CN115873306B - Preparation method of high-length-diameter-ratio and high-whiteness conductive material - Google Patents
Preparation method of high-length-diameter-ratio and high-whiteness conductive material Download PDFInfo
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- CN115873306B CN115873306B CN202211605740.9A CN202211605740A CN115873306B CN 115873306 B CN115873306 B CN 115873306B CN 202211605740 A CN202211605740 A CN 202211605740A CN 115873306 B CN115873306 B CN 115873306B
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- 239000004020 conductor Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 26
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 19
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 19
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 19
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 229910052604 silicate mineral Inorganic materials 0.000 claims abstract description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims description 44
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 34
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 34
- 239000001119 stannous chloride Substances 0.000 claims description 34
- 235000011150 stannous chloride Nutrition 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 22
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000007792 addition Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229960000892 attapulgite Drugs 0.000 claims description 12
- 229910052625 palygorskite Inorganic materials 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 claims description 2
- QLCPUVSLEIUUEM-UHFFFAOYSA-G tetrachlorotitanium trichlorotitanium Chemical compound Cl[Ti](Cl)(Cl)[Ti](Cl)(Cl)(Cl)Cl QLCPUVSLEIUUEM-UHFFFAOYSA-G 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
- YULBFWISFJEMQB-UHFFFAOYSA-N oxotin titanium Chemical compound [Sn]=O.[Ti] YULBFWISFJEMQB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000706 filtrate Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
The invention relates to the technical field of conductive composite materials, and discloses a preparation method of a conductive material with high length-diameter ratio and high whiteness. The invention firstly adds fibrous silicate mineral material into the mixed solution of titanium tetrachloride and titanium trichloride, and the surface of silicate mineral grows rutile phase nano titanium dioxide in situ. And depositing tin dioxide and stannous oxide on the surface of the material, fully mixing the obtained material with ammonium phosphate, drying, introducing nitrogen, and performing heat treatment in a nitrogen atmosphere to obtain the white conductive powder. According to the invention, rutile phase nano titanium dioxide grows on the surface of silicate minerals in situ, so that the whiteness of the product is improved, the interfacial binding force between a nuclear body and a doped tin oxide conductive layer is increased, ammonia generated by decomposition of ammonium phosphate can reduce and dope titanium tin oxide in the heating doping process, and decomposed phosphorus can dope titanium tin oxide, so that the conductivity of the product is obviously improved, and the high-length-diameter-ratio and high-whiteness conductive material is obtained.
Description
Technical Field
The invention relates to a preparation method of a high-length-diameter-ratio and high-whiteness conductive material, in particular to a preparation method of a high-length-diameter-ratio and high-whiteness conductive material.
Background
The inorganic conductive material is widely applied to the fields of plastics, rubber, chemical fibers, paint and the like, can endow the material with the functions of conductivity, static resistance and electromagnetic wave shielding, and has wide application prospect. The conductive material is mainly granular and fibrous in shape, and the fibrous conductive material with high length-diameter ratio has a certain excellent reinforcing-toughening effect on the material due to less addition. In addition, the color of the conductive material directly affects the color and the appearance of the terminal product, and the white conductive material is added to manufacture the product, so that the product is popular among people, and one of the important research directions is to improve the whiteness of the inorganic conductive powder. The fibrous light inorganic conductive material represents products such as rod-shaped conductive titanium dioxide and rod-shaped conductive potassium titanate. The preparation process includes the first preparing rod-shaped titania and rod-shaped potassium titanate material, and the subsequent chemical deposition, doping and other steps to prepare the rod-shaped conducting material. Although these conductive fiber materials have excellent properties, their nuclei are artificially synthesized, and the preparation conditions are severe and the cost is high.
Disclosure of Invention
Aiming at the problems existing in the background technology, the invention provides a method for preparing a high-length-diameter-ratio and high-whiteness conductive material by taking a fibrous silicate mineral material as a nucleus. The specific preparation method of the material comprises the following steps:
1. titanium dioxide grows on the surface: adding fibrous silicate mineral material into a titanium tetrachloride-titanium trichloride mixed solution, reacting for 30-60 hours at 10-30 ℃, then heating to 80-100 ℃ at 0.2-0.5 ℃/min, and preserving heat for reacting for 8-26 hours; filtering, and washing until the electric conductivity of the filtrate is less than or equal to 300 mu S/cm, thus obtaining a filter cake. The surface of silicate mineral grows rutile phase nano titanium dioxide in situ.
