Kugadzirwa kwe lithium mabhatiri

Kwakabva bhatiri mudziyo unogona kutanga nekuwanikwa kwebhodhoro reLeiden. Bhodhoro reLeiden rakatanga kugadzirwa nemusayendisiti wechiDutch Pieter van Musschenbroek muna 1745. Chirongo cheLeyden iprimitive capacitor device. Inoumbwa nemashizha maviri esimbi akaparadzaniswa ne insulator. Iyo simbi yesimbi iri pamusoro inoshandiswa kuchengeta uye kuburitsa charge. Paunobata tsvimbo Kana bhora resimbi rinoshandiswa, bhodhoro reLeiden rinogona kuchengeta kana kubvisa mukati mesimba remagetsi, uye nheyo yayo uye kugadzirira zviri nyore. Chero ani anofarira anogona kuzviita ega kumba, asi iyo yekuzviburitsa yega chiitiko chakanyanya kuomarara nekuda kwegwara rayo riri nyore. Kazhinji, magetsi ose achabudiswa mumaawa mashomanana kusvika kumazuva mashoma. Nekudaro, kubuda kwebhodhoro reLeiden kunoratidza nhanho nyowani mukutsvaga kwemagetsi.

Mumakore ekuma1790, musayendisiti wokuItaly Luigi Galvani akawana kushandiswa kwezingi newaya dzemhangura kubatanidza makumbo edatya ndokuona kuti makumbo edatya aizozununguka, saka akaronga pfungwa ye "bioelectricity." Kuwanikwa uku kwakaita kuti musayendisiti wokuItaly Alessandro azununguke. Kupikisa kwaVolta, Volta anotenda kuti kukwenya kwemakumbo edatya kunobva pamagetsi anogadzirwa nesimbi kwete magetsi ari padatya. Kuti arambe dzidziso yaGalvani, Volta akaronga yake yakakurumbira Volta Stack. Iyo voltaic stack inosanganisira zinc nemhangura mapepa ane makadhibhokisi akanyikwa mumvura yemunyu pakati. Iyi ndiyo prototype yekemikari bhatiri yakatsanangurwa.
Iyo electrode reaction equation yevoltaic cell:

electrode yakanaka: 2H^++2e^-→H_2

negative electrode: Zn→〖Zn〗^(2+)+2e^-

Muna 1836, musayendisiti wekuBritain John Frederic Daniell akagadzira bhatiri raDaniel kugadzirisa dambudziko remabhuru emhepo mubhatiri. Bhatiri raDaniel rine chimiro chekutanga chebhatiri remakemikari razvino. Inoumbwa nezvikamu zviviri. Chikamu chakanaka chinonyudzwa mumhangura sulfate solution. Chimwe chikamu chemhangura i zingi yakanyudzwa mune zinc sulfate solution. Bhatiri rekutanga raDaniel raive rakazadzwa necopper sulfate solution mumudziyo wemhangura ndokuisa ceramic porous cylindrical container pakati. Muchigaba ichi checeramic, pane zinc rod uye zinc sulfate se electrode yakaipa. Mune mhinduro, maburi madiki mumudziyo weceramic anobvumira makiyi maviri kuchinjanisa ions. Mazuva ano mabhatiri aDaniel anonyanya kushandisa mabhiriji emunyu kana semi-permeable membranes kuita izvi. Mabhatiri eDaniel akashandiswa sesimba remagetsi kune network yetelegraph kusvika mabhatiri akaoma avatsiva.

Iyo electrode reaction equation yebhatiri raDaniel:

