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Hi hlathlainak nih hin NH4+ thurhnawmhnak le thlaici zat nih nickel sulfate hexahydrate tthanchonak le riantuan ning cung ah a chuahpimi thil kha a pehzulh lomi lumternak crystallization tangah a hlathlai, cun NH4+ thurhnawmhnak nih nickel sulfate hexahydrate tthanchonak, lumternak sining le riantuannak phu cung ah a chuahpimi thil kha a zohfel. Thil thurhnawmhnak tlawmte ah, Ni2+ le NH4+ ions nih SO42− he pehtlaihnak caah an i zuam, cu nih cun crystal chuahnak le tthanchonak a zorter i crystalization riantuannak thazaang a karhter. Thil thurhnawmhnak a sangmi ah, NH4+ ions cu crystal sining ah aa tel i a harmi chiti (NH4)2Ni(SO4)2 6H2O a ser. A harmi chiti sernak nih crystal chuahnak le tthanchonak a karhter i crystallization riantuannak thazaang a zorter. NH4+ ion a sang le a niam a ummi nih lattice thlennak a chuahter, cun crystals cu 80 °C tiang lumnak ah lumternak ah a fekmi an si. Cun, NH4+ thurhnawmhnak nih crystal ṭhanchonak lam cungah huham a ngeihmi cu thlaici zat nakin a tam deuh. Thil thurhnawmhnak a tlawm tikah, thurhnawmhnak cu crystal ah aa peh a fawi; a tlawm tikah, a thurhnawmmi cu crystal chungah luh a fawi. Thlaici zat nih crystal chuahnak kha tampi a karhter khawh i crystal thianhlimnak kha tlawmpal a tthanchoter khawh.
Nickel sulfate hexahydrate (NiSO4 6H2O) cu a tu ahcun chawlehnak phunphun ah hmanmi a biapi tukmi thilri a si cang, cu hna ahcun battery sernak, electroplating, catalysts, le rawl, chiti le rimhmui sernak hmanh ah an hman. 1,2,3 A biapitnak cu electric mawtaw a rang tukmi tthanchonak he a karh chin lengmang, cu hna cu nickel-based lithium-ion (LiB) battery cungah aa hngatmi an si. NCM 811 tibantuk a tammi nickel cawhmi hmannak nih 2030 ah a uk lai tiah ruah a si, cu nih cun nickel sulfate hexahydrate herhnak a karhter chin. Sihmanhsehlaw, thilri tlawm tuk ruangah, thilchuahmi nih a karh cuahmahmi herhbaunak he aa tlak kho lo, cu nih cun pekmi le halmi karlak ah thleidannak a chuahter. Hi tlamtlin lonak nih hin thilri hmuh khawhnak le man tthatnak kongah lungretheihnak a chuahter, a thiangmi, a fekmi battery-grade nickel sulfate ttha tein chuah a herhnak a langhter. 1,4
Nickel sulfate hexahydrate chuah khawhnak cu a tlangpi in crystallization in tuah khawh a si. Lam phunphun lakah, lumternak lam cu a tam deuh hmanmi lam a si, cu nih cun thazaang tlawmte hmannak le a thiangmi thilri chuah khawhnak ṭhatnak a ngei. 5,6 Nickel sulfate hexahydrate cu a pehzulh lomi lumternak hmangin a tthangchonak kong hlathlainak nih tthanchonak tampi a chuahpi. Atu lio ah, hlathlainak tam deuh nih cun lumnak, lumternak rate, thlaici ngan le pH tibantuk parameters pawl kha ttha tein sernak thawngin crystallization kalning tthanchoternak ah an i hngat. 7,8,9 A hmuitinh cu hmuhmi lungvar hna i lungvar chuah khawhnak le thianhlimnak karhter kha a si. Sihmanhsehlaw, hi parameters pawl hi tling tein hlathlainak tuah a si ko nain, thil thurhnawm, a bik in ammonium (NH4+) nih crystallization results cungah huham a ngeihnak kongah lungthin peknak ah tthennak nganpi a um rih.
