Kukula kwa mabatire a lithiamu

Chiyambi cha chipangizo cha batri chingayambe ndi kupezeka kwa botolo la Leiden. Botolo la Leiden linapangidwa koyamba ndi wasayansi wachi Dutch Pieter van Musschenbroek mu 1745. Botolo la Leyden ndi chipangizo choyambirira cha capacitor. Zimapangidwa ndi mapepala awiri azitsulo olekanitsidwa ndi insulator. Chitsulo pamwambachi chimagwiritsidwa ntchito kusunga ndi kumasula mtengo. Mukakhudza ndodo Pamene mpira wachitsulo umagwiritsidwa ntchito, botolo la Leiden likhoza kusunga kapena kuchotsa mphamvu yamagetsi yamkati, ndipo mfundo yake ndi kukonzekera kwake ndi kosavuta. Aliyense amene ali ndi chidwi atha kuzipanga yekha kunyumba, koma kudziletsa kwake kumakhala kowopsa chifukwa cha kalozera wake wosavuta. Nthawi zambiri, magetsi onse adzatulutsidwa m'maola ochepa kapena masiku angapo. Komabe, kutuluka kwa botolo la Leiden kumawonetsa gawo latsopano mu kafukufuku wamagetsi.

M'zaka za m'ma 1790, wasayansi wa ku Italy, Luigi Galvani, adapeza kugwiritsa ntchito zinki ndi mawaya amkuwa kuti agwirizane ndi miyendo ya chule ndipo adapeza kuti miyendo ya chule imagwedezeka, choncho adapereka lingaliro la "bioelectricity." Kupeza kumeneku kunapangitsa wasayansi wa ku Italy Alessandro kugwedezeka. Potsutsa za Volta, Volta amakhulupirira kuti kugwedezeka kwa miyendo ya chule kumachokera ku mphamvu yamagetsi yopangidwa ndi chitsulo osati mphamvu yamagetsi pa chule. Kuti atsutsane ndi chiphunzitso cha Galvani, Volta anapempha Volta Stack yake yotchuka. Milu ya voltaic imakhala ndi zinc ndi mapepala amkuwa okhala ndi makatoni oviikidwa m'madzi amchere pakati. Ichi ndi chitsanzo cha batri yamankhwala yomwe ikufuna.
Ma electrode reaction equation ya voltaic cell:

elekitirodi yabwino: 2H^++2e^-→H_2

electrode negative: Zn→〖Zn〗^(2+)+2e^-

Mu 1836, wasayansi wa ku Britain John Frederic Daniell anapanga batri ya Daniel kuti athetse vuto la mpweya mu batire. Batire ya Daniel ili ndi mawonekedwe oyambira a batire lamakono lamankhwala. Lili ndi magawo awiri. Gawo labwino limamizidwa mumkuwa wa sulphate. Mbali ina ya mkuwa ndi nthaka yomizidwa mu zinc sulfate solution. Batire yoyambirira ya Daniel idadzazidwa ndi mkuwa wa sulfate mumtsuko wamkuwa ndikuyika chidebe cha ceramic porous cylindrical pakati. Mu chidebe cha ceramic ichi, pali ndodo ya zinki ndi zinki sulphate monga electrode yoipa. Mu yankho, mabowo ang'onoang'ono mu chidebe cha ceramic amalola makiyi awiriwo kuti asinthe ma ions. Mabatire amakono a Daniel nthawi zambiri amagwiritsa ntchito milatho yamchere kapena nembanemba yolowera pang'ono kuti akwaniritse izi. Mabatire a Daniel ankagwiritsidwa ntchito ngati magwero a mphamvu pa netiweki ya telegraph mpaka mabatire owuma atalowa m’malo mwake.