Positive electrode: 〖Cu〗^(2+)+2e^-→Cu

negative electrode: Zn→〖Zn〗^(2+)+2e^-

Kusvika pari zvino, chimiro chekutanga chebhatiri chakatemwa, icho chinosanganisira iyo yakanaka electrode, iyo inegetive electrode, uye electrolyte. Pahwaro hwakadaro, mabhatiri akava nekukura nokukurumidza mumakore 100 anotevera. Mazhinji mabhatiri masisitimu matsva akaonekwa, kusanganisira musayendisiti wechiFrench Gaston Planté akagadzira mabhatiri e-lead-asidhi muna 1856. Mabhatiri e-lead-asidhi Kubuda kwayo kukuru kwazvino uye mutengo wakaderera kwakakwezva kutarisisa kukuru, saka inoshandiswa mumidziyo yakawanda yemafoni, semagetsi ekutanga. motokari. Inowanzo shandiswa sesimba rekuchengetedza simba kune zvimwe zvipatara uye zviteshi zvepasi. Lead-asidhi mabhatiri anonyanya kuumbwa nelead, lead dioxide, uye sulfuric acid solution, uye voltage yawo inogona kusvika ku2V. Kunyange munguva dzazvino uno, mabhatiri e<em>lead-asidhi haana kubviswa nemhaka younyanzvi hwawo hworuzivo rwokuzviwanira hwakura, mitengo yakaderera, uye gadziriro dzakachengeteka dzemvura.

Iyo electrode reaction equation yelead-asidhi bhatiri:

Positive electrode: PbO_2+〖SO〗_4^(2-)+4H^++2e^-→Pb〖SO〗_4+2H_2 O

Negative electrode: Pb+〖SO〗_4^(2-)→Pb〖SO〗_4+2e^-

Nickel-cadmium bhatiri, rakagadzirwa nemusayendisiti wekuSweden Waldemar Jungner muna 1899, rinoshandiswa zvakanyanya mumidziyo midiki yemagetsi, senge mawalkmans ekutanga, nekuda kwekuwanda kwayo kwesimba kupfuura mabhatiri e-lead-acid. Zvakafanana nemabhatiri ekutungamirira-asidhi. Nickel-cadmium mabhatiri akashandiswawo zvakanyanya kubva kuma1990, asi huturu hwawo hwakanyanya, uye bhatiri pacharo rine chaiyo yekurangarira maitiro. Ndosaka tichiwanzonzwa vamwe vanhu vakuru vachiti bhatiri rinofanirwa kuburitswa risati rachaja uye kuti mabhatiri emarara achasvibisa nyika, zvichingodaro. (Cherechedza kuti kunyange mabhatiri emazuva ano ane chepfu uye haafanire kuraswa kwose kwose, asi mabhatiri eLithium emazuva ano haana zvikomborero zvekuyeuka, uye kunyanya-kubuda kunokuvadza kuhupenyu hwebheteri.) Nickel-cadmium mabhatiri ari kunyanya kukuvadza zvakatipoteredza, uye Yavo. kupikisa kwemukati kuchachinja nekupisa, izvo zvinogona kukonzera kukuvadzwa nekuda kwekunyanyisa ikozvino panguva yekuchaja. Nickel-hydrogen mabhatiri akaibvisa zvishoma nezvishoma makore akapoteredza 2005. Kusvika ikozvino, nickel-cadmium mabhatiri haawanzoonekwa pamusika.

Electrode reaction equation yenickel-cadmium bhatiri:

Positive electrode: 2NiO(OH)+2H_2 O+2e^-→2OH^-+2Ni〖(OH)〗_2

Negative electrode: Cd+2OH^-→Cd〖(OH)〗_2+2e^-

Lithium simbi bhatiri nhanho

Muma1960, vanhu vakazopinda zviri pamutemo munguva yemabhatiri e lithium.

Lithium simbi pachayo yakawanikwa muna 1817, uye vanhu vakakurumidza kuona kuti lithium simbi yemuviri uye kemikari zvivakwa zvinogara zvichishandiswa semidziyo yemabhatiri. Iyo ine yakaderera density (0.534g 〖cm〗^(-3)), yakakura simba (theoretical kusvika 3860mAh g ^(-1)), uye yakaderera kugona kwayo (-3.04V zvichienzaniswa neyakajairika hydrogen electrode). Ava vanenge vachiudza vanhu kuti ndiri negative electrode material yebhatiri rakakodzera. Nekudaro, lithium simbi pachayo ine matambudziko makuru. Inonyanya kushanda, inopindirana nechisimba nemvura, uye ine zvinodiwa zvakakwirira panzvimbo yekushanda. Nokudaro, kwenguva refu, vanhu vakanga vasingagoni kuzvibatsira nazvo.

