貯氫合金新進展中英文對照

Newdevelopmentofhydrogenstorage:Thisprintroducesthebasicprincipleofmetalhydridereaction,thebasictypesofhydrogenstoragealloys,productionprocess,acomprehensivereviewbeenmoremature,butthehydrogenstoragedensityisnothigh.HighcapacityvanadiumsolidsolutionalloyandMgbasedalloysarenewtrendsinthedevelopmentofhydrogenstoragealloys.Keywords:hydrogenstoragealloys;productiontechnology;reviewofapplication;newdevelopmentAsglobalwarmingandenvironmentalpollutionis ingincreasinglyseriousinrecentyears,thecleanenergyespeciallytheresearchanddevelopmentofhydrogen,thehydrogenstoragealloyasanewfunctionalmaterialsandenergymaterialscausedthegreatattentionofpeople.Thehydrogenstoragealloys,suchasrareearthsystem,titanium,magnesium,zirconium,etc..AB5typerareearthhydrogenstoragealloyswerestudiedcomparatively,andtheapplicationiswide.Thedevelopmentandapplicationofhydrogenstoragealloysarereviewedinthisp BasicprinciplesofmetalhydrideTheamountofhydrogenabsorbedinhydrogenstoragealloyis1000timesmorethanthevolumeofthealloy,andhydrogenstoragealloyhasthecharacteristicsofverysafe.TheworkingprincipleofhydrogenabsorptionanddesorptioncanbeexpressedIntheformula,M-metal,MHx-metalhydride,H-reactionThehydrogenabsorptionanddesorptionprocessofhydrogenstoragealloysisandtheabsorptionofheatintheprocessofdehydrogenation.Thus,hydrogenstoragealloysabsorbhydrogenatalowertemperatureorincreasingpressure.Incontrast,hydrogenisreleasedatanelevatedtemperatureorpressure.ThehydrogenabsorptioncharacteristicsofhydrogenstoragealloyswithdifferentconditionsandthecharacteristicsofthethermaleffectsarewidelyusedinthefieldofscienceandLaNiFeTi類有稀土系、LavesTiMgA及與不吸氫類(用BA5型、2型、BABTypesofhydrogenstorageAftermanyyearsofresearch,thehydrogenstoragealloyshavebeendeveloped.Accordingtothenumberofgroupscanbedividedintotwoyuan,threeyuanandmultidepartment.ThetypicalrepresentativeofthetwoelementsystemhasFeTi,LaNi5,etc..Accordingtotheclassificationofthemetalmatrixofthealloy,therareearthsystem,Lavesphasesystem,Tisystem,Mgsystem,etc..Ifthemetalisdividedintoahydrogenabsorbingclass(A)andanonhydrogenabsorption(B),thealloycanbedividedintoAB5type,AB2type,ABtypeandA2Btype.A5LaNi5CaCu5（2.1(LaNi51.4wt%anNiRareearthhydrogenstorageAlsoknownastheAB5typehydrogenstoragealloy,LaNi5wasthetypicalrepresentative,andhasCaCu5sixsquarecrystalstructure(seeFigure2.1).Thecurrentresearchismoremature,commercialproduction.Ithasthecharacteristicsofhighhydrogenstoragecapacity(1.4wt%),easyactivation,etc.,butthecyclicstabilityispoor,andnowthemixedrareearthpartialreplacementofLa,Fe,Mn,CoandotherelementstoreplaceNi,inthehydrogenstoragecapacityofaslightdecreaseinthepremiseofimprovingthecyclestability. 圖 圖A2MgZn2MgCu2MgNi2A5LavesA5LavesphasehydrogenstorageAlsoknownasAB2typehydrogenstoragealloy,atpresentknownMgZn2type,MgCu2typeandMgNi2typethreekinds.ComparedwiththeAB5typehydrogenstoragealloys,theLavestypeAB2phasehydrogenstoragealloyshavethefollowingadvantages:highcapacity,strongcorrosion.Inalkalisolution,thesurfaceofthealloycanformalayerofdenseoxidefilmtoinhibittheoxidationofthealloyelectrode.Thedisadvantageofthistypeofalloyisthatitisdifficulttoactivate,andtheoxidefilmformedonthesurfaceofthealloycausesthedecreaseofitsactivationproperty.Theuseoftheelementismuorepreciousmetal,whichismuchhigherthanthatofAB5typehydrogenstoragealloy.BCsClTiFe但其最大的缺點是活化，抗性能差。