2. Surface deposition of tin dioxide and stannous oxide: and (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 5-15%, heating to 50-75 ℃, respectively adding a mixed aqueous solution of tin tetrachloride and stannous chloride and an alkali solution while stirring, maintaining the pH value of a reaction system to 3.0-6.0, continuing to keep the temperature and stirring for 20-60 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is less than or equal to 300 mu S/cm, thus obtaining the filter cake. And further depositing a tin hydroxide-stannous hydroxide coprecipitate on the surface of the rutile phase nano titanium dioxide in-situ grown on the surface of the silicate mineral, namely depositing tin dioxide and a stannous oxide conductive layer precursor on the surface.
3. Nitrogen-phosphorus co-doping: and (3) fully mixing the filter cake obtained in the step (2) with ammonium phosphate, drying, introducing nitrogen, and performing heat treatment for 1-6 hours in a nitrogen atmosphere to obtain the white conductive powder.
The fibrous silicate mineral material in the step 1 is one of attapulgite, sepiolite, halloysite and wollastonite.
The titanium tetrachloride and the titanium trichloride in the step 1 are added according to the mass of titanium dioxide generated by the complete reaction, wherein the mass ratio of the titanium dioxide to the fibrous silicate mineral material is 0.3-0.6:1.
The total concentration of the titanium tetrachloride and the titanium trichloride in the step 1 is 0.3-1.0 mol/L, and the mol ratio of the titanium trichloride to the titanium tetrachloride in the solution is 0.2-0.5:1
And (2) adding the tin tetrachloride and the stannous chloride in a mass ratio of 0.32-0.86:1 based on the mass of the tin dioxide generated by the complete reaction of the tin tetrachloride and the stannous chloride.
The total concentration of the stannic chloride and the stannous chloride in the step 2 is 1.0-2.5 mol/L, and the mol ratio of the stannous chloride to the stannic chloride in the solution is 0.1-0.3:1.
The alkali in the step 2 is one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate.
And (3) the ratio of the mole number of ammonium phosphate to the total mole number of titanium tin is 0.05-0.2:1.
The heat treatment temperature in the step 3 is 400-700 ℃.
The beneficial effects of the invention are as follows:
1. the rutile phase nano titanium dioxide grows on the surface of silicate mineral in situ, so that the whiteness of the product is improved, and the interfacial binding force between the nucleus and the tin oxide doped conductive layer is increased.
2. In the invention, a great amount of hydrogen ions are released in the process of generating nano titanium dioxide by the titanium salt hydrolysis, and the hydrogen ions can replace chromogenic ions of silicate minerals such as iron ions and the like, so that the whiteness of the product can be improved.
3. In-situ doping of trivalent titanium with tetravalent titanium and stannous with tetravalent tin helps to further improve the conductivity of the product.
4. In the heating doping process, ammonia gas and structural change generated by decomposition of ammonium phosphate can play a role in disintegration and dispersion, and conductive powder with good dispersibility can be obtained without damaging the crushing procedure of the length of the rod crystal, so that the characteristic of high length-diameter ratio of the conductive powder is ensured, and uniform doping is facilitated to improve the conductivity of the product.
5. The ammonia generated by the decomposition of the ammonium phosphate can reduce and dope titanium tin oxide, and the decomposed phosphorus can dope titanium tin oxide so as to remarkably improve the conductivity of the product.
Drawings
The invention will be further described with reference to the drawings and examples.
Fig. 1 is a TEM photograph of the conductive material obtained in example 3.
Detailed Description
The volume resistivity of the conductive powder is measured: 10.0g of conductive powder is put into a polyacrylate glass tube with scales, the conductive powder is pressed between two metal sheets by using the pressure of 1MPa, the resistance between the two metal sheets is measured by using a universal meter, and the resistivity of the conductive powder is calculated according to the thickness and the sectional area of a powder layer.
Rsp＝R×A/L
Wherein: rsp is volume resistivity (Ω·cm), R is measured resistance (Ω), A is inner diameter cross-sectional area (cm) of the glass tube 2 ) L is the height (cm) of the conductive powder layer.
