4 2

1998 5

Vol. 4 No. 2
May 1998

EL ECTROCHEM ISTR Y

3
( 510275)

4f 0 14 ,

, . ,
. , ,
. ,
.

,
, .

1
, Nd2Fe2B
,Nd Nd2Fe . ,
.
[ 1 ,2 ] .
SD K Li F2NdF3 Nd2Fe , 99. 9 % ,
85 % ; 3 kA , 800 [ 3 ] . Nd2Fe2B , Dy Nd ,

. NdF32DyF32Nd2 O32Dy2 O3 Nd2

Dy [ 4 ] , Dy Nd2Fe2B .

, Sm2Fe2N
,
, [ 5 ] ; Nd2Fe2B , [ 6 ] .
2 Gd2Co Ho2Co Gd2Fe Tb2Fe ,
. 2 , . ,
. , .
, .
2 , Sm2Co Gd2Co
Nd2Fe
Dy2Fe ( 1) [ 7 - 12. ] .

1997211226
3

 1998

122

1 2
Tab. 1 Electrodeposition of rare eart h2iron group alloys in organic electrolytes

Sm2Co

PC

Sm ( NO3 ) 32Co ( NO3 ) 2

Gd2Co

GdCl32CoCl2

DMF

Dy2Fe

DMF

RE2Ni Fe ,Co

PC ,DMF ,DMSO

Nd2Fe

0. 1mol
L

- 1

NdCl32FeCl2

0. 1mol
L

- 1

DyCl32FeCl2

0. 1mol
L

- 1

,
B Hmax 10M GOe

, Gd2Co [ 8 ] . 2
DM F Nd2Dy , 5 mA cm - 2 , ;

, 515 mA
cm - 2 , 60 %[ 11 ] .
: ( 1 )
, . ( 2)
,
, . ,
, .
100 2 , La2Co
Nd2Fe Tb2Ni Tm2Co
Yb2Co 2 , [ 13 ] .

2
CoOO H MnO2 L nCoO3 L nMnO3

,
. ,
. La ( NO3 ) 3 Co ( Ac) 2 Mn ( NO3 ) 2
, L nCoO3 L nMnO3 . L n3 + CoOO H MnO2
, CoOO H MnO2 , Co2O .
CoOO H : Yb3 + > Y3 + > Dy3 + > Gd3 + Sm3 + Nd3 + > Pr3 + > La3 + [ 14 ] .
( SDC) ( YSZ) , L n1 - xA x MnO3 ( A =
) Ni2 , .
, ( CeO2 ) 0. 8 ( SmO1. 5 ) 0. 2 . Ni2 YSZ
Ni2CeO x
Ni2SDC Ni2PrO x ,
[ 15 ] . L n1 - xA x MnO3 , Gd1 - xA x MnO3 ,
, , YSZ [ 16 ] . Gd CeO2
500600 , [ 17 ] .
MnO2 , .

, . CaMnO3 , Ca

 2 :

123

, . , Ca0. 9 Nd0. 1 - y MnO3 - 1. 0 102

S
cm - 1 . , , ,

[ 18 ] .
LaNi5
, . ,

, , , MmNi3. 5 Co 0. 5 Mn0. 4Al0. 3

. Ni LaCl3 KCl2NaCl , La2Ni ,
; 923 K , LaNi5
[ 19 ] . 2
2ED TA2 , La2Ni [ 20 ] .

3
, .
.
, ,
. YCl3 TbCl3 6 H2 O DM F , Y Tb
, . AlCl3 , Y2 Tb2Al
, [ 21 ] .
Dy3 +
Sm3 + ,22 ( MSM )
. MSM 180 V , . RE3 + ,
RE3 + , [ 22 ] .

,
. Tb3 +
, : / In2SnO/ / Tb / Al ,
. Eu3 + , : /
In2SnO/ Eu3 + / / Mg/ Ag , 12 V [ 23 ] .

Y 6 mol/ L KO H ,
, .
, Y Pd. , YH3 H Y .
, [ 24 ] .

4
2 2 ,

,
. ( 2 ) ,
, [ 25 - 27 ] .