預處理、合金化、機械化等均能有效地改善T-eTisystemhydrogenstorageAlsoknownasABtypehydrogenstoragealloywithCsCltypestructure.Atpresent,thedevelopmentandresearchofTibasedhydrogenstoragealloyhasatitanium,titanium,titanium,titanium,titanium,etc..TiFesystemisverypopularinthehydrogenstoragealloys,whichisofgreatstoragecapacity,cheapandabundantresources,butitsbiggestdrawbackisthatitisdifficulttobeactivated,andhaspoorperformanceofantipoisoning.TheactivationpropertiesofTi-Fecanbeimprovedbythepretreatment,alloyingandmechanicalproperties,sothatthealloycanabsorbhydrogenwithouttheneedofdemandingactivation.又稱A2B型貯氫合金，具有Mg2Ni六方晶結構。Mg重量輕，資源豐富，因此鎂系合金最MgsystemhydrogenstorageA2Btypehydrogenstoragealloysarealsoknownastypehydrogenstoragealloys,whichhavethestructureofMg2Ni.Mgislightinweight,richinresources,sothebiggestadvantageofMgbasedalloysisthelowcostandthehydrogenstoragecapacityisverylarge,butatpresent,theproductperformanceispoor,thereactionrateisslow,andthepositiontemperatureofthehydrideishigh,whichneedsfurtherresearchandimprovement.釩可與氫生成VH2、VH兩種氫化物。釩基固溶體型貯氫合金的特點是可逆貯氫量大、可研究開發(fā)的是鎳氫電池用貯氫合金V3TiNi0.56Mx,其中添加元素M可提高合金充放電的循環(huán)穩(wěn)VanadiumbasedsolidsolutiontypehydrogenstorageVanadiumcanproduceVH2andVHtwokindsofhydride.Vanadiumbasedsolidsolutiontypehydrogenstoragealloyischaracterizedbyreversiblehydrogenstoragecapacity,andcanbeachievedatroomtemperature,thehydrogenabsorptionanddesorptionrateishigh,butthealloysurfaceiseasytoproduceoxidefilm,increasingthedifficultyofactivation.Atpresent,themainresearchanddevelopmentofhydrogenstoragealloyV3TiNi0.56Mx,whichaddedelementMcanimprovethecyclestabilityofthealloychargeanddischarge,butthehydrogenstoragecapacityisreduced.貯氫合金的工各類型的合金有不同的方法，表3-1為貯氫材料制造方法及特征TechnologyforproducinghydrogenstorageDifferenttypesofalloyshavedifferentproductionmethods,table3-1isthemethodandcharacteristicsofhydrogenstoragematerials.不需，成本Table3-ManufacturingAlloyArcmelting（電弧熔煉法NearequilibriumphaseandsegregationMacrosegregationoccurswhentheslowcoolingNanocrystallinestructureandnonequilibriumWhenthethermaldiffusionisnotenough,thecompositionisnotSuitableforexperimentandafewproductionHighfrequencyinductionheatingmethodLowcost,suitableformassproduction（高頻感應加熱法MeltquenchingEasy（熔體急冷法GasatomizationSphericalpowder,noto（氣體霧化法MechanicalalloyingPowderrawmaterial,lowtemperaturetreatment（ReductiondiffusionWithoutcrushing,low0.2%（質量）Mg[2]。