CN1847156A - Prepn process of composite tin oxide conducting powder with blended antimony and RE - Google Patents
Prepn process of composite tin oxide conducting powder with blended antimony and RE Download PDFInfo
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- CN1847156A CN1847156A CN 200610025108 CN200610025108A CN1847156A CN 1847156 A CN1847156 A CN 1847156A CN 200610025108 CN200610025108 CN 200610025108 CN 200610025108 A CN200610025108 A CN 200610025108A CN 1847156 A CN1847156 A CN 1847156A
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Abstract
The preparation process of composite tin oxide conducting powder with blended antimony and RE includes the following steps: 1. compounding mixture solution with RE oxide(s), tin powder, antimony oxide, complexant and nitric acid; 2. compounding alkali solution with ammonia water; 3. dispersing conducting core material in water solution; 4. dropping simultaneously the mixture solution a the alkali solution into deionized water while stirring to obtain precipitant; and 5. washing the precipitant separately with deionized water and organic solvent under stirring, stoving, grinding, sieving and calcining to obtain the composite tin oxide conducting powder with blended antimony and RE. Thus prepared composite tin oxide conducting powder has obviously raised use temperature over 900 deg.c.
Description
Technical field
The present invention relates to a kind of preparation method who can be used for the conducting powder of conductive coating, electro-conductive fiber and conductive plastics, relate to a kind of preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth in particular.
Background technology
Conductive powder makes an addition in fiber, coating, plastics, rubber, the synthetical glue etc. as a kind of functional stuffing, make it have functions such as conduction, antistatic, shielding electromagnetic wave, be widely used in industries such as Aeronautics and Astronautics, military affairs, electronics, automobile, communication, information.Now developed metal system, carbon system, burning system and compound be conductive powder.Metal is that powder mainly is silver powder, nickel powder and copper powder etc.Silver powder has that chemical property is stable, non-corrosibility is strong, electroconductibility is high, but price is expensive, be mainly used in the important military field, copper has cheap cost, suitable with the electroconductibility of silver, but its easy oxidation, the electroconductibility instability, need it is carried out special processing, could obtain more stable copper is conductive powder.The electroconductibility of nickel is also bad, but the focus of Recent study, its reason is the moderate cost of nickel, chemical stability is good, erosion resistance is strong, and ferromegnetism is good, and the electromagnetic shielding that is used for electronics is especially effective, but its ratio is great, sedimentation easily, and color is darker.The carbon black low price, raw material is easy to get, and proportion is less, but carbon black, graphite are aterrimus, and color is single, and decorative effect is poor.Therefore in recent years, be devoted to develop the compound-type conducting powder.The compound-type conducting powder be material with a kind of inexpensive, light weight as substrate or core, coat one deck or which floor chemical stability is good, erosion resistance is strong, specific conductivity is high conducting material on its surface and the matrix material that obtains.Material as substrate (or core) has mica, graphite, barite, titanium dioxide, carbon fiber, trichroite, lime feldspar, pyrophyllite, kaolin etc.; Conducting material has silver, copper, nickel and contains mix in antimony oxidation tin crystal and the tindioxide Sb, F, In and the semiconductor powder that forms.It is the defective of conductive powder that the conductive powder of the compound series of wherein light metal oxide has been filled up carbon black system, metal well.In China, the base material of use has mica, barite, titanium dioxide etc., and electro-conductive material is at SnO
2Middle doping Sb, F.But above-mentioned composite conductive powder use temperature is on the low side, is no more than 800 ℃ usually.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth, and this method can improve the use temperature of composite conductive powder.