Ma electrode reaction equation ya batri ya Daniel:

Elekitirodi yabwino: 〖Cu〗^(2+)+2e^-→Cu

electrode negative: Zn→〖Zn〗^(2+)+2e^-

Pakalipano, mtundu woyamba wa batri watsimikiziridwa, womwe umaphatikizapo electrode yabwino, electrode negative, ndi electrolyte. Pamaziko oterowo, mabatire apita patsogolo mofulumira m’zaka 100 zikubwerazi. Mabatire ambiri atsopano awonekera, kuphatikizapo wasayansi wa ku France Gaston Planté anapanga mabatire a lead-acid mu 1856. Mabatire a asidi-lead magalimoto. Nthawi zambiri amagwiritsidwa ntchito ngati chosungira magetsi kuzipatala zina ndi malo oyambira. Mabatire a acid-lead amapangidwa makamaka ndi lead, lead dioxide, ndi sulfuric acid solution, ndipo mphamvu yake imatha kufika pafupifupi 2V. Ngakhale m’nthaŵi zamakono, mabatire a asidi amtovu sanachotsedwepo chifukwa cha luso lawo laumisiri lokhwima, mitengo yotsika, ndi njira zotetezereka za madzi.

Ma electrode reaction equation ya batri ya lead-acid:

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

Elekitirodi yolakwika: Pb+〖SO〗_4^(2-)→Pb〖SO〗_4+2e^-

Batire ya nickel-cadmium, yopangidwa ndi wasayansi waku Sweden Waldemar Jungner mu 1899, imagwiritsidwa ntchito kwambiri pazida zing'onozing'ono zamagetsi, monga ma walkman oyambilira, chifukwa chakuchulukira kwake kwamphamvu kuposa mabatire a lead-acid. Zofanana ndi mabatire a lead-acid. Mabatire a nickel-cadmium akhala akugwiritsidwa ntchito kwambiri kuyambira zaka za m'ma 1990, koma kawopsedwe kawo ndi kawopsedwe, ndipo batireyo imakhala ndi kukumbukira kwina. Ichi ndichifukwa chake nthawi zambiri timamva achikulire ena akunena kuti batri iyenera kutulutsidwa mokwanira musanabwerekenso komanso kuti mabatire otayika adzaipitsa nthaka, ndi zina zotero. (Dziwani kuti ngakhale mabatire amakono ndi oopsa kwambiri ndipo sayenera kutayidwa kulikonse, koma mabatire a lithiamu omwe alipo panopa alibe phindu la kukumbukira, ndipo kutulutsa kwambiri kumawononga moyo wa batri.) Mabatire a nickel-cadmium amawononga kwambiri chilengedwe, ndipo kukana kwamkati kudzasintha ndi kutentha, komwe kungayambitse kuwonongeka chifukwa cha kuchulukirachulukira panthawi yolipira. Mabatire a nickel-hydrogen adachotsa pang'onopang'ono kuzungulira 2005. Mpaka pano, mabatire a nickel-cadmium samawoneka kawirikawiri pamsika.

Electrode reaction equation ya batri ya nickel-cadmium:

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

Elekitirodi yolakwika: Cd+2OH^-→Cd〖(OH)〗_2+2e^-

Gawo la batri la lithiamu

M'zaka za m'ma 1960, anthu adalowa m'nthawi ya mabatire a lithiamu.

Lithium zitsulo zokha zinapezeka mu 1817, ndipo posakhalitsa anthu adazindikira kuti zinthu zakuthupi ndi zamankhwala za lithiamu zitsulo zimagwiritsidwa ntchito ngati zida zamabatire. Ili ndi kachulukidwe otsika (0.534g 〖cm〗^(-3)), mphamvu yayikulu (yoyerekeza mpaka 3860mAh g^(-1)), komanso kuthekera kwake kotsika (-3.04V poyerekeza ndi elekitirodi wa hydrogen). Awa akungouza anthu kuti ndine ma electrode negative a batire yoyenera. Komabe, lithiamu zitsulo palokha ali ndi mavuto aakulu. Imagwira ntchito kwambiri, imachita zachiwawa ndi madzi, ndipo imakhala ndi zofunika kwambiri pamalo ogwirira ntchito. Chotero, kwa nthaŵi yaitali, anthu analibe chochita nacho.

Mu 1913, Lewis ndi Keyes anayeza kuthekera kwa electrode yachitsulo ya lithiamu. Ndipo adayesa batire ndi lithiamu ayodini mu propylamine yankho ngati electrolyte, ngakhale idalephera.