The whiteness of the conductive powder is measured by a WSD-3C full-automatic whiteness meter (Beijing Kang Guang optical instrument Co., ltd.).
Example 1
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to a mixed solution of 12.5 liters of titanium tetrachloride and titanium trichloride having a total concentration of 0.3 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.5:1, reacted at 10℃for 60 hours, then heated to 80℃at 0.5℃per minute, reacted at a constant temperature for 26 hours, filtered, and washed to a filtrate conductivity of 287. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 5%, heating to 50 ℃, adding 2.123 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 1 mole/liter (wherein the mole ratio of the stannous chloride to the stannic chloride is 0.1:1) and 2 moles/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 3.0, continuing to keep the temperature and stirring for 20 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 186 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 43.8 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 400 ℃ for 6 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 9.6Ω·cm, the whiteness is 90, the average diameter is 40 nanometers, and the average length is 3500 nanometers.
Example 2
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) is added into 7.5L of a mixed solution composed of titanium tetrachloride and titanium trichloride with total concentration of 1 mol/L, the mol ratio of the titanium trichloride to the titanium tetrachloride in the solution is 0.2:1, the mixture is reacted for 30 hours at 30 ℃, then the mixture is heated to 100 ℃ at 0.2 ℃/min, the mixture is kept for 8 hours, and the mixture is filtered and washed until the electric conductivity of the filtrate is 126 mu S/cm, thus obtaining a filter cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 15%, heating to 75 ℃, adding 2.283 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 2.5 mol/liter (wherein the mol ratio of the stannous chloride to the stannic chloride is 0.3:1) and 4 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 6.0, keeping the temperature and stirring for 60 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 165 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 393.8 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 700 ℃ for 6 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 12.1 Ω & cm, the whiteness is 96, the average diameter is 45 nanometers, and the average length is 3500 nanometers.
Example 3
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to 10 liters of a mixed solution of titanium tetrachloride and titanium trichloride having a total concentration of 0.5 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.3:1, reacted at 25℃for 45 hours, then heated to 90℃at 0.3℃per minute, reacted at a temperature maintained for 15 hours, filtered, and washed to a filtrate conductivity of 215. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of mixed aqueous solution of stannic chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.2:1) and 3 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 4.0, continuing to keep the temperature and stirring for 40 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 199 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 141.6 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 600 ℃ for 3 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 8.9Ω & cm, the whiteness is 93, the average diameter is 42 nanometers, and the average length is 3450 nanometers.
Example 4
1. 1000 g of sepiolite (average diameter 50 nm, average length 4800 nm) was added to 10 liters of a mixed solution of titanium tetrachloride and titanium trichloride having a total concentration of 0.6 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.25:1, reacted at 20℃for 45 hours, then heated to 95℃at 0.2℃per minute, reacted at a constant temperature for 12 hours, filtered, and washed to a filtrate conductivity of 210. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 8%, heating to 70 ℃, adding 3 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.25:1) and 1.5 mol/liter of ammonium carbonate solution respectively while stirring, maintaining the pH value of the reaction system to be 5.0, keeping the temperature and stirring for 50 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 236 mu S/cm to obtain the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 235 g of ammonium phosphate, drying, introducing nitrogen, and obtaining white conductive powder at 650 ℃ for 4 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 13.2 Ω & cm, the whiteness is 95, the average diameter is 65 nanometers, and the average length is 4750 nanometers.
Example 5
1. 1000 g of halloysite (average diameter 63 nm, average length 2600 nm) was added to a 10 liter mixed solution of titanium tetrachloride and titanium trichloride at a total concentration of 0.4 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.28:1, reacted at 22℃for 50 hours, then heated to 88℃at 0.4℃per minute, reacted at a constant temperature for 18 hours, filtered, and washed to a filtrate conductivity of 108. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 12%, heating to 55 ℃, adding 4 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 1.2 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.35:1) and 1 mol/liter of sodium carbonate solution respectively while stirring, maintaining the pH value of a reaction system to be 3.5, keeping the temperature and stirring for 30 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 95 mu S/cm to obtain the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 105 g of ammonium phosphate, drying, introducing nitrogen, and obtaining white conductive powder at 680 ℃ for 2 hours under a nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 7.5 Ω & cm, the whiteness is 91, the average diameter is 80 nanometers, and the average length is 2580 nanometers.