InductionmeltingAtpresent,thehighfrequencyinductionmeltingmethodisthemostcommonlyusedinindustry.Ithastheadvantagesofmassproductionandlowcost.Thedisadvantageisthatthepowerconsumptionislarge,thealloyisdifficulttocontrol.Productionofalloy,usuallyinaninertatmosphere,themethodduetoelectromagneticinductionstirringsolutionalongthemagneticlinesofforcecontinuetorolltomeltfullymixedanduniformtexturemelting,easytogethomogeneousalloy.However,duetothereactionofmoltenmetalandcruciblematerial,asmallamountofcruciblematerialismeltedintothealloy.Mgmeltintotherareearthalloyswith0.2%(mass)ofthealloywhenmeltingintotherareearthalloys[2].31的水冷錠模中使熔體冷卻而且為使冷卻速度更大采用了面冷卻的薄層圓盤式水3Ar（急冷在很大的冷卻速度下使熔體的方法例如將熔融合金噴射在旋轉冷卻的軋輥上卻速度為（02106K·1[2]。Differentcastingtechnologycanbetakenafteralloymelting,differentmethodshavedifferentcharacteristics,andcanbechosenaccordingtotheirspecificcircumstances.Atpresent,large-scaleindustrialproductionintheuseofsingleordoublecoolingoftheingotmoldcasting.Table3-1isacharacteristicofthehydrogenabsorptionalloysinvariouscastingdirections.Ingotmouldcastingmethodisthemeltingofalloyinjectionshofwater-cooledingotmould,themeltsolidificationandmakethecoolingspeedisgreater,thecoolingsurfaceofthindisctypewater-cooledmould.Gasatomizationprocessisanewtypeofcoalproductiontechnology,whichisdividedinto3steps,suchassmelting,gasspray,solidificationandsoon.Thehigh-frequencyinductionmeltingandmeltintotundish,withthemeltfromthepackageinatrickleoutatthesametime,atitsoutlet,high-pressureinertgas(Ar)ejectedfromatomeltintosmalldroplets,dropletinspraytowersidesfallingedgeiscakyintosphericalpowdercollectedatthebottomofthetower.Themethodcanpreventthesegregationofthecomponents,themicrostructureofthealloyandreducethepollution.Meltquenching(rapidcooling)methodisamethodofmakingthemeltcuringunderthegreatcoolingrate.Forexample,themoltenalloyissprayedontheroller,andthecoolingrateis（102-106）K·s-1,whichismadeofathinstripbyrapidcooling[2].3-1-大大小小Table3-1characteristicsofhydrogenabsorptionalloysmadebyvariouscastingCastingMeltCoolingrate（K·s-AlloySheetbyEqual-Crystallineparticlesize/(micron)Latticedeformation等［3］利用懸浮熔煉高鈮TiAl合金澆注到直徑50mm高120mm的高純石墨AlNi當?shù)睦鋮s速度和第三種合金元素，gEricA.Lass等［4］利用快速凝固技術納米晶Mg-Ni-(Y,La)-Pd貯氫合金，發(fā)現(xiàn)合金貯氫量（質量分數(shù)）為4.5％，已經(jīng)大大超過Mg２Ni相的理論容量（質量分數(shù)3.6％）。其Mg２NiZhangZhiyong［3］,preparedhighniobiumTiAlalloybysuspensionsmelting,pouredintothediameter50mm,highpuritygraphitemoldof120mm,exceptforAl,otherelementsdistributedevenly,thereisnorawmaterialandlocalenrientoftheformationandanization.ThesuspensionmeltingoftheliquidphaseoftheintenseagitationtoacceleratethespeedofNiatomstotheliquidphasediffusion,sothattheliquidphasecompositionismoreuniform,tobeappropriatecoolingrateandthirdkindsofalloyelements,Mgwillgetagoodinhibition.A.LassEric［4］usedrapidsolidificationtechniquetoMg-Ni-(Y,La)-Pdhydrogenstoragealloys.Thehydrogenstoragecapacity(massfraction)ofthealloyswas4.5%,whichwassignificantlymorethanthetheoreticalcapacityofMg２Ni(massfraction3.6%).Thereasonistheformationofotherhighhydrogenstoragecapacity,andthereasonsforrestrictingtheeffectivehydrogenstoragecapacityofMg２sstillnotexplained.機械合金化（MA）或機械磨碎法（MG）是20世紀60年代末由J.C.Benjamin發(fā)展起來性逐步，直到最后形成均勻的亞穩(wěn)結構。