Muna 1913, Lewis naKeyes vakayera kugona kwe lithium metal electrode. Uye yakaita bvunzo yebhatiri ne lithium iodide mupropylamine mhinduro se electrolyte, kunyangwe yakakundikana.

Muna 1958, William Sidney Harris akataura muchirevo chake chechiremba kuti akaisa lithium simbi mune zvakasiyana organic ester mhinduro uye akacherechedza kuumbwa kwenhevedzano yepassivation layers (kusanganisira lithium simbi mu perchloric acid). Lithium LiClO_4

Chiitiko chiri muPC solution yepropylene carbonate, uye iyi mhinduro yakakosha ye electrolyte system mumabhatiri e-lithium mune ramangwana), uye imwe ion transmission phenomenon yakaonekwa, saka mamwe mapreliminary electrodeposition experiments akaitwa zvichibva pane izvi. Izvi zviedzo zvakatungamira zviri pamutemo kugadzirwa kwemabhatiri e-lithium.

Muna 1965, NASA yakaita ongororo yakadzama pamusoro pekuchaja nekuburitsa zvinhu zveLi||Cu mabhatiri mu lithium perchlorate PC solutions. Mamwe maelectrolyte masisitimu, anosanganisira kuongororwa kweLiBF_4, LiI, LiAl〖Cl〗_4, LiCl, Tsvakurudzo iyi yamutsa kufarira kukuru muorganic electrolyte masisitimu.

Muna 1969, patent yakaratidza kuti mumwe munhu akanga atanga kuedza kutengesa organic solution mabhatiri achishandisa lithium, sodium, uye potassium simbi.

Muna 1970, Japan's Panasonic Corporation yakagadzira Li‖CF_x ┤ bhatiri, uko reshiyo ye x inowanzoita 0.5-1. CF_x ifluorocarbon. Kunyangwe gasi refluorine rine muchetura zvakanyanya, iyo fluorocarbon pachayo ndeye-chena isina-chepfu poda. Kubuda kweLi‖CF_x ┤ bhatiri inogona kunzi ndiyo yekutanga chaiyo yekutengesa lithium bhatiri. Li‖CF_x ┤ bhatiri ibhatiri rekutanga. Zvakadaro, huwandu hwayo hwakakura, iyo theoretical kugona ndeye 865mAh 〖Kg〗^(-1), uye yayo yekuburitsa voltage yakagadzikana kwazvo muhurefu-refu. Nokudaro, simba racho rakagadzikana uye chiitiko chekuzvibudisa chidiki. Asi ine abysmal rate performance uye haigone kubhadhariswa. Nokudaro, inowanzobatanidzwa ne manganese dioxide kuti iite Li‖CF_x ┤-MnO_2 mabhatiri, ayo anoshandiswa semabhatiri emukati kune mamwe ma sensors maduku, wachi, nezvimwewo, uye haana kubviswa.

Positive electrode: CF_x+xe^-+x〖Li〗^+→C+xLiF

Negative electrode: Li→〖Li〗^++e^-

Muna 1975, Sanyo Corporation yekuJapan yakagadzira Li‖MnO_2 ┤ bhatiri, rakatanga kushandiswa mumakarukureta ezuva. Izvi zvinogona kutorwa seyekutanga rechargeable lithium bhatiri. Kunyange zvazvo chigadzirwa ichi chakanga chiri kubudirira kukuru muJapan panguva iyoyo, vanhu vakanga vasina kunzwisisa kwakadzama kwezvinhu zvakadaro uye vakanga vasingazivi lithium uye manganese dioxide. Ndechipi chikonzero chiri kukonzera kuita kwacho?

Panenge panguva imwecheteyo, maAmerican aitsvaga bhatiri reusable, iyo yatinodaidza kuti yechipiri bhatiri.

Muna 1972, MBArmand (mazita emamwe masayendisiti haana kushandurirwa pakutanga) akakurudzirwa mubepa remusangano M_(0.5) Fe〖(CN)〗_3 (apo M isimbi yealkali) nezvimwe zvinhu zvine chimiro chebhuruu chePrussia. , Uye akadzidza ayo ion intercalation phenomenon. Uye muna 1973, J. Broadhead nevamwe veBell Labs vakadzidza nezve intercalation phenomenon yesarufa neatomu ayodhine musimbi dichalcogenides. Izvi zvidzidzo zvekutanga pane ion intercalation phenomenon ndiyo inonyanya kukosha simba rekufambisira mberi zvishoma nezvishoma kwemabhatiri e lithium. Tsvagiridzo yepakutanga ndeyechokwadi nekuda kwezvidzidzo izvi izvo gare gare lithium-ion mabhatiri anogoneka.