Mu 1958, William Sidney Harris anatchula chiphunzitso chake udokotala kuti anaika lifiyamu zitsulo mu njira zosiyanasiyana organic ester ndipo anaona mapangidwe angapo zigawo passivation (kuphatikizapo lifiyamu zitsulo mu asidi perchloric). Lithiyamu LiClO_4

Chodabwitsa mu njira ya PC ya propylene carbonate, ndipo yankho ili ndilofunika kwambiri la electrolyte mu mabatire a lithiamu m'tsogolomu), ndipo chodabwitsa cha ion transmission chawonedwa, kotero kuyesa koyambirira kwa electrodeposition kwachitika potengera izi. Zoyeserera izi zidapangitsa kuti pakhale mabatire a lithiamu.

Mu 1965, NASA idachita kafukufuku wozama pazacharging ndi kutulutsa kwa mabatire a Li||Cu mu lithiamu perchlorate PC solutions. Makina ena a electrolyte, kuphatikiza kusanthula kwa LiBF_4, LiI, LiAl〖Cl〗_4, LiCl, Kafukufukuyu adzutsa chidwi chachikulu pamakina a electrolyte.

Mu 1969, patent idawonetsa kuti wina adayamba kuyesa kugulitsa mabatire a organic solution pogwiritsa ntchito zitsulo za lithiamu, sodium, ndi potaziyamu.

Mu 1970, Panasonic Corporation yaku Japan idapanga batire ya Li‖CF_x ┤, pomwe chiyerekezo cha x nthawi zambiri chimakhala 0.5-1. CF_x ndi fluorocarbon. Ngakhale mpweya wa fluorine ndi wakupha kwambiri, fluorocarbon palokha ndi ufa wosayera wopanda poizoni. Kutuluka kwa Li‖CF_x ┤ batire tinganene kuti ndi batire yoyamba yamalonda ya lithiamu. Li‖CF_x ┤ batire ndi batire yoyamba. Komabe, mphamvu yake ndi yayikulu, mphamvu yongoyerekeza ndi 865mAh 〖Kg〗^(-1), ndipo magetsi ake otulutsa amakhala okhazikika patali. Chifukwa chake, mphamvuyo ndi yokhazikika komanso chodziwikiratu chochepa. Koma ili ndi magwiridwe antchito abysmal ndipo sangayimbitsidwe. Chifukwa chake, nthawi zambiri amaphatikizidwa ndi manganese dioxide kuti apange mabatire a Li‖CF_x ┤-MnO_2, omwe amagwiritsidwa ntchito ngati mabatire amkati a masensa ang'onoang'ono, mawotchi, ndi zina zambiri, ndipo sanachotsedwe.

Elekitirodi yabwino: CF_x+xe^-+x〖Li〗^+→C+xLiF

Elekitirodi yolakwika: Li→〖Li〗^++e^-

Mu 1975, Sanyo Corporation yaku Japan idapanga batire ya Li‖MnO_2 ┤, yomwe idagwiritsidwa ntchito koyamba pama calculator a sola. Izi zitha kuwonedwa ngati batri yoyamba yowonjezeredwa ya lithiamu. Ngakhale kuti mankhwalawa anali opambana kwambiri ku Japan panthawiyo, anthu analibe kumvetsetsa kwakukulu kwa zinthu zoterezi ndipo sankadziwa kuti lifiyamu ndi manganese dioxide. Kodi ndi chifukwa chotani chimene chimachititsa zimenezi?

Pafupifupi nthawi yomweyo, Achimereka anali kufunafuna batri yogwiritsidwanso ntchito, yomwe tsopano timatcha batri yachiwiri.

Mu 1972, MBArmand (mayina a asayansi ena sanamasuliridwe pachiyambi) anaperekedwa mu pepala la msonkhano M_(0.5) Fe〖(CN)〗_3 (pomwe M ndi chitsulo cha alkali) ndi zipangizo zina zokhala ndi buluu wa Prussia. , Ndipo adaphunzira zochitika zake za ion intercalation. Ndipo mu 1973, J. Broadhead ndi ena a Bell Labs anaphunzira chodabwitsa intercalation cha maatomu sulfure ndi ayodini mu zitsulo dichalcogenides. Maphunziro oyambirirawa pazochitika za ion intercalation phenomenon ndiye mphamvu yoyendetsera pang'onopang'ono ya mabatire a lithiamu. Kafukufuku woyambirira ndi wolondola chifukwa cha maphunzirowa omwe pambuyo pake mabatire a lithiamu-ion amatha.