Mechanicalalloying(MG,MA)Mechanicalalloying(MA)ormechanicalgrindingmethod(mg)isthe20thcentury60'sbyofasystemJ.C.Benjamindevelopedpreparingalloypowdertechnology.extrusiondeformation,thefractureandwelding,extrusiontoformintermediatecomplex.Anewatomicsurfaceisgeneratedcontinuously,andthelayeredstructureisrefined,whichshortensthedistancebetweenthesolidparticles.Becauseoftheinteratomicdiffusion,thecharacteristicsoftheoriginalparticlesgraduallydisappear,untiltheformationofahomogeneousmetastablestructure.24用機械合金化貯氫合金在Mg系貯氫合金材料的應用較多。Kronberger[4]利用噴射條帶法的納米合金晶的AB5型化合物,與同成分的粗晶相比，電極放電性能更優(yōu)，活化速度更快。Kadir等[5]對稀土鎂系AB型合金進行了研究,結果表明機械合金化所的LaMgNi400mAhg-1。242ThemechanicalalloyingmethodisoftenappliedintheproductionoftheMgsystemofhydrogenstoragealloys.TheAB5typecompoundofnanoalloypreparedbythespraystripmethodwasusedtopreparetheKronberger[4]compoundwiththesamecomposition,theelectrodedischargeperformanceismoreexcellent,andtheactivationrateisfaster.InKadir’s[5]studyofAB,theresultsshowthatthedischargecapacityofLaMgNi4alloypreparedbymechanicalalloyingisashigh2400mAhg-度和保溫時間等因素。其主要應用主要在于MmNi5和TiNi系合金。ReductiondiffusionReductiondiffusionmethodisamethodforthedirectproductionofintermetalliccompoundsinthesameoperationprocessbytheprocessofreductionoftheelementsandthereactiondiffusionprocess.Generally,theproductofthereductiondiffusionmethoddependsonthematerialcomposition,theamountofreducingagent,processtemperatureandholdingtime.ThemainapplicationareintheproductionofMmNi5andTiNialloys.共沉淀還原法是在還原擴散法的基礎上發(fā)展起來的，是一種化學的方法。采用各組后，再用金屬鈣或CaH2還原而制得貯氫合金的法。共沉淀還原法貯氫合金有一CoprecipitationreductionCoprecipitationreductionmethodisdevelopedonthebasisofthereductiondiffusionmethod,whichisachemicalsynthesismethod.Thecomponentsofsolution,addingprecipitant(suchasNaCO3)bycoprecipitation,thatis,ofremovalofalloycompounds,burningintotheoxideandthenthemetalcalciumorCaH2reductionandamethodofhydrogenstoragealloy.Thereareaseriesofadvantagessuchastheuseofindustrialgrademetalsaltasrawmaterial,thesynthesismethodissimple,thecompositionisuniform,thealloyhasalargesurfacearea,andthealloyiseasytobeactivated.（ 下以600℃進行熱擴散使合金均勻化，得到MgNi或MgCu[1]。這種方法的合金表面上布（ Displacementdiffusion Becausemagnesiumisakindofactivemetal,itcannotbeusedtosynthesizemagnesiumalloys.Scientificandtechnicalnelinourcountrydesignedthedisplacementdiffusionmethodbythechemicalactivityofthemetalmagnesium.ThatistodissolvedanhydroussaltNiClorCuCl2inananicsolvent,(suchasdimethylformamide),withanexcessofmagnesiumreplacement,copperornickelsmoothlydepositioninmagnesium,removecleaninganddryingintothehightemperaturefurnaceunderaprotectiveatmosphereto600℃heatdiffusiontohomogeneousalloy,MgNiorMgCu[1.Inthismethod,thesurfaceofthealloyiscoveredwithcracks,andtheactivityisveryhigh,anditiseasytobeactivated.Reactioniscarriedoutasfollows: NiCl2(anicsolvent)+3Mg→2MgNi+MgCl2用該法還可一系列多元鎂合金如Mg2Ni1-xCu,Mg2Ni1-xPtx等Aseriesofmagnesiumalloyscanbesynthesizedbythis燃燒燃燒法（簡稱CS法）是將Ｍg粉和Ｎi粉混合均勻，在850k（低于Ｍg的,燃燒后直接制得Mg2Ni合金。用燃燒法制造貯氫合金，有利于提高合金吸氫能力，具有不需bustionsynthesisCombustionsynthesismethod(CSmethod)isamixtureofMgpowderandNipowderevenly,inthe850k(lowerthanthemeltingpointofMg,afterburningdirectlyMg2Nialloy.Usingthecombustionsynthesismethodtoproducehydrogenstoragealloy,itisbeneficialtoimprovethehydrogenabsorptioncapacity,andithasnoneedofactivationtreatment,lessenergyconsumptionandsoon.