Ammonium thurhnawmhnak cu chuahnak tuah lio ah ammonium thurhnawmhnak a um caah nickel crystallization caah hmanmi nickel cawhmi ah a um kho men. Ammonia cu a tlangpi in saponifying agent ah hman a si, cu nih cun nickel cawhmi ah NH4+ tlawmpal a chiah. 10,11,12 Ammonium thurhnawmhnak cu hmunkip ah a um ko nain, crystal sining, tthanchonak lam, lumnak sining, thianhlimnak, tbk. hna cungah an thlennak cu ttha tein theihthiam a si rih lo. An thlennak kong hlathlainak tlawmte lawng a ummi cu a biapi tukmi a si, zeicahtiah thurhnawmhnak nih crystal ṭhanchonak kha a kham khawh asiloah a thlen khawh i, thil sining cheukhat ahcun, khamtu bantukin rian a ṭuan, metastable le stable crystalline phun karlak i thlennak kha a hnorsuan khawh. 13,14 Cucaah hi thil sining hna hngalhthiamnak cu riantuannak lei hmuhning in a biapi tukmi a si, zeicahtiah thil thurhnawm nih thilri tthatnak a hrawh khawh.
Biahalnak pakhat cung ah hram bunh in, hi hlathlainak nih hin ammonium thurhnawmhnak nih nickel crystals sining cung ah a chuahpimi thil sining hlathlainak tuah aa tinh. Thil thurhnawmhnak hna nih an chuahpimi thil hngalhthiamnak thawngin, an chiatnak hna kha uk khawhnak le tlawmter khawhnak ding caah lam thar ser khawh a si. Hi hlathlainak nih hin thil thurhnawm tlawmtam le thlaici zat thlennak karlak pehtlaihnak zong a hlathlai. Thlaici cu thilchuahnak ah tampi hman a si caah, hi hlathlainak ah thlaici parameters hman a si, cun hi thil pahnih karlak pehtlaihnak hngalhthiam a herh. 15 Hi thil pahnih hna nih an chuahpimi thil hna cu lungvar chuah khawhnak, lungvar ṭhanchonak lam, lungvar sining, a muisam le a thianghlimnak hlathlainak caah hman a si. Cun, NH4+ thurhnawmhnak lawng nih a ukmi crystal pawl i an cawlcangh ning, an lumnak sining le an riantuannak phu pawl kha hlathlainak an tuah chap.
Hi hlathlainak ah hmanmi thilri hna cu GEM nih a pekmi nickel sulfate hexahydrate (NiSO 6H2O, ≥ 99.8%) an si; Tianjin Huasheng Co., Ltd. in cawkmi ammonium sulfate ((NH)SO, ≥ 99%); ti thiang. A hmanmi thlaici crystal cu NiSO 6H2O a si, 0.154 mm tluk aa khatmi thil hme tete hmuh khawhnak ding caah an cawh i an thlet. NiSO 6H2O sining cu Table 1 le Figure 1 ah hmuh khawh a si.
NH4+ thurhnawmhnak le thlaici zat nih nickel sulfate hexahydrate a tthawnnak ah a chuahpimi thil kha a caancaan ah lumternak hmangin hlathlainak tuah a si. Hneksaknak vialte cu a hramthawk lumnak 25 °C ah tuah a si. 25 °C cu thlennak tuah lio ah lumternak uknak rikhiahnak hna kha ruah in crystallization lumternak ah thim a si. Lungthawhnak tlawmte Buchner funnel hmangin a lummi cawhnuk hna thlet lio ah ruahlo piin lumnak aa thlengmi nih crystallization a chuahter khawh. Hi thil kalning nih hin thil kalning, thil thurhnawm laknak le lungvar sining phunphun kha tampi in a hnorsuan khawh.
Nickel cawhmi cu 224 g NiSO4 6H2O kha 200 ml ti thiang ah cawh in a hmasa bik ah an ser. Thimmi tlawmtam cu a tlawm deuhmi (S) = 1.109 he aa tlak. Supersaturation cu 25 °C ah a rawkmi nickel sulfate crystals le nickel sulfate hexahydrate a cawh khawhnak tahchunhnak in tuak a si. A niam deuhmi supersaturation cu a hramthawk lumnak ah a niamter tikah amah tein a tthawnnak khamnak caah thim a si.
NH4+ ion tlawmtam nih crystallization kalning ah a chuahpimi thil cu nickel cawhmi ah (NH4)2SO4 cawh in hlathlainak tuah a si. Hi hlathlainak ah hmanmi NH4+ ion tlawmtam cu 0, 1.25, 2.5, 3.75, le 5 g/L an si. Cu cawhmi cu 60 °C ah 30 min chung lumter a si i 300 rpm in cawh in aa khatmi cawh khawhnak ding caah a si. Cu hnu ah a cawhmi cu a duhmi thlennak lumnak tiang lumter a si. Lungthawhnak 25 °C a phak tikah, a phunphun in thlaici crystals (thlaici zat 0.5%, 1%, 1.5%, le 2%) kha cawhmi ah an cawh. Thlaici zat cu thlaici rit le cawhmi chung i NiSO4 6H2O rit tahchunhnak in tuak a si.
