Nghiên cứu chế tạo điện cực chì dioxit trên nền thép oxi hóa bằng phương pháp kết tủa điện hóa, định hướng ứng dụng làm cực dương trong nguồn điện dự trữ

B GIO DC V O TO VIN HN LM KHOA HC V CễNG NGH VIT NAM HC VIN KHOA HC V CễNG NGH .*** NGễ TH LAN NGHIấN CU CH TO IN CC CHè DIOXIT TRấN NN THẫP OXI HểA BNG PHNG PHP KT TA IN HểA, NH HNG NG DNG LM CC DNG TRONG NGUN IN D TR LUN N TIN S HểA HC H Ni, 2017 VIN HN LM KHOA HC B GIO DC V O TO V CễNG NGH VIT NAM HC VIN KHOA HC V CễNG NGH .*** NGễ TH LAN NGHIấN CU CH TO IN CC CHè DIOXIT TRấN NN THẫP OXI HểA BNG PHNG PHP KT TA IN HểA, NH HNG NG DNG LM CC DNG TRONG NGUN IN D TR LUN N TIN S HểA HC Chuyờn ngnh : Húa lý thuyt v húa lý Mó s: 62.44.01.19 Ngi hng dn khoa hc: PGS TS inh Th Mai Thanh i tỏ, TS Doón Anh Tỳ H Ni, 2017 LI CAM OAN Tụi xin cam oan lun ỏn ny l cụng trỡnh nghiờn cu ca riờng tụi di s hng dn khoa hc ca PGS TS inh Th Mai Thanh v i tỏ, TS Doón Anh Tỳ Lun ỏn khụng trựng lp vi bt k cụng trỡnh khoa hc no khỏc Cỏc kt qu v s liu lun ỏn l trung thc v cha c cụng b trờn no ngoi nhng cụng trỡnh ca tỏc gi Tỏc gi lun ỏn Ngụ Th Lan i LI CM N Tụi xin by t lũng bit n sõu sc ti PGS TS inh Th Mai Thanh v i tỏ TS Doón Anh Tỳ ó ó tn tõm hng dn khoa hc, nh hng nghiờn, cu ng viờn khớch l v to mi iu kin thun li cho tụi sut quỏ trỡnh thc hin lun ỏn Tụi xin trõn trng cm n ban lónh o Vin K thut Nhit i vin Hn lõm Khoa hc v Cụng ngh Vit Nam cựng cỏc cỏn b Vin ó quan tõm giỳp v to iu kin thun li cho tụi quỏ trỡnh hc v nghiờn cu ti Vin Tụi xin chõn thnh cm n th trng b mụn Cụng ngh Húa hc, th trng khoa Húa Lý K thut- Hc vin K thut Quõn s ó luụn giỳp , ng h v to iu kin v thi gian cho tụi sut quỏ trỡnh thc hin v bo v lun ỏn Cui cựng tụi xin by t li cm n sõu sc nht n gia ỡnh, ngi thõn v bn bố ó luụn quan tõm, khớch l, ng viờn v to mi iu kin thun li cho tụi sut thi gian thc hin lun ỏn ny Tỏc gi lun ỏn Ngụ Th Lan ii MC LC Trang M U CHNG TNG QUAN 1.1 Cu trỳc tinh th v tớnh cht húa lý ca chỡ ioxit 1.2 Cỏc phng phỏp tng hp chỡ ioxit 1.2.1 Tng hp bng phng phỏp húa hc 1.2.1.1 Phng phỏp oxi húa 1.2.1.2 Phng phỏp thy phõn 1.2.2 Tng hp bng phng phỏp in húa 1.2.2.1 C ch quỏ trỡnh kt ta in húa PbO2 1.2.2.2 Ch to in cc chỡ ioxit trờn nn kim loi quý 1.2.2.3 Ch to in cc chỡ ioxit trờn nn niken 1.2.2.4 Ch to in cc chỡ ioxit trờn nn titan 1.2.2.5 Ch to in cc chỡ ioxit trờn vt liu nn nhụm v ng 10 1.2.2.6 Ch to in cc chỡ ioxit trờn nn thộp khụng g 12 1.2.2.7 Ch to in cc chỡ ioxit trờn nn graphit 