The technical solution adopted in the present invention: a kind of preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth comprises the following steps:
Mixture and glass putty, antimonous oxide, complexing agent and the nitric acid that a. will be selected from a kind of rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or the scandium or more than one rare earth oxides mix, the preparation mixing solutions, the concentration of tin is controlled to be 0.05～2.5mol/L in the described mixing solutions, and the mol ratio of tin and rare earth oxide, antimonous oxide is controlled to be n
Sn: n
RE: n
Sb=40～95: 0.0735～30: 0.1～30, described complexing agent is selected from C
2～C
8Organic acid or its mixture, the mol ratio of complexing agent and tin, rare earth oxide and antimonous oxide sum is n
Complexing agent: n
(Sn+Sb+RE)=0.1～2: 1, concentration of nitric acid is controlled to be 0.5～12mol/L;
B. prepare the alkali lye of 0.5～12mol/L with ammoniacal liquor;
C. conductive core material is dispersed in the aqueous solution, described conductive core material is selected from one or more the mixture in quartz, kaolin, mica, lime feldspar, pyrophyllite or the trichroite, or a kind of oxide compound or more than one hopcalites in the titanium, magnesium, calcium, barium, strontium, nickel, iron, or a kind of vitriol in the calcium, barium, strontium or the mixture of more than one vitriol, the mol ratio of conductive core material and tin, rare earth oxide and antimonous oxide sum is n
Conductive core material: n
(Sn+Sb+RE)=1～85: 15～99, under agitation with and the mode that adds of drip add above-mentioned mixing solutions and alkali lye, control pH value is 3-11, temperature of reaction is 1-80 ℃, the acquisition coprecipitate.Under constantly stirring evenly and drip add by the mixing solutions of step a preparation and described alkali lye in deionized water, obtain throw out, control pH value is 3～11, temperature of reaction is 1～80 ℃;
D. use deionized water and C respectively
1-C
3The organic solvent washing throw out, the throw out after the washing grinds, crosses the 100-200 mesh sieve at 100～105 ℃ of following oven dry 1～2h, the throw out after sieving obtains mixing the composite tin oxide conducting powder body of antimony and rare earth at 400～1100 ℃ of calcining 0.5～5h down.
Complexing agent described in the step a is selected from citric acid or tartrate or citric acid and tartaric mixture.
C described in the steps d
1～C
3Organic solvent be ethanol.
The invention has the beneficial effects as follows: the use temperature of the composite tin oxide conducting powder of mixing antimony and rare earth of the present invention's preparation obviously improves, can be above 900 ℃.
Embodiment
Below by embodiment the present invention is described in further detail: a kind of preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth, comprise the following steps: that a. will be selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, a kind of rare earth oxide in yttrium or the scandium or the mixture and the glass putty of more than one rare earth oxides, antimonous oxide, complexing agent and nitric acid mix, the preparation mixing solutions, the concentration of tin is controlled to be 0.05～2.5mol/L in the described mixing solutions, tin and rare earth oxide, the mol ratio of antimonous oxide is controlled to be n
Sn: n
RE: n
Sb=40～95: 0.0735～30: 0.1～30, described complexing agent is selected from C
2～C
8Organic acid or its mixture, the mol ratio of complexing agent and tin, rare earth oxide and antimonous oxide sum is n
Complexing agent: n
(Sn+Sb+RE)=0.1～2: 1, concentration of nitric acid is controlled to be 0.5～12mol/L; B. prepare the alkali lye of 0.5～12mol/L with ammoniacal liquor; C. conductive core material is dispersed in the aqueous solution, described conductive core material is selected from one or more the mixture in quartz, kaolin, mica, lime feldspar, pyrophyllite or the trichroite, or a kind of oxide compound or more than one hopcalites in the titanium, magnesium, calcium, barium, strontium, nickel, iron, or a kind of vitriol in the calcium, barium, strontium or the mixture of more than one vitriol, the mol ratio of conductive core material and tin, rare earth oxide and antimonous oxide sum is n
Conductive core material: n
(Sn+Sb+RE)=1～85: 15～99, under agitation with and the mode that adds of drip add above-mentioned mixing solutions and alkali lye, control pH value is 3-11, temperature of reaction is 1-80 ℃, the acquisition coprecipitate.Under constantly stirring evenly and drip add by the mixing solutions of step a preparation and described alkali lye in deionized water, obtain throw out, control pH value is 3～11, temperature of reaction is 1～80 ℃; D. use deionized water and C respectively
1～C
3The organic solvent washing throw out, the throw out after the washing grinds, crosses the 100-200 mesh sieve at 100～105 ℃ of following oven dry 1～2h, the throw out after sieving obtains mixing the composite tin oxide conducting powder body of antimony and rare earth at 400～1100 ℃ of calcining 0.5～5h down.Complexing agent described in the step a is selected from citric acid or tartrate or citric acid and tartaric mixture.C described in the steps d
1～C
3Organic solvent be ethanol.