Thlaici crystals pawl kha cawhmi ah an cawh hnu ah, crystallization cu amah tein a cang. Crystallization cu minutes 30 chung a rau. Cu cawhmi cu filter press hmangin a cawhmi chungin a tlummi crystals pawl kha thleidan chinchin awkah an thlet. Thianhhlimhnak tuah lio ah, crystals pawl cu ethanol in an tawl tawn hna i, a thar in a chuah khawhnak ding le crystals cunglei ah a ummi thil thurhnawm pawl an i hngat khawhnak ding caah a si. Ethanol cu ​​crystal pawl tawl awkah thim a si, zeicahtiah crystal pawl cu ethanol ah an cawh kho lo. A thletmi lungvar pawl cu 50 °C ah laboratory incubator ah an chiah hna. Hi hlathlainak ah hmanmi a tlingmi hneksaknak tahfung hna cu Table 2 ah langhter an si.
Crystal sining cu XRD thilri (SmartLab SE—HyPix-400) hmangin hngalh khawh a si i NH4+ compound a um le um lo hmuh khawh a si. Crystal sining hlathlainak caah SEM sining (Apreo 2 HiVac) tuah a si. Crystals hna i an lumnak sining cu TGA thilri (TG-209-F1 Libra) hmangin tuak a si. Riantuannak phu pawl cu FTIR (JASCO-FT/IR-4X) hmangin an hlathlai hna. Sample thianhlimnak cu ICP-MS thilri (Prodigy DC Arc) hmangin tuak a si. Sample cu 0.5 g crystals kha 100 mL ti thiang ah cawh in timhtuahnak a si. Crystallization yield (x) cu a chuakmi crystal ritnak kha a luhtermi crystal ritnak he formula (1) ningin tthen in tuak a si.
cuka ah x cu 0 in 1 tiang aa dangmi lungvar chuahmi a si, mout cu a chuakmi lungvar (g) rit a si, min cu luhtermi lungvar (g) rit a si, msol cu ​​cawhmi lungvar rit a si, cun mseed cu thlaici lungvar rit a si.
Crystallization chuahmi cu crystal tthanchonak kinetics hngalh khawhnak ding le riantuannak thazaang man tuaktan khawhnak ding caah hlathlainak tuah chap a si. Hi hlathlainak cu 2% thlaici cinnak ratio le hlan bantuk hneksaknak tuah ning he tuah a si. Isothermal crystallization kinetics parameters cu crystallization caan (10, 20, 30, le 40 min) aa dangmi le a hramthawk lumnak (25, 30, 35, le 40 °C) ah crystal chuahmi tuaktannak in an tuak. A hramthawk lumnak ah thimmi tlawmtam hna cu 1.109, 1.052, 1, le 0.953 tlukruannak (S) man he aa tlak. Supersaturation man cu a hramthawk lumnak ah a rawkmi nickel sulfate crystals le nickel sulfate hexahydrate a rawk khawhnak tahchunhnak in tuak a si. Hi hlathlainak ah, NiSO4 6H2O cu ti 200 mL ah a lum le lum lo aa dangmi ah thurhnawmhnak um loin a cawh khawhnak cu hmanthlak 2 ah hmuh khawh a si.
Johnson-Mail-Avrami (JMA theory) cu isothermal crystallization ziaza hlathlainak caah hman a si. JMA theory cu thim a si, zeicahtiah crystallization process cu seed crystals pawl kha a cawhmi ah an cawh hlan tiang a cang lo. JMA theory cu a tanglei bantuk in a langhter:
x(t) nih caan t ah thlennak a aiawh, k nih thlennak rate aa thleng lomi a aiawh, t nih thlennak caan a aiawh, cun n nih Avrami index a aiawh. Formula 3 cu formula (2) in a chuakmi a si. Crystallization riantuannak thazaang cu Arrhenius equation hmangin tuak a si:
Kg cu thlennak rate aa thleng lomi a si, k0 cu aa thleng lomi a si, Eg cu crystal ṭhanchonak riantuannak thazaang a si, R cu molar gas aa thleng lomi (R=8.314 J/mol K), cun T cu isothermal crystallization temperature (K) a si.