13 1.2.2.8 Ch to in cc chỡ ioxit trờn nn cacbon thy tinh (glassy cacbon) 14 1.2.2.9 Ch to in cc chỡ ioxit trờn nn ebonex 15 1.2.2.10 Ch to in cc chỡ ioxit dng composit 16 1.3 ng dng ca chỡ ioxit 17 1.3.1 17 PbO2 dựng cht thut 1.3.2 19 in cc tr PbO2 1.3.2.1 in cc tr PbO2 dựng tng hp in húa 19 1.3.2.2 in cc tr PbO2 dựng cụng ngh x lý mụi trng 20 1.3.2.3 in cc tr PbO2 dựng lm anụt bo v catụt bng phng phỏp 22 dũng ngoi 1.3.3 22 in cc PbO2 dựng ngun in chỡ 1.3.3.1 Phõn loi ngun in chỡ 22 iii 1.4 1.5 1.3.3.2 in cc dng PbO2 dựng c quy chỡ 24 1.3.3.3 in cc dng PbO2 pin chỡ d tr 28 Oxit st v cỏc phng phỏp tng hp mng oxit v ng dng 32 1.4.1 32 Cỏc loi oxit st 1.4.2 33 Cỏc phng phỏp tng hp mng oxit st 1.4.2.1 33 To lp oxit phỏt trin trờn nn thộp bng phng phỏp húa hc 1.4.2.2 To lp oxit phỏt triờn trờn nn thộp bng phng phỏp oxi húa in húa 35 1.4.3 37 Kh nng ng dng ca vt liu mng oxit Tỡnh hỡnh nghiờn cu v tng hp v ng dng PbO2 nc 40 CHNG II THC NGHIM 44 2.1 Húa cht v iu kin thc nghim 44 2.1.1 44 Húa cht 2.1.2 45 Oxi húa nn thộp bng phng phỏp húa hc 2.2 Cỏc phng phỏp nghiờn cu 46 2.2.1 46 Cỏc phng phỏp in húa 2.2.1.1 Phng phỏp quột th ng 46 2.2.1.2 Phng phỏp dũng tnh 47 2.2.2 49 Cỏc phng phỏp phõn tớch 2.2.2.1 Kớnh hin vi in t quột (SEM) 49 2.2.2.2 Nhiu x tia X( XRD )v tớnh thnh phn pha t ph XRD s dng phn 49 mm 2.2.2.3 Tỏn x nng lng tia X (EDX) 52 2.2.2.4 Phng phỏp chun Pb2+ 52 2.2.3 Phng phỏp o bỏm dớnh ca PbO2 vi nn thộp 53 2.24 Phng phỏp o dy ca mng oxit 53 CHNG III KT QU V THO LUN 54 3.1 Nghiờn cu ch to nn thộp oxi húa dựng cho in cc PbO2 54 3.1.1 54 Oxi húa nn thộp bng phng phỏp húa hc 3.1.1.1 nh hng ca nng NaOH 54 iv 3.1.1.2 nh hng ca nng NaNO3 55 3.1.1.3 nh hng ca nng NaNO2 57 3.1.1.4 nh hng ca nhit 59 3.1.1.5 nh hng ca thi gian oxi húa 61 3.1.1.6 Phõn tớch thnh phn, hỡnh thỏi pha ca mng oxit 62 3.1.2 65 Oxi húa nn thộp bng phng phỏp in húa 3.1.2.1 Xỏc nh in th oxi húa thộp dung dch kim 65 3.1.2.2 nh hng ca mt dũng 66 3.1.2.3 nh hng ca nng NaOH 69 3.1.2.4 nh hng ca nhit 71 3.1.2.5 nh hng ca thi gian oxi húa 74 Phõn tớch thnh phn, hỡnh thỏi cu trỳc pha ca mng oxit 76 3.1.3 Kho sỏt iu kin kt ta in húa PbO2 lờn nn thộp oxi húa v la 79 chn lp vt liu chuyn tip 3.1.3.1 Xỏc nh in th kt ta PbO2 ca dung dch Pb(NO3)2 79 3.1.3.2 80 nh hng ca mt dũng n bỏm dớnh ca lp PbO2 3.1.3.3 84 nh hng ca mt dũng n hỡnh thỏi hc ca lp PbO2 3.1.3.4 86 nh hng ca mt dũng n thnh phn pha ca lp PbO2 3.1.3.5 88 Kho sỏt kh nng phúng in