 1998

124

2
Tab. 2 Electrodeposition of rare eart h chakogenides

/ mo1L - 1
0. 05 Y( NO) 3 + 0. 05CH3 CSN H2 + 0. 05NaAc

, , ITO

Y2S , :1. 85 eV

0. 05 Y( NO) 3 + 0. 05SeO2 + 0. 05

Y2Se

0. 05 Y( NO) 3 + TeO2 + 0. 05NaAc

Y2 Te

( )

Sm2 Te

Nd ( NO3 ) 3 Cu ( NO3 ) 2 , , 940

Nd2 CuO4 , [ 28 ] .

5
,

,
Y2Ba2Cu2O . ,
.
, . Y
( NO3 ) 3
6 H2 O2Ba ( NO3 ) 22Cu ( NO3 ) 2 8 H2 O2DMSO , Ag ,

, 3 [ 29 ] .
3 DMSO
Tab. 3 Electrodepostion of YBaCu in DMSO

MgO ( )

- 2. 5 V ( vs Ag/ AgNO3 )

: Y/ Ba/ Cu/ O/ S/ Ag

T c/ K

1/ 2. 58/ 5. 15/ 11. 39/ 0. 52/ 0. 14

24 V

1/ 2. 5/ 3. 1/ 8. 1/ 0. 27/ 0. 13

78

YSZ ( )

24 V

1/ 2. 1/ 2. 73/ 7/ 0. 38/ 0. 1

91

Ni

24 V

1/ 2. 6/ 3. 28/ 7. 9/ 0. 67/ 0

74

YBa2 Cu3 O72.

, , 98 K , ,
T c [ 30 ] . ,
.

6

, .
Ce ( ) , 20 .
,
[ 31 ] . Ce ( SO4 ) 2 ,

 2 :

125

,
[ 32 ] . Zn2Ni Ce ( SO4 ) 2 ,
, [ 33 ] . Ni2Fe
Sm2 O3 , , ,
[ 34 ] . Ni2S CeCl3 , Ni2Ce2S , S 30 % ,
;Ce [ 35 ] .
, , La2 O3
, Ag2La2 O3 ,

,
, [ 36 ,37 ] . Ni2SiC ,
, SiC , , .
f , , SiC ,
, SiC [ 38 ] .

7
, . NiSO4
+ N H4 Cl + H3BO322La2 O3 , Ni2La2 O3 , ( 9002
1000 ) . , La2 O3 ,
NiO2La2 O3 . , La3 + , Ni

, [ 39 ] . , Fe26CrlMo
, 512 m Ni2La2 O3 , [ 40 ] .
. Cl -
1000 pp mCeCl3
PrCl3
NdCl3 AA7075 10 .
, [ 41 ] . Sm3 + L Y12CZ
Cl - , ,
, ( 4) [ 42 ] .
4 SmCl3 L Y12CZ NaCl
Tab. 4 Corrosion inhibition of SmCl3 on L Y12CZ aluminium alloy in NaCl solution

/ day

10

20

30

/ mm 0. 5 mol/ L NaCl

0. 018

0. 045

0. 075

0. 107

0. 05 mol/ L NaCl + 1 000 ppm SmCl3

0. 018

0. 011

0. 015

0. 017

/ %

550. 5

75. 6

83. 6

86. 0

( SDS) , .
SDS ( 80 pp m) La3 + , La3 + 100 120 pp m ,La3 + SDS

126

1998

[ 43 ] .

8
8. 1
. SmCl3
,O2 + 2 H + 2e O 3 Sm3 + + H2 O. O 3 ,
, .
2

, [ 44 ] .

8. 2 CeO2
Ce ( NO3 ) 3
6 H2 O N H4 NO3 0. 1 mol/ L Ce ( ) 0. 1 mol/ L N H4 NO3 ,
, , CeO2 . 26 80 , 6 nm
16 nm. 0. 5 mA/ cm2 3. 0 mA/ cm2 , 18 nm 6 nm [ 45 ,46 ] .