Figure 3a nih a langhter mi cu thlaici cinnak zat le dopant tlawmtam nih nickel crystals chuah khawhnak ah huham a ngei. Ti chung i dopant tlawmtam cu 2.5 g/L tiang a karh tikah, crystal chuahmi cu 7.77% in 6.48% (thlaici zat 0.5%) le 10.89% in 10.32% (thlaici zat 2%) tiang a zor. Dopant tlawmtam a karh chin lengmangmi nih cun aa tlakmi crystal chuahmi a karhter. A sang bik cinmi cu 17.98% a phan tikah thlaici cinnak ratio cu 2% a si i dopant tlawmtam cu 5 g/L a si. Dopant tlawmtam a karh tikah crystal chuah ning thlennak cu crystal ṭhanchonak lam thlennak he aa pehtlaimi a si kho. Dopant tlawmtam a tlawm tikah, Ni2+ le NH4+ ions pawl cu SO42− he pehtlaihnak caah an i zuam, cu nih cun a cawhmi ah nickel a cawh khawhnak a karhter i crystal chuah khawhnak a zorter. 14 Thil thurhnawmhnak a tam tikah, zuamnak cu a cang peng ko, asinain NH4+ ions cheukhat cu nickel le sulfate ions he an i pehtlaih i nickel ammonium sulfate chiti pahnih an ser. 16 Chiti pahnih a chuah tikah a cawhmi thil a tlawmter, cucaah lungvar chuah khawhnak a karhter. Thlaici cinmi zat karhternak nih lungvar chuahmi kha a tthanter peng khawh. Thlaici nih nucleation kalning le amah tein crystal ṭhanchonak kha a thawk khawh i, solute ions pawl kha a hramthawknak hmunhma a pek hna i crystal pawl kha a dirh khawh hna i a ser khawh hna. Seeding ratio a karh tikah, ions pawl an i fonh khawhnak ding caah a hramthawknak hmun cu a karh, cucaah crystal tam deuh a chuak kho. Cucaah, thlaici tuhnak zat karhternak nih crystal ṭhanchonak le crystal chuah khawhnak cungah direct in huham a ngei. 17
NiSO4 6H2O parameters: (a) crystal chuahmi le (b) nickel cawhmi pH cu thlopbulnak tuah hlan le hnu ah.
Figure 3b nih a langhter mi cu thlaici zat le dopant tlawmtam nih thlaici chap hlan le chap hnu ah nickel cawhmi pH kha a hnorsuan. Thil cawhmi pH zohkhenhnak a ruang cu cawhnuk chung i chemical tlukruannak thlennak hngalhthiam awkah a si. Seed crystals pawl chap hlanah, H+ protons a chuahtertu NH4+ ions a um caah a cawhmi pH cu a zor deuh tawn. Dopant tlawmtam karhternak nih H+ proton tam deuh a chuahter, cucaah cawhmi pH a zorter. Seed crystals pawl na cawh hnu ah, a cawhmi vialte pH cu a karh. pH sining cu crystal chuah ning sining he aa pehtlaimi a si. A niam bik pH man cu dopant tlawmtam 2.5 g/L le thlaici zat 0.5% ah hmuh a si. Dopant tlawmtam cu 5 g/L tiang a karh tikah, a cawhmi pH cu a karh. Hi thil cangmi hi hngalhthiam khawh ngai a si, zeicahtiah cawhmi chung i NH4+ ions hmuh khawhnak cu laknak ruangah maw, asiloah aa telmi ruangah maw, asiloah NH4+ ions pawl kha crystals nih a laknak le aa telnak ruangah a zor.