Mu 1975, Martin B. Dines wa Exxon (m'mbuyo wa Exxon Mobil) anachita kuwerengetsera koyambirira ndi kuyesa pa intercalation pakati pa mndandanda wa kusintha zitsulo dichalcogenides ndi zitsulo zamchere ndi chaka chomwecho, Exxon anali dzina lina Scientist MS Whittingham anasindikiza patent. pa Li‖TiS_2 ┤ dziwe. Ndipo mu 1977, Exoon adagulitsa batire yozikidwa pa Li-Al‖TiS_2┤, momwe lithiamu aluminium alloy imatha kupititsa patsogolo chitetezo cha batri (ngakhale pali chiwopsezo chachikulu). Pambuyo pake, machitidwe a batire otere akhala akugwiritsidwa ntchito motsatizana ndi Eveready ku United States. Kutsatsa kwa Battery Company ndi Grace Company. Batire ya Li‖TiS_2 ┤ ikhoza kukhala batire yoyamba yachiwiri ya lifiyamu m'lingaliro lenileni, komanso inali yotentha kwambiri panthawiyo. Panthawiyo, mphamvu zake zinali pafupifupi nthawi 2-3 kuposa mabatire a acid-acid.

Elekitilodi yabwino: TiS_2+xe^-+x〖Li〗^+→〖Li〗_x TiS_2

Elekitirodi yolakwika: Li→〖Li〗^++e^-

Nthawi yomweyo, wasayansi waku Canada MA Py adapanga batire ya Li‖MoS_2┤ mu 1983, yomwe imatha kukhala ndi mphamvu ya 60-65Wh 〖Kg〗^(-1) pa 1/3C, yomwe ikufanana ndi Li‖TiS_2┤ batire. Kutengera izi, mu 1987, kampani yaku Canada ya Moli Energy idakhazikitsa batire ya lithiamu yogulitsa kwambiri, yomwe idafunidwa kwambiri padziko lonse lapansi. Ichi chikuyenera kukhala chochitika chofunikira kwambiri m'mbiri, koma chodabwitsa ndichakuti zikupangitsanso kuchepa kwa Moli pambuyo pake. Kenako chakumapeto kwa 1989, Kampani ya Moli idakhazikitsa m'badwo wake wachiwiri wa batri wa Li‖MoS_2┤. Kumapeto kwa masika a 1989, mtundu woyamba wa batri wa Moli Li‖MoS_2┤ udaphulika ndikuyambitsa mantha akulu. M’chilimwe cha chaka chomwecho, zinthu zonse zimene anagulazo zinakumbukiridwa, ndipo ozunzidwawo analipidwa. Kumapeto kwa chaka chomwecho, Moli Energy adalengeza kuti bankirapuse ndipo idagulidwa ndi NEC yaku Japan kumapeto kwa 1990. Ndikoyenera kutchula kuti mphekesera zimamveka kuti Jeff Dahn, wasayansi waku Canada panthawiyo, anali kutsogolera ntchito ya batri ku Moli. Mphamvu ndikusiya ntchito chifukwa chotsutsa kutsatiridwa kwa mabatire a Li‖MoS_2 ┤.

Elekitirodi yabwino: MoS_2+xe^-+x〖Li〗^+→〖Li〗_x MoS_2

Elekitirodi yolakwika: Li→〖Li〗^++e^-

Pakalipano, mabatire a lithiamu zitsulo pang'onopang'ono achoka pamaso pa anthu. Titha kuwona kuti kuyambira 1970 mpaka 1980, kafukufuku wa asayansi pa mabatire a lithiamu adangoyang'ana kwambiri pazinthu za cathode. Cholinga chomaliza chimakhala chokhazikika pa transition metal dichalcogenides. Chifukwa cha mawonekedwe awo osanjikiza (kusintha zitsulo dichalcogenides tsopano akuphunziridwa kwambiri ngati zinthu ziwiri-dimensional), zigawo zawo ndi Pali mipata yokwanira pakati pa zigawo kuti agwirizane ndi kuyika kwa ayoni a lithiamu. Panthawiyo, panali kafukufuku wochepa kwambiri pazinthu za anode panthawiyi. Ngakhale kafukufuku wina ayang'ana kwambiri pa kuphatikizika kwa chitsulo cha lithiamu kuti chikhale chokhazikika, chitsulo cha lithiamu chokha ndichosakhazikika komanso chowopsa. Ngakhale kuphulika kwa batri ya Moli kunali chochitika chomwe chinadabwitsa dziko lapansi, pakhala pali Milandu yambiri ya kuphulika kwa mabatire a lithiamu zitsulo.