Comparative example 1
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to 10 liters of titanium tetrachloride solution having a total concentration of 0.5 mol/liter, reacted at 25℃for 45 hours, then reacted at a temperature of 0.3℃per minute to 90℃for 15 hours with heat preservation, filtered, and washed to a filtrate conductivity of 201. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of mixed aqueous solution of stannic chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.2:1) and 3 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 4.0, continuing to keep the temperature and stirring for 40 minutes after the addition, filtering, and washing until the conductivity of the filtrate is 178 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 141.6 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 600 ℃ for 3 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 197.2 Ω & cm, the whiteness is 92, the average diameter is 42 nanometers, and the average length is 3300 nanometers.
Comparative example 2
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to 10 liters of a titanium trichloride solution having a total concentration of 0.5 mol/liter, reacted at 25℃for 45 hours, then reacted at a temperature of 0.3℃per minute to 90℃for 15 hours with heat preservation, filtered, and washed to a filtrate conductivity of 192. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.2:1) and 3 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 4.0, continuing to keep the temperature and stirring for 40 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 173 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 141.6 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 600 ℃ for 3 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 369.8Ω·cm, the whiteness is 91, the average diameter is 43 nanometers, and the average length is 3460 nanometers.
Comparative example 3
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) is added into 10L of mixed solution composed of titanium tetrachloride and titanium trichloride with total concentration of 0.5 mol/L, the mol ratio of titanium trichloride and titanium tetrachloride in the solution is 0.3:1, the mixture is reacted for 45 hours at 25 ℃, then the mixture is heated to 90 ℃ at 0.3 ℃/min, the mixture is kept for 15 hours, and the mixture is filtered and washed until the electric conductivity of the filtrate is 245 mu S/cm, thus obtaining filter cakes.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of tin tetrachloride with the total concentration of 1.5 mol/liter and 3 mol/liter of sodium hydroxide solution while stirring, maintaining the pH value of a reaction system at 4.0, continuing to keep the temperature and stirring for 40 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 183 mu S/cm to obtain the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 141.6 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 600 ℃ for 3 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 1138.9 Ω & cm, the whiteness is 93, the average diameter is 42 nanometers, and the average length is 3390 nanometers.
Comparative example 4
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) is added into 10L of mixed solution composed of titanium tetrachloride and titanium trichloride with total concentration of 0.5 mol/L, the mol ratio of titanium trichloride and titanium tetrachloride in the solution is 0.3:1, the mixture is reacted for 45 hours at 25 ℃, then the mixture is heated to 90 ℃ at 0.3 ℃/min, the mixture is kept for 15 hours, and the mixture is filtered and washed until the electric conductivity of the filtrate is 268 mu S/cm, thus obtaining a filter cake.
And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of mixed aqueous solution of stannous chloride with the total concentration of 1.5 mol/liter and 3 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of a reaction system to be 4.0, keeping the temperature and stirring for 40 minutes after the addition is finished, filtering, and washing to the electric conductivity of 240 mu S/cm of the filtrate to obtain the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 141.6 g of ammonium phosphate, drying, introducing nitrogen, and obtaining the white conductive powder at 600 ℃ for 3 hours under the nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 945.3 ohm cm, the whiteness is 93, the average diameter is 42 nanometers, and the average length is 3270 nanometers.
Comparative example 5
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to 10 liters of a mixed solution of titanium tetrachloride and titanium trichloride having a total concentration of 0.5 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.3:1, reacted at 25℃for 45 hours, then heated to 90℃at 0.3℃per minute, reacted at a temperature maintained for 15 hours, filtered, and washed to a filtrate conductivity of 276. Mu.S/cm, to obtain a cake.
2. And (3) fully mixing the filter cake obtained in the step (2) with 74.5 g of ammonium phosphate, drying, introducing nitrogen, and obtaining white conductive powder at 600 ℃ for 3 hours under a nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 8980 Ω & cm, the whiteness is 94, the average diameter is 36 nanometers, and the average length is 3100 nanometers.