２近年來東學利用燃燒法成功地了Mg1%Ni貯氫合金，該合金不必進行活化處理，其吸氫量高達7.2[2]Zhu［5］利氫化燃燒法MgNi貯氫金，隨5hMg(OH)２531m·h／g２２Inrecentyears,Mg-1%Nihydrogenstoragealloywassynthesizedbycombustionsynthesismethod,whichisnotnecessaryforactivationtreatment,andthehydrogenabsorptioncapacityofthealloyis7.2%[2].ProductionofMgNihydrogenstoragealloywaspreparedbyhydrogencombustionsynthesismethodbyZhu[5],andthenby5hmechanicalmillingtoaddavarietyofcarbonmaterials,includinggraphite,multiwallcarbonnanotubes,carbongasgel,carbonnanofibers.TheMg(OH)２phaseinthemodifiedmaterialwasaddedtothealloy,andtheelectrochemicalperformanceindexeswereincreased,andtheumdischargecapacityanddynamicperformanceof531mA·h／gwasdemonstratedbygraphite.２51. 0. 西安交通大學的唐睿等[6]的研究表明，LaCaMgNiPuNiLaNiLaNi5LaNi2.28第二相構成1.6MPa氫壓和300K下,合金的貯氫量達到1.68%（質量分數(shù)),LaNi20%，395mA·h·g151. 0. 3.7Addotherelements(Ce,Mn,Ni,Ca,51. 0. ResearchofTangRui[6],Xi'anJiaoTongUniversity,showsthattheLaCaMgNiconsistsofmainphasewithPuNi3structureandthesecondphaseofLaNi5,LaNi2.28.Onthepressureof1.6MPaand300k,thehydrogenstoragecapacityofthealloywas1.68%(massfraction),20%morethanpureLaNi5.Andthedischargecapacityofthealloywas395mA·h·g-1,23%morethanAB.After10051. 0. 0.7- 0. 2. 0.HonggePan[6]CeLaCeMginCo0.7- 0. 2. 0.HonggEPan[6]CedidsystemresearchesonthestructureandelectrochemicalpropertiesofLa0.7-xCexMg0.3Ni2.875Mn0.1Co0.525(x=0～0.5)whenCecontentwasaddedinto.FromtheP-C-Tdiagram,itisindicatedthatthepressureincreasesrapidlywiththeincreaseofCecontentinthealloy,andtheplateauregionesnarrowsteep.Atthesametime,withtheincreaseofCecontent,thedischargecapacitydecreasesandthecyclelifecanbeimproved.HydrogenstorageHydrogenstoragealloysarewidelyusedinvarioustypesofbatteriesandenergyconversiontechnology.Intheapplicationofbatteriescanbedividedintosmallcivilianbatteries,electricvehiclebatteriesandfuelcellsthreecategories.Hydrogenstoragetechnologyandheatstoragetechnologyaremainlyusedintheenergyconversiontechnologyofhydrogenstoragealloys.貯氫合金作為鎳-氫化物電池的負極材料,既是電池的關鍵材料,也是目前貯氫合金應用最成領域。鎳氫電池在通訊、筆記本電腦、機、數(shù)碼相機、電動自行車、NiHNi(OH)M（A5）KHSmallbatteryandelectricvehicleHydrogenstoragealloysasanodematerialsfornickelhydridebatteriesarethekeymaterialsfortheproductionofbatteries,andthemostmaturefieldofhydrogenstoragealloys.Nickelmetalhydridebatteriesinthecommunicationsphone,notebookcomputers,cameras,digitalcameras,electricbicycles,electricmotorcyclesandelectricvehicles(singleelectricvehiclesandhybridelectricvehicles),etc..Ni-MHbattery(Ni/Nibattery)positiveactivematerialisNi(OH)2,thenegativeelectrodeisthehydrogenstoragealloyM(mainlyAB5typerareearthsystem),theelectrolyteisKOHwatersolution.Inchargeanddischarge,thepositiveandnegativereactionsarerespectively:2 Negativ:M+xHO+xe-≒MH2 