Embodiment 1
In the beaker of 1000ml, add 0.0748g lanthanum sesquioxide, 0.0911g antimonous oxide, the glass putty of 29.6725g, the citric acid of 48g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 5000ml, add 226g silica powder (400 order), add deionized water 2000ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing lanthanum and antimony of 201.5 Ω cm.
Embodiment 2
In the beaker of 1000ml, add 0.0773g neodymium sesquioxide, 0.0911g antimonous oxide, the glass putty of 29.6725g, the citric acid of 48g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 300ml that is made into 3mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 17.57g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 1000 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of the neodymium-doped of 12.0 Ω cm and antimony.
Embodiment 3
In the beaker of 1000ml, add 13.7652g samarium sesquioxide, 11.5066g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 300ml that is made into 3mol/L in the beaker of 1000ml is stand-by.
In the beaker of 5000ml, add 367g silica powder (400 order), add deionized water 3000ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 1100 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing samarium and antimony of 210 Ω cm.
Embodiment 4
In the beaker of 1000ml, add 14.3091g Gadolinium trioxide, 11.5066g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 17.57g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing gadolinium and antimony of 27.3 Ω cm.
Embodiment 5
In the beaker of 1000ml, add 0.0857g erbium oxide, 0.1777g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 5000ml, add 227g silica powder (400 order), add deionized water 300ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of the er-doped of 170 Ω cm and antimony.
Embodiment 6
In the beaker of 1000ml, add 0.0739g praseodymium sesquioxide, 0.1777g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 17.60g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing praseodymium and antimony of 2.1 Ω cm.
Embodiment 7
In the beaker of 1000ml, add 12.6582g cerous oxide, 11.2414g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 5000ml, add 364g silica powder (400 order), add deionized water 3000ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing cerium and antimony of 180 Ω cm.
Embodiment 8
In the beaker of 1000ml, add 13.9798g Dysprosium trioxide, 11.2414g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 28.33g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing dysprosium and antimony of 4.5 Ω cm.
Embodiment 9
In the beaker of 1000ml, add 0.5012g europiumsesquioxide, 1.9575g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 51g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing europium and antimony of 3.5 Ω cm.
Embodiment 10
In the beaker of 1000ml, add 0.4012g terbium sesquioxide, 1.9875g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 32g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing terbium and antimony of 2.0 Ω cm.
Embodiment 11
In the beaker of 1000ml, add 0.4098g holmium oxide, 2.5375g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 41g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing holmium and antimony of 2.0 Ω cm.
Embodiment 12
In the beaker of 1000ml, add 0.4915g thulium oxide, 2.0575g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 39g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing thulium and antimony of 1.0 Ω cm.
Embodiment 13
In the beaker of 1000ml, add 0.4756g yttria, 2.3576g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 31g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing ytterbium and antimony of 1.0 Ω cm.
Embodiment 14
In the beaker of 1000ml, add 0.4563g three oxidations two lutetiums, 2.1675g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2 00ml, add 35g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing lutetium and antimony of 1.0 Ω cm.
Embodiment 15
In the beaker of 1000ml, add 0.3012g scandium oxide, 1.9575g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 35g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing scandium and antimony of 15.0 Ω cm.