ca in cc PbO2 3.2 Nghiờn cu cỏc yu t nh hng n quỏ trỡnh kt ta in húa PbO2 93 trờn nn thộp oxi húa in húa 3.2.1 93 nh hng ca mt dũng 3.2.2 nh hng ca nng Pb(NO3)2 94 3.2.3 98 nh hng ca nhit 3.2.4 102 nh hng ca pH 3.2.5 nh hng ca nng Cu(NO3)2 105 3.3 ỏnh giỏ kh nng lm vic ca in cc PbO2/Fe3O4H/thộp dung 110 dch in li H2SiF6v CH3SO3H 3.3.1 nh hng ca nng dung dch in ly n kh nng lm vic ca v 110 in cc 3.3.2 nh hng ca nhit dung dch in ly n kh nng lm vic ca 115 in cc 3.3.3 nh hng ca ca th tớch dung dch in ly n kh nng lm vic 119 ca in cc KT LUN 122 TI LIU THAM KHO 125 vi DANH MC CC K HIU V CH VIT TT dE/dt : S bin i in th theo thi gian EDX : Tỏn x nng lng tia X E0 : in th mch h MRB : B ngun in chỡ d tr loi nh MRB-S : B ngun in chỡ d tr loi nh cú mt rónh dn dung dch in li MRB-D : B ngun in chỡ d tr loi nh cú hait rónh dn dung dch in li MSA : axit metansunfonic M : mol/L FeOhh/thộp : Lp FeO trờn nn thộp c to thnh bng phng phỏp oxi húa húa hc Fe3O4h/thộp : Lp Fe3O4 trờn nn thộp c to thnh bng phng phỏp oxi húa in húa PANi : Polyanilin PVP : Polyvinylpyrolidon PbO2/FeOhh/thộp : Lp PbO2 kt ta in húa trờn mng FeO oxi húa nn thộp bng phng phỏp oxi húa húa hc PbO2/Fe3O4h/thộp : Lp PbO2 kt ta in húa trờn mng FeO oxi húa nn thộp bng phng phỏp oxi húa in húa Pwp : H s tng quan RVC : 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Trung Sn, inh Th Mai Thanh, nh hng ca hỡnh thỏi, cu trỳc pha ca lp PbO2 kt ta in húa trờn nn thộp n kh nng lm vic va in cc PbO2 pin chỡ d tr,Tp Húa hc 54(3)2016, p 321-326 Ngụ Th Lan, Doón Anh Tỳ, on Tin Phỏt, inh Th Mai Thanh, So sỏnh kh nng phúng in ca cp in cc Pb-PbO2trong dung dch axit metasunfonic v axit florosilixic, Tp Húa hc54(5) 2016, p 542-548 Doón Anh Tỳ, Ngụ Th Lan, inh Th Mai Thanh, Bng c quyn sỏng ch: Quy trỡnh sn xut in cc dng ca pin chỡ d tr nng lng cao S 15371, ngy cp bng 11/4/2016 ... ĐÀO TẠO VÀ CÔNG NGHỆ VIỆT NAM HỌC VIỆN KHOA HỌC VÀ CÔNG NGHỆ …… ….***………… NGÔ THỊ LAN NGHIÊN CỨU CHẾ TẠO ĐIỆN CỰC CHÌ DIOXIT TRÊN NỀN THÉP OXI HÓA BẰNG PHƯƠNG PHÁP KẾT TỦA ĐIỆN HÓA, ĐỊNH HƯỚNG ỨNG. .. cực dương cho nguồn điện chì dự trữ Nội dung luận án: Nghiên cứu oxi hóa thép 08K phương pháp hóa học phương pháp điện hóa Nghiên cứu yếu tố ảnh hưởng đến trình kết tủa điện hóa PbO2 thép, thép. .. đioxit thép phương pháp kết tủa điện hóa, định hướng ứng dụng làm điện cực dương nguồn điện đặt với mục tiêu nội dung sau: Mục tiêu luận án: Tổng hợp điện hóa PbO2 thép đáp ứng yêu cầu làm điện cực