Muna 1975, Martin B. Dines weExxon (akatangira Exxon Mobil) akaita masvomhu ekutanga uye ongororo pakudyidzana pakati peshanduko yesimbi dichalcogenides uye alkali simbi uye mugore rimwe chetero, Exxon raive rimwe zita reSainzi MS Whittingham akaburitsa patent. paLi‖TiS_2 ┤ dziva. Uye muna 1977, Exoon yakatengesa bhatiri rakavakirwa paLi-Al‖TiS_2┤, umo lithium aluminium alloy inogona kuwedzera kuchengetedzeka kwebhatiri (kunyangwe pachine njodzi yakakosha). Mushure meizvozvo, masisitimu akadaro ebhatiri akashandiswa zvakatevedzana naEveready muUnited States. Kutengeswa kweBattery Company neGrace Company. Iyo Li‖TiS_2 ┤ bhatiri rinogona kuve rekutanga rechipiri lithium bhatiri mupfungwa yechokwadi, uye yaive zvakare yaipisa bhatiri system panguva iyoyo. Panguva iyoyo, simba rayo raive rinenge 2-3 nguva yebhatiri yelead-acid.

Positive electrode: TiS_2+xe^-+x〖Li〗^+→〖Li〗_x TiS_2

Negative electrode: Li→〖Li〗^++e^-

Panguva imwecheteyo, sainzi weCanada MA Py akagadzira Li‖MoS_2┤ bhatiri muna 1983, iro rinogona kuva nesimba re 60-65Wh 〖Kg〗^(-1) pa 1/3C, iyo yakaenzana neLi‖TiS_2┤ bhatiri. Zvichienderana neizvi, muna 1987, kambani yeCanada Moli Energy yakatanga bhatiri rekutengesa lithium, iro raitsvakwa zvakanyanya pasi rese. Ichi chaifanira kunge chiri chiitiko chakakosha munhoroondo, asi chinoshamisa ndechekuti zviri kukonzera kudzikira kweMoli mushure. Zvino muchirimo cha1989, Moli Kambani yakatanga chizvarwa chechipiri cheLi‖MoS_2┤ bhatiri zvigadzirwa. Pakupera kwechirimo cha1989, chizvarwa chekutanga cheMoli Li‖MoS_2┤ bhatiri chigadzirwa chakaputika uye chakakonzera kutya kukuru. Muzhizha regore rimwe chetero, zvigadzirwa zvese zvakayeukwa, uye vakabatwa vakabhadharwa. Pakupera kwegore rimwe chetero, Moli Energy yakazivisa kubhuroka uye yakawanikwa neJapan NEC muchirimo cha1990. Zvinofanira kutaura kuti kune runyerekupe kuti Jeff Dahn, musayendisiti wekuCanada panguva iyoyo, aitungamira chirongwa chebhatiri kuMoli. Simba uye akasiya basa nekuda kwekupikisa kwake kuenderera mberi kunyorwa kweLi‖MoS_2 ┤ mabhatiri.

Positive electrode: MoS_2+xe^-+x〖Li〗^+→〖Li〗_x MoS_2

Negative electrode: Li→〖Li〗^++e^-

Kusvika pari zvino, mabhatiri e-lithium simbi akasiya zvishoma nezvishoma kuona kwevanhu. Tinogona kuona kuti mukati menguva kubva 1970 kusvika 1980, tsvakiridzo yesainzi nezve lithium mabhatiri yainyanya kutariswa pazvinhu zvecathode. Chinangwa chekupedzisira chinogara chakanangana neshanduko yesimbi dichalcogenides. Nekuda kwemaitiro avo akaturikidzana (transition metal dichalcogenides yava kudzidzwa zvakanyanya sechinhu chine mativi maviri), ma layers uye Pane mikaha inokwana pakati pematanho kuti agone kuiswa kwe lithium ions. Panguva iyoyo, pakanga paine tsvakiridzo shoma pazvinhu zveanode panguva iyi. Kunyangwe zvimwe zvidzidzo zvakanangana nekubatanidzwa kwelithium simbi kuti iwedzere kugadzikana kwayo, lithium simbi pachayo haina kugadzikana uye ine njodzi. Kunyangwe kuputika kwebhatiri raMoli chaive chiitiko chakavhundutsa pasirese, pakave neMakesi mazhinji ekuputika kwemabhatiri esimbi eti lithium.