Embodiment 16
In the beaker of 1000ml, add 0.4512g yttrium oxide, 2.6571g antimonous oxide, the glass putty of 29.6725g, the citric acid of 60g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 450ml that is made into 2mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 31g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 60 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 8, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 1h under 105 ℃, grind, cross 200 mesh sieves, powder after sieving in 900 ℃ of calcining 2h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing yttrium and antimony of 1.1 Ω cm.
Embodiment 17
In the beaker of 1000ml, add 0.2447g mixed rare-earth oxide (wherein lanthanum sesquioxide is 12.34%, neodymium sesquioxide is 82.13%, cerous oxide be 5.53%), 2.98g antimonous oxide, the glass putty of 29.67g, the citric acid of 58g, under constantly stirring, add the 6mol/L salpeter solution until forming transparent pistac mixing solutions.
The ammonia soln 300ml that is made into 3mol/L in the beaker of 1000ml is stand-by.
In the beaker of 2000ml, add 30g silica powder (400 order), add deionized water 600ml again, at room temperature stir into suspension liquid, and be heated to 55 ℃, even also drip adds above-mentioned mixing solutions and ammonia soln under constantly stirring, and the pH value of control reaction solution generates coprecipitate 7, treat the reinforced back stirring 30min that finishes, be cooled to room temperature then, filter, use deionized water wash coprecipitate 2 times, with absolute ethanol washing coprecipitate 1 time, with filter cake dry 2h under 100 ℃, grind, cross 200 mesh sieves, powder after sieving in 850 ℃ of calcining 3h, is promptly got the composite conductive powder of resistivity less than the stannic oxide of mixing rare earth and antimony of 0.2 Ω cm.
Embodiment 18-22 tabulation
| Embodiment | The rare-earth oxidation species | The concentration of tin (mol/ L) | Concentration of nitric acid (mol/ L) | The concentration of ammoniacal liquor (mol/ L) | n Complexing agent ∶n (Sn+ Sb+RE) | n Sn∶ n RE∶ n Sb | n Sn+n RE +n Sb (mol) | N conductive core material: n (Sn+Sb+ RE) | Thermal treatment temp (℃) | The resistivity of product (Ω .cm) |
| 18 | La 2O 3 | 0.05 | 0.5 | 0.5 | 0.1∶1 | 40∶0.0735∶0.1 | 0.5 | 1∶15 | 1000 | 13 |
| 19 | Pr 2O 3 | 1.22 5 | 6 | 6 | 1.5∶1 | 68∶15∶15 | 0.8 | 42∶44 | 800 | 14 |
| 20 | Er 2O 3 | 2.5 | 12 | 12 | 2∶1 | 95∶30∶30 | 0.7 | 85∶99 | 900 | 16 |
| 21 | Nd 2O 3 | 0.06 | 0.4 | 0.4 | 1.9∶1 | 41∶0.08∶29 | 1.1 | 2∶98 | 1100 | 6.2 |
| 22 | Sm 2O 3 | 2.4 | 11 | 11 | 0.2∶1 | 94∶29∶0.2 | 0.8 | 84∶16 | 900 | 239 |
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. a preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth comprises the following steps:
Mixture and glass putty, antimonous oxide, complexing agent and the nitric acid that a. will be selected from a kind of rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or the scandium or more than one rare earth oxides mix, the preparation mixing solutions, the concentration of tin is controlled to be 0.05～2.5mol/L in the described mixing solutions, and the mol ratio of tin and rare earth oxide, antimonous oxide is controlled to be n
Sn: n
RE: n
Sb=40～95: 0.0735～30: 0.1～30, described complexing agent is selected from C
2～C
8Organic acid or its mixture, the mol ratio of complexing agent and tin, rare earth oxide and antimonous oxide sum is n
Complexing agent: n
(Sn+Sb+RE)=0.1～2: 1, concentration of nitric acid is controlled to be 0.5～12mol/L;
B. prepare the alkali lye of 0.5～12mol/L with ammoniacal liquor;
C. conductive core material is dispersed in the aqueous solution, described conductive core material is selected from one or more the mixture in quartz, kaolin, mica, lime feldspar, pyrophyllite or the trichroite, or a kind of oxide compound or more than one hopcalites in the titanium, magnesium, calcium, barium, strontium, nickel, iron, or a kind of vitriol in the calcium, barium, strontium or the mixture of more than one vitriol, the mol ratio of conductive core material and tin, rare earth oxide and antimonous oxide sum is n