Crystal tthanchonak hneksaknak le hlathlainak cu crystal tthanchonak a cawlcangh ning hngalh khawhnak ding le crystal tthanchonak thazaang tuaktannak caah tuah chap a si. Isothermal crystallization kinetics parameters cu Methods timi ah fianternak an tuah. Figure 4 nih Johnson-Mehl-Avrami (JMA) plot a langhter i cu nih cun nickel sulfate crystal tthanchonak a cawlcangh ning a langhter. Plot cu ln[− ln(1− x(t))] man le ln t man (Equation 3) suai in sermi a si. Plot in hmuhmi gradient man hna cu JMA index (n) man hna he aa tlak i cu nih cun a ṭhangchomi crystal le a ṭhanchonak lam kha a langhter. Cutoff value nih cun a zungzal in ln k nih a langhtermi tthanchonak rate a langhter lio ah. JMA index (n) man cu 0.35 in 0.75 karlak a si. Hi n man nih hin lungvar pawl cu a tthenkhat in an tthancho i tthencheunak-ukmi tthanchonak lam an zulh ti a langhter; 0 < n < 1 nih cun a tthenkhat tthanchonak a langhter, cu lio ah n < 1 nih cun karhternak-ukmi tthanchonak lam a langhter. 18 K aa thleng lomi a ṭhancho ning cu lumnak a karh tikah a zor, cu nih cun lumnak a niam deuh tikah crystallization process cu a rang deuh ti a langhter. Mah cu a niam deuhmi lumnak ah a cawhmi thilri a karhmi he aa pehtlai.
Johnson-Mehl-Avrami (JMA) nih nickel sulfate hexahydrate cu aa dangmi lumnak lumternak ah a suaimi a si: (a) 25 °C, (b) 30 °C, (c) 35 °C le (d) 40 °C.
Dopants chapnak nih lumnak kip ah tthanchonak rate aa khatmi a langhter. Dopant tlawmtam 2.5 g/L a si tikah, crystal tthanchonak a zor, cun dopant tlawmtam 2.5 g/L nak tam a si tikah, crystal tthanchonak rate a karh. A hlan deuh ah kan chim cang bantuk in, crystal tthannak rate thlennak cu a cawhmi chung i ion karlak pehtlaihnak mechanism thlennak ruangah a si. Dopant tlawmtam a tlawm tikah, a cawhmi chung i ion karlak i zuamnak nih a cawhmi a cawh khawhnak a karhter, cucaah crystal ṭhanchonak a zorter. 14 Cun, dopants tam tuk chapnak nih tthanchonak kalning kha tampi in a thlen. Dopant tlawmtam nih 3.75 g/L a lonh tikah, a dang crystal nuclei thar a chuak, cu nih cun a cawhmi thilri a tlawmter, cucaah crystal ṭhanchonak a karhter. Crystal nuclei thar sernak cu chiti (NH4)2Ni(SO4)2 6H2O sernak in langhter khawh a si. 16 Crystal ṭhanchonak lam kong kan i ruah tikah, X-ray thlennak hmuhmi nih chiti pahnih a chuah kha a fehter.
JMA plot riantuannak cu crystallization riantuannak thazaang hngalh khawhnak ding caah a dang tein an zohfel. Riantuannak thazaang cu Arrhenius equation (Equation (4) ah langhtermi) hmangin tuak a si. Figure 5a nih ln(kg) man le 1/T man karlak pehtlaihnak a langhter. Cun, riantuannak thazaang cu hmanthlak chungin hmuhmi gradient man hmangin tuak a si. Figure 5b nih a thurhnawmmi tlawmtam aa dangmi tangah crystallization riantuannak thazaang man kha a langhter. A phichuak nih a langhter mi cu thil thurhnawmhnak tlawmtam thlennak nih riantuannak thazaang kha a hnorsuan. Thil thurhnawm um loin nickel sulfate crystal pawl an i thlennak thazaang cu 215.79 kJ/mol a si. Thil thurhnawmhnak tlawmtam cu 2.5 g/L a phak tikah, riantuannak thazaang cu 3.99% in a karh i 224.42 kJ/mol tiang a phan. Riantuannak thazaang a karhmi nih hin crystallization kalning thazaang khamnak a karh ti a langhter, cu nih cun crystal tthanchonak le crystal chuahnak a zorter lai. Thil thurhnawmhnak tlawmtam cu 2.5 g/L nak tam a si tikah, crystallization riantuannak thazaang cu a zor ngaingai. Thil thurhnawmhnak 5 g/l ah, riantuannak thazaang cu 205.85 kJ/mol a si, cucu 2.5 g/l thurhnawmhnak tlawmtam ah riantuannak thazaang nakin 8.27% in a niam deuh. Riantuannak thazaang a zor ahcun crystallization kalning a fawiter ti a langhter, cu nih cun crystal tthanchonak le crystal chuahnak a karhter.
(a) ln(kg) le 1/T le (b) riantuannak thazaang Eg aa dangmi thurhnawmhnak tlawmtam ah crystallization i tlukruannak.
