiab lus yog hais txog. 1.8 wt%). Tsis tas li ntawd, kev hloov kho saum npoo xws li kub alkali impregnation thiab fluorination kev kho mob tuaj yeem txhim kho qhov ua kom sai thiab ceev hydrogen nqi thiab tso tawm kev ua haujlwm ntawm cov hlau.
Titanium / zirconium hydrogen cia alloys feem ntau yog siv nyob rau hauv hlau hydride hydrogen cia tso tsheb hlau luam ntawm hydrogen roj cell tsheb. Tam sim no, AB₂-hom alloys muaj teeb meem xws li teeb meem hauv kev pib ua haujlwm, kev ua haujlwm tsis zoo ntawm cov pa tawm, thiab cov khoom siv raw cov nqi siab rau cov alloys. Txawm li cas los xij, vim tias AB₂-hom alloys muaj qhov zoo ntawm hydrogen cia muaj peev xwm thiab lub neej voj voog ntev, lawv raug suav tias yog cov roj teeb nickel-hlau hydride. Cov tiam tom ntej ntawm cov khoom muaj peev xwm anode.
(3) AB hom hlau-titanium hydrogen cia alloy
AB-hom hydrogen cia alloys suav nrog TiFe-based alloys thiab TiNi-based alloys. TiFe alloy yog ib tug neeg sawv cev ntawm AB-hom hydrogen cia alloy thiab nrhiav tau los ntawm Reilly thiab Wiswall ntawm Brookhaven National Research Institute nyob rau hauv lub tebchaws United States nyob rau hauv 1974. Tom qab TiFe alloy yog qhib, nws muaj peev xwm reversibly nqus thiab tso tawm ib tug loj npaum li cas ntawm hydrogen ntawm chav kub. Qhov theoretical hydrogen cia muaj peev xwm yog 1.86wt.%, thiab qhov sib npaug hydrogen siab ntawm chav tsev kub yog 0.3MPa. Nws yog ze heev rau kev lag luam daim ntawv thov, yog pheej yig, thiab muaj ntau yam kev pab. Nws yog dav siv nyob rau hauv industrial ntau lawm. muaj tej yam zoo. Txawm li cas los xij, TiFe alloys kuj tseem muaj qhov tsis zoo, xws li nyuaj rau kev ua kom muaj zog, tsis zoo tiv thaiv kev lom los ntawm impurity gases, thiab kev ua haujlwm degradation tom qab rov qab nqus thiab tso tawm ntawm hydrogen. Txhawm rau kom kov yeej cov kev tsis txaus no thiab tsim cov alloys tsim nyog, tib neeg tau tsim cov khoom siv tshiab raws li Ti-Fe binary alloys los ntawm kev hloov Fe nrog lwm cov ntsiab lus.
(4) A₂B hom magnesium hydrogen cia alloy
Mg nyob qib yim hauv cov ntsiab lus hauv lub ntiaj teb crust (2.7%) thiab muaj ntau nyob rau hauv reserves. Vim nws cov active tshuaj zog, nws muaj nyob rau hauv cov xwm nyob rau hauv daim ntawv ntawm cov tebchaw los yog minerals. Cov qauv atomic qauv ntawm magnesium hydrogen cia alloy yog pom nyob rau hauv daim duab 3. Ntawm 300 ~ 400 degree thiab siab hydrogen siab, magnesium tuaj yeem ncaj qha cuam tshuam nrog hydrogen los ua MgH₂ thiab tso tawm ntau cov cua sov. Qhov sib npaug ntawm cov tshuaj tiv thaiv yog raws li nram no:
Mg + H₂=MgH₂
Nws cov ntsiab lus theoretical hydrogen tuaj yeem ncav cuag 7.6wt.% H. Ntawm cov hydrides thim rov qab siv rau hydrogen cia, magnesium hydride muaj lub zog siab tshaj plaws (9MJ / kg Mg) thiab yog cov khoom siv muaj peev xwm hydrogen. Txawm li cas los xij, Mg muaj qhov kub siab thermal stability thiab tsis zoo hydrogen tso tawm kev ua haujlwm. Yog li ntawd, magnesium ntshiab tsuas tuaj yeem hydrogenated nyob rau hauv qhov kub thiab txias thiab siab hydrogen siab, thiab dehydrogenated nyob rau hauv kub thiab tsis tshua muaj siab, uas txwv nws cov tswv yim daim ntawv thov.
Daim duab 3 Atomic qauv qauv ntawm magnesium raws li hydrogen cia alloys
Txhawm rau txo qis hydrogen tso tawm qhov kub thiab txias ntawm Mg thiab txhim kho cov thermodynamic zog, Mg yog alloyed nrog Ni, Cr, Co, Fe, Ti, RE (tsis tshua muaj lub ntiaj teb) thiab lwm yam hlau los npaj binary los yog ntau dua alloys thiab hydrides, thiab complex. hydrides Qhov decomposition kub ntawm MgH₂ feem ntau qis dua li ntawm MgH₂. Magnesium-based hydrogen cia alloys tsim nrog lub tswv yim no feem ntau suav nrog Mg-Co, Mg-Cu, Mg-Ni, Mg-Fe, Mg-La, Mg-Al thiab lwm yam tshuab, nrog rau ternary thiab multi-component alloys tsim los ntawm lub hauv paus no. hlau alloy. Kev txhim kho hydrogen nqus thiab desorption tus nqi ntawm cov ntshiab Mg-H hydrogen cia system tuaj yeem ua tiav los ntawm kev hloov kho Mg matrix, ua rau nws qhov chaw ntog kom muaj kev sib raug zoo ntawm matrix nto rau hydrogen, thiab nce qhov diffusion. Ntawm lawv, cov txheej txheem xws li kev sib tsoo pob thiab ntxiv cov catalysts tuaj yeem txhim kho hydrogen nqus thiab tso tawm kev ua tau zoo ntawm Mg matrix thiab txhim kho qhov ua tau zoo ntawm kev siv.
HNRE tau tsim ntau yam tshiab hydrogen cia cov ntaub ntawv thiab tsim ib tug kev tshawb fawb thiab kev loj hlob system nrog ywj siab cov cuab yeej cuab tam, ua kev tshawb fawb ntawm daim ntawv thov ntawm hydrogen cia cov ntaub ntawv, feem ntau yog tsim lub ntiaj teb tsis tshua muaj hydrogen cia, high-purity hydrogen purification tsawg ntiaj teb cov ntaub ntawv, thiab daws ntau yam teeb meem tseem ceeb hauv kev siv engineering. Qee yam khoom siv hydrogen tau txais txiaj ntsig thib ob ntawm National Technical Invention hauv xyoo 1998. HNRE muab tag nrho cov khoom siv hydrogen stroge, tshwj xeeb tshaj yog LaNi, MgNi alloys rau cov neeg siv khoom hauv tsev thiab txawv teb chaws.