BatterytotalNi-MHbatteryishigherthantheenergy,nopollutiontotheenvironment,nomemoryeffect,longcyclelifecanreplacethetoxic,wastebatteriesaredifficulttodisposeofnickelcadmiumbatteries.Inrecentyears,theyieldandqualityofhydrogenstoragealloysandnickelmetalhydridebatterieshavebeenimproved,butintheperformanceandproductconsistencyispoor,isnotconducivetothecombination,intheproductionprocessandproductionscaleisalsonot4.2電電池是一種將存在于與氧化劑中的化學能直接轉化為電能的發(fā)電裝置氫氣是料電池（FC）推廣用貯氫合金，在常溫常壓下可安全貯氫氫的高純度［8］FuelFuelcellisapowergenerationdevicewhichcanbedirectlyconvertedintoelectricalenergyinthepresenceoffuelandoxidant.Hydrogenisthecommongasinthefuelcell,soitcanimprovethepowerofthewholesystem.Thedevelopmentoffuelcell(FC),whichisdevelopedbyWasedaUniversity［8］,isusedtopromotehydrogenstoragealloys,whichcanbesafelystoredatroomtemperatureandundernormalpressure現(xiàn)在廣泛應用于電動汽車的電池是一種稱為質子交換膜的電池(PEMFC)，以氫為，以空氣為氧化劑，能量的轉換效率高，是普通內(nèi)燃機熱效率的2～3倍。同時它還具有無污染、長、啟動迅速、和輸出功率可隨時調整等特性。我國俞濤[9]PEMFCNowwidelyusedinelectricvehicles,fuelcellisakindoffuelcell(PEMFC),astheprotonexchangemembranefuelcell,hydrogenasfuel,airasoxidant,energyconversionefficiencyishigh,about2～3timesthethermalefficiencythanordinaryinternalcombustionengine.Atthesametime,ithasnopollution,longlife,startupquickly,andtheoutputpowercanbeadjustedatanytimeandsoon.TheChineseAcademyofScientist,YuTao[9],etal.,havebeenfullystudiedPEMFC,sayingthattherareearthnickelandtitaniumalloysaresuitableforthissystem.。氫的與輸送是氫能利用中的重要環(huán)節(jié)，其在與輸送中的安全、高效是人們在實Ti、Mg用貯氫合金選擇性吸氫的能力(形成氫化物MH),可成功地進行氫的回收和凈化已把貯氫合金用于宇航器吸收火箭逸出的氫氣中國已把貯氫合金用于氨洗氣中回收氫氣中、用貯氫合金進行氫的和輸送具有很多優(yōu)點:(1)貯氫密度大,容器體積小,可長期;(2)。HydrogenstorageHydrogenstorageandtransportisanimportantpartoftheuseofhydrogenenergy,soitssafetyinstorageandtransportationinthepracticalapplicationispreferred.Inordertoreducetheweightofcontainer,containermaterialsgenerallychooseTi,Mgsystemofhydrogenstoragealloys.Thehydrogenrecoveryandpurificationofhydrogencanbesuccessfullycarriedoutbyusingthehydrogenstoragealloy(MH).Hydrogenhasbeenusedtorecoverhydrogenfromthehydrogenstoragealloysusedinthesynthesisofammoniaandhydrogen,andhydrogenissuccessfullyusedtomaintainthepurityofhydrogeninthehydrogenof99.999%【8】Hydrogenstorageandtransportofhydrogenstoragealloyshasmanyadvantages:(1)thehydrogenstoragedensityislarge,thecontainervolumeissmall,andcanbestoredforalongtime.(2)itissafeandreliable,noexplosiondanger;(3)highpurityhydrogencanbeobtained.做金屬氫化物熱泵[10]。金屬氫化物熱泵是無需燃燒就可以致熱的裝置，也是不使用污HeatstoragetechnologyandheattransferAdevicecalledametalhydrideheatpumpcapableofabsorbingorreleasingtheheatofthereactionbetweentwodifferenthydrogenstoragealloysbymeansofhydrogenabsorptionorrelease.Metalhydrideheatpumpisadevicethatcancausetheheatwithouttheburningoffuelandcanbeusedasarefrigerantwithoutpollutingtheenvironment.Andheatstoragetechnologyistheuseofmetalhydrideheatpump,theexcessheatstorage,untiltheneedtousethemethod,istoimproveenergyuseefficiencyandprotecttheenvironmentisanimportanttechnology.Thistechniquehasthegreatadvantageofthepotentialapplicationinsolarenergy,industrialwasteheat,wasteheatutilizationandpowerloadetc..[10]， 德國GawronK和SchroderJ【11】在對-65～0℃的溫度范圍內(nèi)相變性能的研究后在低溫技術其應用已經(jīng)很普遍。