Crystal ṭhanchonak lam cu XRD le FTIR spectroscopy hmangin hlathlainak tuah a si, cun crystal ṭhanchonak kinetics le riantuan khawhnak thazaang kha hlathlainak tuah a si. Hmanthlak 6 nih XRD phichuak a langhter. Data cu PDF #08–0470 he aa tlak, cucu α-NiSO4 6H2O (red silica) a si ti a langhter. Crystal cu tetragonal system ah aa tel, vancung phu cu P41212 a si, unit cell parameters cu a = b = 6.782 Å, c = 18.28 Å, α = β = γ = 90°, cun a ngan ning cu 840.8 Å3 a si. Hi hmuhmi hna hi Manomenova le a hawile nih an rak chuahmi hmuhmi hna he aa tlak. 19 NH4+ ions luhternak nih (NH4)2Ni(SO4)2 6H2O sernak zong a chuahpi. Data cu PDF No. 31–0062 ah aa tel. Crystal cu monoclinic system ah aa tel, vancung phu P21/a, unit cell parameters cu a = 9.186 Å, b = 12.468 Å, c = 6.242 Å, α = γ = 90°, β = 106.93°, cun a ngan ning cu 688 Å 388 a si. Hi hmuhmi hna hi Su et al.20 nih an rak langhtermi hlathlainak he aa tlak.
Nickel sulfate lungvar hna i X-ray thlennak sining: (a–b) 0.5%, (c–d) 1%, (e–f) 1.5%, le (g–h) 2% thlaici zat. Orhlei hmanthlak cu kehlei hmanthlak a ngan deuhmi hmuhnak a si.
Hmanthlak 6b, d, f le h ah langhter bantuk in, 2.5 g/L cu chiti chap loin cawhmi ah ammonium tlawmtam a sang bik ri a si. Thil thurhnawmhnak tlawmtam cu 3.75 le 5 g/L a si tikah, NH4+ ions cu crystal sining ah aa tel i a harmi chiti (NH4)2Ni(SO4)2 6H2O a ser. Data ning in, a hlei in 2θ 16.47° le 17.44° ah a thurhnawmhnak a karh tikah a harmi chiti a tthawng bik cu a karh. A harmi chiti a sangbik a karhnak cu chemical tlukruannak phunglam ruangah a si. Sihmanhsehlaw, 2θ 16.47° ah a ttha lomi tlang sang cheukhat hmuh khawh a si, cucu lungvar a tthawngmi thlennak ruangah a si kho. 21 Sining langhternak hmuhmi nih a sang deuhmi cinnak ratio nih a harmi chiti a tthawnnak a zorter ti zong a langhter. Thlaici ratio a sang deuhmi nih cun crystallization kalning kha a rangter, cu nih cun a tlawm deuhmi a chuahter. Hi kongah, crystal ṭhanchonak kalning cu thlaici cungah aa hngat, cun a thar in a chuahmi cu a zormi a tlawm deuhmi supersaturation nih a kham. Cu he aa dang in, thlaici zat a tlawm tikah, a tlawm deuh, cun a tlawm deuh, cun a tlawm deuhmi a tlawm deuh. Hi thil sining nih hin a tlawm deuhmi chiti (NH4)2Ni(SO4)2 6H2O a chuah khawhnak a karhter. Chiti pahnih caah a sangbik thazaang data cu Table 3 ah pek a si.
NH4+ ions a um ruangah host lattice ah zeibantuk buainak asiloah sining thlennak a um zongah hlathlainak tuah awkah FTIR sining langhternak tuah a si. 2% tluk aa thleng lomi thlaici cinnak ratio a ngeimi zohchunhmi hna cu an sining an langhter. Figure 7 nih FTIR sining langhternak phichuak a langhter. 3444, 3257 le 1647 cm−1 ah hmuhmi a kau ngaimi tlangpar hna cu molecule hna i O–H an i hlernak ruangah a si. 2370 le 2078 cm−1 i a sangbik hna nih ti molecule karlak i intermolecular hydrogen pehtlaihnak kha a aiawh. 412 cm−1 ah a ummi band cu Ni-O hlernak hninhnak ruangah a si. Cun, a zalongmi SO4− ions nih 450 (υ2), 630 (υ4), 986 (υ1) le 1143 le 1100 cm−1 (υ3) ah a nganmi hninhnak phun li an langhter. Hmelchunhnak υ1-υ4 nih hninhnonak sining hna kha a langhter, cuka ah υ1 nih a rawk lomi sining (aa tlukmi hlernak) a aiawh, υ2 nih a rawkralmi sining pahnih (a tlukmi hlernak) a aiawh, cun υ3 le υ4 nih a rawkralmi sining pathum (asymmetric le aa tlukmi hlernak, pakhat cio) kha a langhter. 22,23,24 Sining langhternak hmuhmi nih ammonium thurhnawmhnak a ummi nih 1143 cm-1 (hmanthlak ah a senmi kuang in hmelchunhmi) wavenumber ah a dang peak a pek ti a langhter. 1143 cm-1 ah a ummi a dang sangbik nih NH4+ ions a ummi nih, a tlawm le tam zoh loin, lattice sining a thlen, cu nih cun crystal chung i sulfate ion molecule hna i an hninhnak a chuahter.