Conductive core material: n
(Sn+Sb+RE)=1～85: 15～99, under agitation with and the mode that adds of drip add above-mentioned mixing solutions and alkali lye, control pH value is 3-11, temperature of reaction is 1-80 ℃, the acquisition coprecipitate.Under constantly stirring evenly and drip add by the mixing solutions of step a preparation and described alkali lye in deionized water, obtain throw out, control pH value is 3～11, temperature of reaction is 1～80 ℃;
D. use deionized water and C respectively
1～C
3The organic solvent washing throw out, the throw out after the washing grinds, crosses the 100-200 mesh sieve at 100～105 ℃ of following oven dry 1～2h, the throw out after sieving obtains mixing the composite tin oxide conducting powder body of antimony and rare earth at 400～1100 ℃ of calcining 0.5～5h down.
2. according to the described preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth of claim 1, it is characterized in that: complexing agent described in the step a is selected from citric acid or tartrate or citric acid and tartaric mixture.
3. according to the described preparation method who mixes the composite tin oxide conducting powder of antimony and rare earth of claim 1, it is characterized in that: C described in the steps d
1～C
3Organic solvent be ethanol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008030486A1 (en) | 2008-06-26 | 2009-12-31 | Binnewies, Michael, Prof. Dr. rer. nat. | Preparing substituted tin(IV)-oxide particle, useful e.g. in solar cell, comprises providing precursor compound, introducing compound suitable for substitution, and converting precursor compound with oxygen/a compound that releases oxygen |
| CN106187161A (en) * | 2016-07-21 | 2016-12-07 | 浙江凯色丽科技发展有限公司 | Heat insulation conductive material of light colour flaky and preparation method thereof |
| CN106987248A (en) * | 2017-04-10 | 2017-07-28 | 江南大学 | A kind of up-conversion based on tin-antiomony oxide |
| CN108997746A (en) * | 2018-09-08 | 2018-12-14 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of Halogen barrier flame-retardant explosion-proof material |
| CN112408481A (en) * | 2020-10-14 | 2021-02-26 | 浙江大学 | Preparation method of high-conductivity layered structure multi-element composite rare earth oxide |
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2006
- 2006-03-27 CN CN 200610025108 patent/CN1847156A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008030486A1 (en) | 2008-06-26 | 2009-12-31 | Binnewies, Michael, Prof. Dr. rer. nat. | Preparing substituted tin(IV)-oxide particle, useful e.g. in solar cell, comprises providing precursor compound, introducing compound suitable for substitution, and converting precursor compound with oxygen/a compound that releases oxygen |
| CN106187161A (en) * | 2016-07-21 | 2016-12-07 | 浙江凯色丽科技发展有限公司 | Heat insulation conductive material of light colour flaky and preparation method thereof |
| CN106187161B (en) * | 2016-07-21 | 2019-06-28 | 浙江凯色丽科技发展有限公司 | Heat-insulated conductive material of light colour flaky and preparation method thereof |
| CN106987248A (en) * | 2017-04-10 | 2017-07-28 | 江南大学 | A kind of up-conversion based on tin-antiomony oxide |
| CN106987248B (en) * | 2017-04-10 | 2019-08-06 | 江南大学 | A kind of up-conversion based on tin-antiomony oxide |
| CN108997746A (en) * | 2018-09-08 | 2018-12-14 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of Halogen barrier flame-retardant explosion-proof material |
| CN112408481A (en) * | 2020-10-14 | 2021-02-26 | 浙江大学 | Preparation method of high-conductivity layered structure multi-element composite rare earth oxide |
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