Turillon[6]LaNiLaNiAl輸入60℃25℃10min， GawronKandJSchroder【11studiedofthephasetransitionpropertiesof65～0℃.Theheatpumpisakindofenergyliftingdevice.Theheatpumpisakindofenergyliftingdevice.Theheatpumpisakindofenergyliftingdevice,whichisusedtoheatuptheenvironment,andthenpassittotheKF?4H20.Conventionalheatincludinggroundsourceheatpump,watersourceheatpump,airsourceheatpumpandotherforms,whichiswidelyusedasairconditioningtechnology.Turillon[6]developedtheheatpumpusinghydrogenstoragealloyswithLaNi5andLaNi4.7Al..Enter60℃or25℃water,10minlater,youcanobtainedvapourat95℃or100℃.Hydrogenstoragealloyheatpumprefrigerationorairconditioninghashighefficiency,lownoise,noFreonpollution.電機內(nèi)氫純度。空氣產(chǎn)品與化學產(chǎn)品公司和MPD公司聯(lián)合開發(fā)的用LaNi5合金做成的回收裝置,回收氨尾氣,氫回收率達75%-95%,產(chǎn)品氫純度達98.9%[6].Applicationofhydrogenstoragealloystootheraspects5.1Hydrogenseparation,recoveryandpurificationThebasicprincipleofhydrogenstoragealloyseparationincludingoneistheformationofmetalhydride,hydrogenafterheatingthereversiblereaction;twohydrogenstoragealloysforhydrogenatomhasaspecialaffinityforothergasimpuritiesareexcluded.Forthepurificationofhydrogen,thehydrogenrecoveryfromthehydrogengasintheammoniaplantisusedtoimprovethehydrogenpurityofterator.UnitedStatesAirProductsandchemicalproductcompanyandMPDcompanyjointlydevelopedwithLaNi5alloymadeofrecyclingdevice,therecoveryofsyntheticammoniatailgas,hydrogenrecoveryrateof75%-95%,producthydrogenpurityof98.9%[6].貯氫合金如LaNi5，Mg2Ni，TiFe等能迅速吸收大量的氫，而且反應可逆。反應時由于氫式中，M；MHx為金屬氫化物CatalyticreactionofhydrogenstorageHydrogenstoragealloyssuchasLaNi5，Mg2Ni，TiFe,etc.canrapidlyabsorblargeamountsofhydrogen,andthereactionisreversible.Sincehydrogenisabsorbedinthereaction,hydrogenispresentonthesurfaceofasingleatom.Thisshowsthatthesurfaceofthesurfaceisverylarge.Ifitisflexibletousehydrogenabsorptioncapacity,hydrogenanddehydrogenationcanbeusedasanunsaturatedcompoundofhydrogenabsorption,orinturn,asasaturatedcompoundofdehydrogenation:Unsaturatedcompounds+MHx≒saturatedcompoundsIntheformula,Misahydrogenabsorptionalloy;MHxisametalCoon[12]CO/H=1/3250℃通LaNi5粉末時，很快進行了如下反應：CO+3H2—ApplicationinthereactionofCoon[12]etal usedtherareearthtransitionmetalhydrogenstoragealloysformethanereaction.WhenCO/H=1/3wasfoundandpassedthroughthepowerofLaNi5at250℃,andthereactionwascarriedoutasfollow:工業(yè)與居民用電都會有期和低峰期為了解決低峰期電力過剩的問題,可利用貯氫材料電能即利用夜間多余的電能供電解水廠生產(chǎn)氫氣然后把氫氣在貯氫合金，然后把氫氣在貯氫合金組成的大型裝置內(nèi)白天用電期使的氫氣出來。或供電池直接發(fā)電，或將氫氣作為生產(chǎn)水蒸氣，驅動備用發(fā)電機組發(fā)電。HydrogenstorageIndustrialandresidentialelectricitywillhaveakandlowpeakperiod.Inordertosolvetheproblemofstorageofelectricityinlowpeakperiod,thestorageofhydrogenstoragematerialscanbeusedtoproducehydrogen,andhydrogenisstoredinhydrogenstoragealloy.Orforthefuelcelltogenerateelectricitydirectly,ortoproducehydrogenasafueltoproducewatervapor,andtodrivethestandbygeneratorset.VacuumheatinsulationtubeforhydrogenstorageWiththeuseofhydrogenstoragealloy,vacuuminsulationtubeistotransporttubewallinsulationlayerintoacertainnumberofhydrogenstoragealloy,hydrogenstoragealloyceilinghydrogenreactiontomaintainthevacuumtubewall.hydrogenstoragealloyplaysaroleofvacuumpump,sealingintheconveyingpipe,doublewalllayer,canmaintainalong-termdeliverypipewallofthevacuumdegree.2對于固體推進劑而言，提高能量水平始終是其發(fā)展的方向。