XRD le FTIR hmuhmi cung ah hram bunh in, crystal tthanchonak le riantuannak thazaang i a cawlcangh ning he aa pehtlaimi, Figure 8 nih NH4+ thurhnawmhnak chapnak he nickel sulfate hexahydrate crystallization kalning a langhter. Thil thurhnawm a um lo ahcun, Ni2+ ions nih H2O he an i pehtlaih lai i nickel hydrate [Ni(6H2O)]2− an ser lai. Cun, nickel hydrate cu SO42− ions he amah tein aa fonh i Ni(SO4)2 6H2O nuclei a ser i nickel sulfate hexahydrate crystals ah a ṭhang. Ammonium thurhnawmhnak tlawm deuh (2.5 g/L asiloah a tlawm deuh) kha cawhmi ah an cawh tikah, [Ni(6H2O)]2− cu SO42− ions he tling tein fonh a har, zeicahtiah [Ni(6H2O)]2− le NH4+ ions pawl cu SO42− ions he fonh awkah an i zuam, asinain ions pahnih he aa pehtlaimi sulfate ions an um rih. Hi thil sining nih hin crystallization riantuannak thazaang a karhter i crystal tthanchonak a zorter. 14,25 Nickel sulfate hexahydrate nuclei cu an ser i crystal ah an ṭhan hnu ah, NH4+ le (NH4)2SO4 ions tampi cu crystal cunglei ah an i hnim. NSH-8 le NSH-12 sample chung i SO4− ion (wavenumber 1143 cm−1) riantuannak phu cu zeicahdah doping tuah loin a um peng timi a fianter. Thil thurhnawmhnak a tam tikah, NH4+ ions cu crystal sining ah an i tel i, chiti pahnih an ser. 16 Hi thil cangmi hi SO42− ions a um lo caah a si, cun SO42− ions nih ammonium ions nakin nickel hydrates ah rang deuh in an i pehtlaih. Hi thil kalning nih hin chiti pahnih hna i an tthanchonak le an tthanchonak a thanchoter. Alloying tuah lio ah, Ni(SO4)2 6H2O le (NH4)2Ni(SO4)2 6H2O nuclei cu hmunkhat te ah an i ser, cu nih cun nuclei hmuhmi a karhter. Nuclei an karh tikah crystal ṭhanchonak a rangter i rianṭuannak thazaang a zorter.
Nickel sulfate hexahydrate kha ti chungah cawh in, ammonium sulfate tlawmpal le tam deuh cawh in, cun crystallization tuahnak ah a tanglei bantuk in langhter khawh a si:
SEM sining langhternak phichuak cu hmanthlak 9 ah hmuh khawh a si. Sining langhternak hmuhmi nih a langhter mi cu ammonium chiti chapmi zat le cinmi zat nih crystal muisam kha tampi in a hnorsuan lo. A chuakmi lungvar hna an ngan ning cu aa thleng lo, asinain hmun cheukhat ahcun lungvar ngan deuh an lang. Sihmanhsehlaw, ammonium chiti tlawm le tam le cinmi zat nih a chuakmi lungvar hna i a tlangpi in a ngan le a hme cung ah a chuahpimi thil sining hngalh khawhnak ding caah a dang sining zohfelnak a herh rih.
NiSO4 6H2O i a vun sining: (a–e) 0.5%, (f–j) 1%, (h–o) 1.5% le (p–u) 2% thlaici zat nih a cunglei in a tanglei tiang NH4+ tlawmtam thlennak a langhter, cucu 0, 1.25, 2.5, 3.75 le 5/L, ciocio an si.