Komanso, anthu sankadziwa chifukwa cha kuphulika kwa mabatire a lithiamu bwino kwambiri. Komanso, lithiamu zitsulo kamodzi ankaona Irreplaceable zoipa elekitirodi zakuthupi chifukwa katundu wake wabwino. Pambuyo pa kuphulika kwa batri la Moli, kuvomereza kwa anthu kwa mabatire a lithiamu zitsulo kunatsika kwambiri, ndipo mabatire a lithiamu adalowa mumdima.

Kuti mukhale ndi batri yotetezeka, anthu ayenera kuyamba ndi zinthu zovulaza za elekitirodi. Komabe, pali mndandanda wa mavuto pano: kuthekera kwa lithiamu zitsulo ndi osaya, ndi kugwiritsa ntchito maelekitirodi ena pawiri zoipa adzawonjezera zoipa elekitirodi kuthekera, ndipo motere, mabatire lithiamu The chonse kuthekera kusiyana adzakhala yafupika, amene kuchepetsa. kachulukidwe mphamvu ya mkuntho. Choncho, asayansi ayenera kupeza lolingana mkulu-voteji cathode zakuthupi. Nthawi yomweyo, electrolyte ya batri iyenera kufanana ndi ma voltages abwino ndi oyipa komanso kukhazikika kwa mayendedwe. Pa nthawi yomweyo, madutsidwe wa electrolyte Ndi kutentha kukana ndi bwino. Mafunso amenewa anadodometsa asayansi kwa nthaŵi yaitali kuti apeze yankho logwira mtima.

Vuto loyamba kuti asayansi athetse ndikupeza chinthu chotetezeka, chovulaza cha electrode chomwe chingalowe m'malo mwa chitsulo cha lithiamu. Lithium zitsulo palokha zimakhala ndi mankhwala ochulukirapo, ndipo zovuta zingapo za kukula kwa dendrite zakhala zowawa kwambiri pazomwe zimagwiritsidwa ntchito komanso momwe zimagwirira ntchito, ndipo sizotetezeka. Graphite tsopano ndi thupi lalikulu la ma elekitirodi oipa a mabatire a lithiamu-ion, ndipo ntchito yake mu mabatire a lithiamu yaphunziridwa kale mu 1976. Mu 1976, Besenhard, JO wachita kafukufuku wochuluka pa kaphatikizidwe ka electrochemical LiC_R. Komabe, ngakhale ma graphite ali ndi zinthu zabwino kwambiri (madulidwe apamwamba, mphamvu zambiri, kuthekera kochepa, kusakhazikika, etc.), panthawiyo, electrolyte yomwe imagwiritsidwa ntchito mu mabatire a lithiamu nthawi zambiri ndi njira ya PC ya LiClO_4 yomwe tatchula pamwambapa. Graphite ili ndi vuto lalikulu. Popanda chitetezo, mamolekyu a PC a electrolyte adzalowanso mumtundu wa graphite ndi intercalation ya lithiamu-ion, zomwe zimapangitsa kuchepa kwa ntchito yozungulira. Choncho, asayansi panthaŵiyo sankakondedwa ndi graphite.

Ponena za zinthu za cathode, pambuyo pa kafukufuku wa siteji ya batri ya lithiamu zitsulo, asayansi adapeza kuti zinthu za lithiamu anode palokha ndizosungirako zosungirako za lithiamu zomwe zimakhala bwino, monga LiTiS_2, 〖Li〗_x V〖Se〗_2 (x =1,2) ndi zina zotero, ndipo pamaziko awa, 〖Li〗_x V_2 O_5 (0.35≤x<3), LiV_2 O_8 ndi zipangizo zina zapangidwa. Ndipo asayansi pang'onopang'ono adziwa njira zosiyanasiyana za 1-dimensional ion (1D), 2-dimensional layered ion intercalation (2D), ndi 3-dimensional ion transmission network.