Ｈ２其具有密度小，燃燒放熱大的特點將Ｈ２在推進劑組分中使其在發(fā)工作時出并參與推進劑的燃燒，MgNiH4（ＡＰ［13[14]Ｍg1.3％MgNiH4和Ｍg2u－ＡＰ／Ａｌ／ＨＴPＢ14.5鎂基合金氫化物基合金氫化物對ＡＰ／Ａｌ／ＨＴＰＢ復合推進劑熱分解的作用效果與其含氫量呈現(xiàn)正相關的關系[14-15]。2ApplicationofhydrogenstoragematerialsinhighenergysolidrocketForsolidpropellant,theimprovementofenergylevelisthecoreofitsdevelopment.Ｈ２hasthecharacteristicsofsmalldensityandheatrelease,andtheＨ２isstoredinthepropellantcomponent,sothatitcanreleaseandparticipateinthecombustionofthepropellant,whichcaneffectivelyimprovetheenergylevelofthesolidpropellant.ThestudyfoundthatMg2NiH4onpropellantusedoxidizerperchlorateammonium(AP)thermal positionhasabettercatalyticactivity,cansignificantlypromotetheAPthermal position,andreducethehightemperature positiontemperature,increasingtheapparent positionheat［13］.TheeffectofＭg2Cu-Honthethermal positionofAPinMgCualloyhydrogenstoragematerialwasstudiedbyLiuLeili[14-15].TheeffectofonthethermalpositionofAPwasfoundtobebetterthanthatofＭg2Cu.TheburningrateofAl/AP/HTPBcompositewasincreasedby3.5%and14.5%bymassfractionof1.3%Mg2NiH4andＭg2Cu－Ｈ.Inaddition,theeffectofAP/Al/HTPBcompositepropellantonthethermalpositionofMgbasedalloysispositivelyrelatedtothehydrogen，主要成分是基質，但是基質自身沒有感度，它必須通過物理或化學方法敏化制成后才能起爆傳統(tǒng)敏化方式有化學敏化、物理敏化（常用玻璃微球和珍珠巖敏化，但這些敏化材料不是含能材料，對提高能量沒有幫助。貯氫合金ＭgH2和ＴiH2是新型含能材料，在一定條件下基質中的貯氫材料ＭgＨ２和ＴiＨ２會水解出Ｈ２，起到敏化作用；氫氣的能量密度較高，是液態(tài)碳氫的３倍，因而，以增加的；Ｈ２同氧氣作用時，唯一產(chǎn)物是水，不產(chǎn)生任何污染；通過向ApplicationofhydrogenstoragealloysinemulsionThemaincomponentofemulsionexplosiveistheemulsionmatrix,butithasnosenseofbeing.Ithastobemadebyphysicalorchemicalmethod,whichcanbeusedtomakeemulsionexplosive,andthetraditionalmethodofemulsionexplosiveischemicalsensitization,physicalsensitization,butthesearenotenergeticmaterials.HydrogenstoragealloysＭgＨ２andＴiＨ２arenewenergeticmaterials,whichcanbeusedtoproduceＨ２,whichcanincreasetheexplosivepowerofexplosive.TheＨ２andＴiＨ２canincreasetheexplosivepowerofexplosive.Theonlyproductiswater,withoutspecialrequirements.Therefore,ithasgreatapplicationprospect.HydrogenstoragealloysＭgＨ２andＴiＨ２haveadualroleintheemulsionexplosives,whichplaysadualroleinthesensitizationandtheenergeticmaterials.5.7ApplicationinDifferentusesofthebrakearemadebythehydrogenpressuredifferencecausedbyhydrogenstoragealloy.Ifthehydrogenstoragealloyisheatedinasealedcontainer,alargeamountofhydrogenisgeneratedandahighpressure,whichisgeneratedwhencooling.Thisprocesshastheadvantagesofsmallsizeandlightweight,andcangeneratehighpower,nonoise,simplestructure,andcanbeoperatedindependentlyandhavetheadvantagesofbuffer.Accordingtotheaboveprinciple,hydrogenstoragealloycanbemadeintoofthemechanicalbrake,theslowmovementoftheliftingdevice,theoperationofthecompressorandcontrolvalve[16].目前已開發(fā)研究的貯氫合金品種類型雖然眾多,但成不多,主要還是稀土系AB5型合金,實用的貯氫合金新品種;貯氫合金應用領域雖然廣闊,但在很多領域的應用仍然處于試驗開發(fā)階段,只是在鎳-氫化物二次電池中