8. 3 RuO2 / Ti
RuO2 / Ti , RuO2 / Ti
RuO2 , . SnO2 ,

. RuCl3 LaCl3 ( Ru
La = 7
3 ) RuO 2 - La2 O3 / Ti , H2 SO4
, RuO2 / Ti .
, , , [ 47 ] .

8. 4
, 0. 120. 5 %. ,
,CaCl2 , 1223 K , ,
O2 - CO CO2 , 0. 57 % 0. 01 % .
, [ 48 ] .

8. 5 Ce SnO2
H2 S , ,
. SnO2 H2 S
, SnO2 [ 49 ] .

8. 6
,


, .
,
[ 50 ] .

 2 :

127

Electrochemical Preparation of Rare Eart h Functional Materials

and Application of Rare Eart h to Electrochemistry
Yang Qiqin 3 Tong Yexiang
( School of Chem . an d Chem . Engi n . , Zhongshan U ni v . , Gu uan gz hou 510275)

Abstract The

new progress and related mechanism of t he elect rochemical preparation

of rare eart h materials ( magnet s , magneto2optic materials , battery materials , luminescent devices ,
semiconductors , superconductors) and t he application of rare eart h to t he elect rochemical areas ( e.
g. elect roplating ,corrosion ,elect rosynt hses) have int roduced.

Key words Rare eart h f unctional material , Application of

rare eart h , Elect rochemical

preparation

Reference s
1 Yang Qiqin et al. Preparation of rare eart h alloys by cat hodic alloying. Rare Metals ,1994 ,14 ( 1) :13
2 Tong Xexiang ,Liu Guankun , Yang Qiqin , Hong Huichan , Preparation of yttrium2barium2copper tinary master
alloy by electrolysis from molten fluoride2oxide. J Rare Eart hs ,1995 ,12 ( 4) :271
3 Tamamura H. Process for preparation of neodymium or neodymium alloy. US 4 ,966 ,661
4 Hasegawa T , Mizuguchi T. Manufacture of neodymium2dysprosium alloy for magnets. J P 07 138 ,779
5 Tooda H. Rare eart h2iron2nitrogen magnet power and its manufacture. J P 07 310 ,102
6 , . Nd2Fe2Bx . ,1997 ,26 ( 23) :24
7 Sato Y et al. Electrodeposition of Sm2Co from formamide solution. Chemistry Letters ,1990 , ( 4) :1471
8 Sato Y et al. Electrolytic preparation of samarium2cobalt t hin films and t heir magnetic properties. Plating and
Surface Finishing ,1993 ,90 :72
9 Usuzaka N , Yamaguchi H , Watanabe Y. Preparation and magnetic properties of Co2 Gd amorp hous alloy film by
t he electroplating met hod. Mater. Sci. Eng. ,1988 ,99 :105
10 Yoshimoto N et al. Nd2Fe electrodeposition in organic electrolyte. Denki Kagaku ,1994 ,62 ( 10) :982
11 . 2 . , ( ) ,1992 ,43 ( 1) :36
12 Shinors O. Electroplating magnetic t hin and its manufacture. J P 05 217 ,744
13 . 22 . ,
1997
14 Matsumoto Y , Ohmura H , Guto T. Effect of lant hanide ions on t he electrodeposition of cobalt and manganese
oxides. J . Electroanal. Chem ,1995 ,399 ( 122) :91
15 Egchi K et al. Activities of rare2containng oxides as electrode for oxide conductor. J . Alloys and Compounds ,