Uyezve, vanhu havana kuziva chikonzero chekuputika kwemabhatiri e-lithium zvakanaka kwazvo. Pamusoro pezvo, lithium simbi yaimboonekwa sechinhu chisingachinjiki chisina kunaka che electrode nekuda kwehunhu hwayo hwakanaka. Mushure mekuputika kwebhatiri raMoli, kugamuchirwa kwevanhu kwemabhatiri e-lithium simbi kwakaderera, uye mabhatiri e-lithium akapinda munguva yerima.

Kuti tive nebhatiri rakachengeteka, vanhu vanofanira kutanga nezvinhu zvinokuvadza zve electrode. Kunyange zvakadaro, kune matambudziko akawanda pano: kukwanisa kwe lithium metal haina kudzika, uye kushandiswa kwemamwe magetsi emagetsi emagetsi kuchawedzera kukanganisa kwe electrode, uye nenzira iyi, mabhatiri e-lithium Musiyano mukuru unogona kuderedzwa, izvo zvichaderedza. kuwanda kwesimba redutu. Naizvozvo, masayendisiti anofanirwa kuwana inoenderana yakakwira-voltage cathode zvinhu. Panguva imwecheteyo, electrolyte yebhatiri inofanirwa kuenderana neiyo yakanaka uye yakaipa voltages uye kutenderera kugadzikana. Panguva imwecheteyo, conductivity ye electrolyte Uye kupisa kupisa kuri nani. Iyi nhevedzano yemibvunzo yakanetsa masayendisiti kwenguva refu kuti awane mhinduro inogutsa.

Dambudziko rekutanga resainzi kugadzirisa nderekutsvaga yakachengeteka, inokuvadza electrode zvinhu zvinogona kutsiva lithium simbi. Lithium simbi pachayo ine yakawandisa kemikari kuita, uye nhevedzano yematambudziko ekukura kwedendrite anga akanyanya kuomarara pamamiriro ekushandisa uye mamiriro, uye haina kuchengetedzeka. Graphite iye zvino ndiyo mutumbi mukuru we electrode yakaipa ye lithiamu-ion mabhatiri, uye kushandiswa kwayo mumabhatiri e-lithium kwakadzidzwa kare kare 1976. Muna 1976, Besenhard, JO akaita chidzidzo chakanyanya pamusoro pe electrochemical synthesis yeLiC_R. Zvisinei, kunyange zvazvo graphite ine zvinhu zvakanakisa (high conductivity, high capacity, low potential, inertness, etc.), panguva iyoyo, electrolyte inoshandiswa mumabhatiri e lithium inowanzova PC solution yeLiClO_4 yataurwa pamusoro apa. Graphite ine dambudziko rakakura. Mukushaikwa kwedziviriro, iyo electrolyte PC mamorekuru anozopindawo muchimiro chegraphite neiyo lithium-ion intercalation, zvichikonzera kudzikira kwekuita kutenderera. Naizvozvo, graphite yakanga isingafadzwi nemasayendisiti panguva iyoyo.

Kana zviri zvecathode zvinhu, mushure mekutsvagisa kweiyo lithium simbi bhatiri nhanho, masayendisiti akawana kuti lithiation anode zvinhu pachayo zvakare iri lithium yekuchengetedza zvinhu zvine reversibility yakanaka, senge LiTiS_2, 〖Li〗_x V〖Se〗_2 (x =1,2) zvichingodaro, uye pachikonzero ichi, 〖Li〗_x V_2 O_5 (0.35≤x<3), LiV_2 O_8 nezvimwe zvinhu zvakagadzirwa. Uye masayendisiti zvishoma nezvishoma akajairana neakasiyana 1-dimensional ion nzira (1D), 2-dimensional layered ion intercalation (2D), uye 3-dimensional ion transmission network zvimiro.