Figure 10a nih a thurhnawmmi tlawmtam aa dangmi lungvar hna i TGA tliknak kha a langhter. TGA hlathlainak cu 2% thlaici cinnak ratio he sample pawl cungah tuah a si. A chuakmi thilri pawl hngalh khawhnak ding caah NSH-20 sample cung ah XRD hlathlainak zong tuah a si. Figure 10b ah langhtermi XRD hmuhmi nih crystal sining thlennak kha a fehter. Thermogravimetric tahnak nih a langhter mi cu sermi lungvar vialte nih 80°C tiang lumnak fek tein an langhter. Cu hnu ah, 200°C tiang lumnak a kai tikah crystal rit cu 35% in a zor. Crystals pawl an ritnak cu a rawhnak ruangah a si, cu ah cun NiSO4 H2O sernak caah ti molecule 5 a tlau. Lungthawhnak cu 300-400°C tiang a kai tikah, lungvar hna an ritnak cu a zor tthan. Crystals pawl an ritmi cu 6.5% hrawng a si, cu lio ah NSH-20 crystal sample ritnak cu tlawmpal a sang deuh, 6.65% tluk a si. NSH-20 sample chung i NH4+ ions pawl NH3 gas ah an i tthennak nih tlawmpal a sang deuhmi tlawmternak a chuahter. Lungthawhnak 300 in 400°C tiang a kai tikah, lungvar hna an ritnak a zor, cu nih cun lungvar vialte cu NiSO4 sining an ngei dih. 700°C in 800°C tiang lumnak karhternak nih crystal sining cu NiO ah a thlen i, SO2 le O2 gas a chuahter.25,26
Nickel sulfate hexahydrate crystals thianhlimnak cu DC-Arc ICP-MS thilri hmangin NH4+ tlawmtam tuaktannak in tuak a si. Nickel sulfate crystals thianhlimnak cu formula (5) hmangin tuak a si.
Ma cu crystal chung i thil thurhnawm hna an rit (mg), Mo cu crystal rit (mg), Ca cu cawhmi chung i thil thurhnawm hna an tamnak (mg/l), V cu cawhmi thilri volume (l) a si.
Figure 11 nih nickel sulfate hexahydrate crystals thianhlimnak a langhter. Thianhlimnak man cu sining 3 i a tlangpi man a si. A phichuak nih a langhter mi cu cinmi zat le thurhnawmhnak tlawmtam nih a chuakmi nickel sulfate crystals thianhlimnak kha direct in a hnorsuan. Thil thurhnawmhnak a tam deuhdeuh ahcun, thurhnawmhnak pawl nih an lak khawh deuhdeuh, cu nih cun a chuakmi lungvar pawl an thianhlimnak a niamter. Sihmanhsehlaw, thil thurhnawm hna an i lak ning cu thil thurhnawm an tlawm le tam cungah aa hngat in aa thleng kho, cun a phichuak graph nih a langhter mi cu thil thurhnawm hna nih an lak ning cu a dihlak in aa thleng lo. Cun, hi hmuhmi nih hin a sang deuhmi cinnak ratio nih crystals thianhlimnak a tthanchoter khawh ti zong a langhter. Hi thil hi a cang khomi a si, zeicahtiah a chuakmi crystal nuclei tam deuh cu nickel nuclei cungah an i fonh tikah, nickel ions cu nickel cungah an i khon khawhnak a sang deuh. 27
Hlathlainak nih a langhter mi cu ammonium ions (NH4+) nih nickel sulfate hexahydrate crystals i a tthawnnak le a tthawnnak sining kha tampi in a hnorsuan, cun a tthawnnak ah thlaici zat nih a chuahpimi huham zong a langhter.
Ammonium 2.5 g/l cung a um ahcun, crystal chuahmi le crystal ṭhanchonak a zor. Ammonium 2.5 g/l cung a um ahcun, crystal chuahmi le crystal ṭhanchonak a karh.
Nickel cawhmi ah thil thurhnawm chapnak nih NH4+ le [Ni(6H2O)]2− ions karlak ah SO42− caah zuamnak a karhter, cu nih cun riantuannak thazaang a karhter. Thil thurhnawm tam tuk chap hnu ah riantuannak thazaang a zornak cu NH4+ ions pawl kha crystal sining chungah an luh caah a si, cucaah chiti (NH4)2Ni(SO4)2 6H2O pahnih a ser.
A sang deuhmi cinnak ratio hmannak nih nickel sulfate hexahydrate i a tthannak, a tthannak le a thianghlimnak a tthanchoter khawh.
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