128

1998

1993 ,192 :59

16 Takeda Y ed al. Gd1 - xAx MnO3 for t he electrode of solid fuel cells. J . Electrochem. Soc. ,1997 ,144 :2810
17 Sirman J , Kilner J , Surface exchange properties of Ce0. 9 Gd0. 1 O2 - x coated wit h L SFC. J . Electrochem. Soc. ,
1996 ,3 ( 10) :L229
18 Morimoto H , Esaka T , Kamata M. Preparation of t he Perovskite2type oxide Ca0. 9 Nd0. 1 - y MnO3 - . Denki Ka2
gaku. 1996 ,64 ( 10) :1 084
19 Okido M , Ichino R , Tamura R. Formation of LaNi5 film on Ni substrate by electrolysis in molten chloride and
its hydrogen absoption property. Proc2Electrochem. Soc. ,1996 ,96 - 7 ( molten Salts) :320
20 . ,1995 ,11 ( 12) :1110
21 . . ( ) ,1995 ,46 ( 12) :1193
22 Bachir S et al. Electroluminescence of Dy3 + ions in polycrystalline semiconducting zinc oxide. J Phys. Chem ,
1995 ,99 ( 15) :5 674
23 Kido J , Nagai K , Okamoto Y. Organic electroluminescent devices using complexes. J . Alloy and Compounds ,
1993 ,193 :30
24 Notten P et al. Optical switching of Y2hydride t hin film electrodes. J . Electrlchem. Soc. , 1996 , 143 ( 10 ) :
3 348
25 Mohite U K , et al. Electrosynt hesis of yttrium chalcogenides from a non2aqueous bat h. Appl. Surf . Sci. ,
1996 ,92 :151
26 J undale S B , Lodhande C D. Electrosynt hesis of Sm2 Te films. Mater. Chem. Phys. ,1994 ,37 ( 4) :333
27 Jodgudri S A et al. Electrosynt hesis of Sn sulfide and Y sulfide films. J . Pure Appl. Phys. ,1994 ,32 ( 9) :772
28 Janes R et al. Electrodeposition t hin film of rare eart h metal oxocuprates. J . Mater ,Chem ,1996 ,6 ( 2) :183
29 Bhattacharya R N et al. YBaCuO superconductor t hin films via an electrodeposition process. J . Electrochem.
Soc. 1991 ,138 ( 6) :1643
30 Tomkiewicz M et al. Electrochemical deposition of high Tc superconducting t hin films. Proceedings of t he So2
ciety of Photo2Optical Instrumentation Engineers , Vol. 1287 ( 1990) :48
31 . . ,1994 ,27 ( 9) :4
32 . . ,1990 ,23 ( 7) :28
33 , . . ,1992 , ( 3) :18
34 . . ,1995 ,14 ( 1) :40
35 . Ni2CeiS . ,1994 ,13 ( 4) :18
36 . Ag2La2 O3 . ,1990
37 , . Ag2La2 O3 . ( ) ,1995 ,46 ( 3) :253
38 . . ,1995 15 ( 4) :11
39 . Ni2La2 O3 . ,1995 ,13 ( 4) :328
40 . Ni2La2 O3 Fe26CrlMo . ,1997 ,15 ( 1) :40
41 Arnott D R , Hinton B and Ryan N F. Cationic2film forming inhibitor for t he protection of t he AA7705 alumi2
um alloy against coorosion in aqueous chloride solution. Corrosion ,1989 ,45 ( 1) :12
42 , , . Sm . ,1997 ,9

 2 :

129

( 1) :44
43 Mu G N et al. Effect of metallic cations on corrosion inhibition of an anionic surfactant for mild steel Corrosion ,
1996 ,52 ( 11) :853
44 Yamanaka I , Otsuka K. Partial oxidation of alkanes and aromatics wit h activated oxygen over an SmCl3 - em2
bedded grap hite cat hode. J . Alloy and Compounds ,1993 ,193 :56
45 Zhou Y , Phillips R , Switzer J . Electrochemical synt hesis and sintering of nanocrystalline cerium ( IV ) oxide
powers. J . Am. Ceram. Soc. ,1995 ,78 ( 4) :981
46 Zhou Y , Switzer J . Growt h of cerium ( IV) oxide films by electrochemical generation of base met hod. J . Alloys
and Compounds ,1996 ,237 :1
47 Murakami Y et al. Effects of rare eart h chlorides on t he preparation of porous rut henium oxide electrodes. J .
Alloys and Compounds ,1996 ,239 :111
48 Okabe T et al. Electrochemical deoxidation of Y2O solid solutions. J . Alloys and Compounds ,1996 ,237 :150
49 ,Ce SnO2 . 1997 ,15 ( 1) :11
50 , , . . ,1996 ,14 ( 1) :72