Tsvakurudzo yaProfessor John B. Goodenough yakakurumbira paLiCoO_2 (LCO) yakaitikawo panguva ino. Muna 1979, Goodenougd et al. vakafuridzirwa nechinyorwa chechimiro cheNaCoO_2 muna 1973 uye vakawana LCO uye vakaburitsa chinyorwa patent. LCO ine akaturikidzana intercalation chimiro chakafanana neshanduko simbi disulfides, umo lithium ion inogona kudzoreredzwa kuiswa uye kutorwa. Kana iyo lithium ions yakabviswa zvachose, chivako chepedyo cheCoO_2 chichaumbwa, uye chinogona kuiswa zvakare ne lithium ions ye lithium (Zvechokwadi, bhatiri chaiyo haizobvumiri kuti lithium ions ibudiswe zvachose, iyo ichaita kuti kugona kuore nekukurumidza). Muna 1986, Akira Yoshino, uyo akanga achiri kushanda kuAsahi Kasei Corporation muJapan, akabatanidza zvitatu zveLCO, coke, uye LiClO_4 PC mhinduro kekutanga, ikava yekutanga yemazuva ano lithium-ion yechipiri bhatiri uye ikava yazvino lithium. bhatiri. Sony yakakurumidza kuona iyo "yakanaka zvakakwana" yekare LCO patent uye yakawana mvumo yekuishandisa. Muna 1991, yakatengesa LCO lithium-ion bhatiri. Pfungwa ye lithium-ion bhatiri yakaonekwawo panguva ino, uye pfungwa yayo Inoendererawo nanhasi. (Zvakakosha kucherechedza kuti mabhatiri ezera rekutanga reLithium-ion eSony uye Akira Yoshino anoshandisawo kabhoni yakaoma seye electrode isina kunaka pachinzvimbo chegraphite, uye chikonzero ndechekuti PC iri pamusoro ine intercalation mugraphite)

Positive electrode: 6C+xe^-+x〖Li〗^+→〖Li〗_x C_6

Negative electrode: LiCoO_2→〖Li〗_(1-x) CoO_2+x〖Li〗^++xe^-

Nekune rimwe divi, muna 1978, Armand, M. akakurudzira kushandiswa kwe polyethylene glycol (PEO) seyakasimba polymer electrolyte kugadzirisa dambudziko riri pamusoro apa kuti graphite anode inonyudzwa nyore nyore mumamorekuru ePC anonyungudutsa (iyo mainstream electrolyte panguva iyoyo ichiripo. inoshandisa PC, DEC yakasanganiswa mhinduro), iyo yakaisa graphite mu lithium bhatiri system kekutanga, uye yakakurudzira pfungwa yekuzunguza-chair bhatiri (rocking-chair) mugore rinotevera. Pfungwa yakadaro yakaenderera mberi kusvika nhasi. Magadzirirwo azvino emagetsi emagetsi, akadai seED/DEC, EC/DMC, zvichingodaro, akaonekwa zvishoma nezvishoma muma1990 uye anga achishandiswa kubva ipapo.

Munguva imwe cheteyo, masayendisiti akaongororawo nhevedzano yemabhatiri: Li‖Nb〖Se〗_3 ┤ mabhatiri, Li‖V〖SE〗_2 ┤ mabhatiri, Li‖〖Ag〗_2 V_4 ┤ O_11 mabhatiri, Li‖Cucues,O Li ‖I_2 ┤Mabhatiri, zvichingodaro, nekuti haanyanyi kukosha iye zvino, uye hapana mhando dzakawanda dzetsvagiridzo kuitira kuti ndisazozvizivisa zvakadzama.

• Li-ion bateri siteji

Nguva yelithium-ion battery development mushure me1991 ndiyo nguva yatave ikozvino. Pano ini handizopfupikisa nzira yekuvandudza zvakadzama asi muchidimbu kusuma kemikari yemabhatiri mashoma e-lithium-ion.

Nhanganyaya kune yazvino lithium-ion bhatiri masisitimu, heino chikamu chinotevera.