Kafukufuku wodziwika kwambiri wa Pulofesa John B. Goodenough pa LiCoO_2 (LCO) adachitikanso panthawiyi. Mu 1979, Goodenougd et al. adauziridwa ndi nkhani yokhudzana ndi kapangidwe ka NaCoO_2 mu 1973 ndipo adapeza LCO ndikusindikiza nkhani yovomerezeka. LCO ili ndi mawonekedwe osanjikizana omwe amafanana ndi kusintha kwachitsulo disulfides, momwe ma ayoni a lithiamu amatha kulowetsedwa ndikuchotsedwa. Ngati ma ion a lithiamu atachotsedwa kwathunthu, dongosolo lodzaza kwambiri la CoO_2 lidzapangidwa, ndipo likhoza kubwezeretsedwanso ndi lithiamu ion ya lithiamu (Zowonadi, batri yeniyeniyo silingalole kuti ma lithiamu atulutsidwe kwathunthu, omwe zidzachititsa kuti mphamvuyo iwonongeke mwamsanga). Mu 1986, Akira Yoshino, amene anali akugwirabe ntchito pa Asahi Kasei Corporation ku Japan, pamodzi atatu a LCO, coke, ndi LiClO_4 PC njira kwa nthawi yoyamba, kukhala woyamba masiku lifiyamu-ion batire yachiwiri ndi kukhala lifiyamu panopa batire. Sony idazindikira mwachangu patent ya LCO ya "zabwino" ndipo adalandira chilolezo choigwiritsa ntchito. Mu 1991, idagulitsa batire ya LCO lithiamu-ion. Lingaliro la batri la lithiamu-ion lidawonekeranso panthawiyi, ndipo lingaliro lake likupitirizabe mpaka lero. (Ndikoyenera kudziwa kuti mabatire a lithiamu-ion a Sony a m'badwo woyamba ndi Akira Yoshino amagwiritsanso ntchito mpweya wolimba ngati electrode yolakwika m'malo mwa graphite, ndipo chifukwa chake ndi chakuti PC yomwe ili pamwambayi ili ndi intercalation mu graphite)

Elekitirodi yabwino: 6C+xe^-+x〖Li〗^+→〖Li〗_x C_6

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

Komano, mu 1978, Armand, M. anapempha ntchito polyethylene glycol (PEO) monga olimba polima electrolyte kuthetsa vuto pamwamba kuti graphite anode mosavuta ophatikizidwa mu zosungunulira mamolekyu PC (wamba electrolyte pa nthawi imeneyo akadali akadali). amagwiritsa PC, DEC njira wosanganiza), amene anaika graphite mu lifiyamu dongosolo batire kwa nthawi yoyamba, ndipo akufuna lingaliro la akugwedeza-mpando batire (kugwedeza-mpando) mu chaka chotsatira. Lingaliro loterolo lapitilira mpaka pano. Makina amakono a electrolyte, monga ED/DEC, EC/DMC, ndi zina zotero, adawonekera pang'onopang'ono m'ma 1990 ndipo akhala akugwiritsidwa ntchito kuyambira pamenepo.

Nthawi yomweyo, asayansi adafufuzanso mabatire angapo: Li‖Nb〖Se〗_3 ┤ mabatire, Li‖V〖SE〗_2 ┤ mabatire, Li‖〖Ag〗_2 V_4 ┤ O_11 mabatire, Li‖Mabatire,O Li ‖I_2 ┤Mabatire, ndi zina zotero, chifukwa ndizochepa tsopano, ndipo palibe mitundu yambiri ya kafukufuku kotero kuti ndisawafotokozere mwatsatanetsatane.

• Batoni ya i-ion siteji

Nthawi ya chitukuko cha batri ya lithiamu-ion pambuyo pa 1991 ndi nthawi yomwe takhalamo. Pano sindifotokoza mwachidule ndondomeko yachitukuko mwatsatanetsatane koma mwachidule kufotokoza ndondomeko ya mankhwala a mabatire ochepa a lithiamu-ion.

Chiyambi cha machitidwe a batri a lithiamu-ion, apa pali gawo lotsatira.