Comparative example 6
1. 1000 g of attapulgite (average diameter of 25 nanometers and average length of 3500 nanometers) is dispersed in deionized water to prepare slurry with the solid content of 10 percent, the temperature is raised to 65 ℃, 3 liters of mixed aqueous solution of stannic chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.2:1) and 3 mol/liter of sodium hydroxide solution are respectively added while stirring, the pH value of a reaction system is maintained to be 4.0, and after the addition, the heat preservation and stirring are continued for 40 minutes, and filtration and washing are carried out until the electric conductivity of filtrate is 218 mu S/cm, thus obtaining a filter cake.
2. And (3) fully mixing the filter cake obtained in the step (2) with 67.1 g of ammonium phosphate, drying, introducing nitrogen, and obtaining gray conductive powder at 600 ℃ for 3 hours under a nitrogen atmosphere. The volume resistivity of the obtained conductive powder is 560 ohm cm, the whiteness is 57, the average diameter is 35 nanometers, and the average length is 3250 nanometers.
Comparative example 7
1. 1000 g of attapulgite (average diameter 25 nm, average length 3500 nm) was added to 10 liters of a mixed solution of titanium tetrachloride and titanium trichloride having a total concentration of 0.5 mol/liter, the molar ratio of titanium trichloride to titanium tetrachloride in the solution was 0.3:1, reacted at 25℃for 45 hours, then heated to 90℃at 0.3℃per minute, reacted at a temperature maintained for 15 hours, filtered, and washed to a filtrate conductivity of 213. Mu.S/cm, to obtain a cake.
2. And (3) redispersing the filter cake obtained in the step (1) in deionized water to prepare slurry with the solid content of 10%, heating to 65 ℃, adding 3 liters of mixed aqueous solution of stannous chloride and stannous chloride with the total concentration of 1.5 mol/liter (the mol ratio of the stannous chloride to the stannic chloride is 0.2:1) and 3 mol/liter of sodium hydroxide solution respectively while stirring, maintaining the pH value of the reaction system to be 4.0, continuing to keep the temperature and stirring for 40 minutes after the addition, filtering, and washing until the electric conductivity of the filtrate is 207 mu S/cm, thus obtaining the filter cake.
3. And (3) fully mixing the filter cake obtained in the step (2) with 93.1 g of phosphoric acid, drying, introducing nitrogen, and crushing at 600 ℃ for 3 hours under a nitrogen atmosphere to obtain white conductive powder. The volume resistivity of the obtained conductive powder is 760 Ω & cm, the whiteness is 87, the average diameter is 42 nanometers, and the average length is 320 nanometers.
Claims (5)
1. A preparation method of a high-length-diameter ratio and high-whiteness conductive material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Adding fibrous silicate mineral material into a titanium tetrachloride-titanium trichloride mixed solution, reacting for 30-60 hours at 10-30 ℃, then heating to 80-100 ℃ at a speed of 0.2-0.5 ℃/min, preserving heat, reacting for 8-26 hours, filtering, and washing to obtain a filter cake; the fibrous silicate mineral material is one of attapulgite, sepiolite and halloysite;
(2) Re-dispersing the filter cake obtained in the step 1 in deionized water to prepare slurry with the solid content of 5-15%, heating to 50-75 ℃, respectively adding a mixed aqueous solution of tin tetrachloride and stannous chloride and an alkali solution while stirring, maintaining the pH value of a reaction system to be 3.0-6.0, continuing to keep the temperature and stirring for 20-60 minutes after the addition, filtering, and washing to obtain a filter cake with a precursor of a surface deposited conductive layer;
(3) And (3) fully mixing the filter cake of the precursor with the conductive layer deposited on the surface obtained in the step (2) with ammonium phosphate, drying, introducing nitrogen, and performing heat treatment in a nitrogen atmosphere to obtain the white conductive powder.
2. The method for preparing a high aspect ratio and high whiteness conductive material according to claim 1, wherein: the total concentration of the titanium tetrachloride and the titanium trichloride in the step (1) is 0.3-1.0 mol/liter, and the mol ratio of the titanium trichloride to the titanium tetrachloride in the solution is 0.2-0.5:1; the titanium dioxide and the fibrous silicate mineral material are added according to the mass ratio of 0.3-0.6:1 based on the mass of titanium tetrachloride and titanium trichloride which are completely reacted to form titanium dioxide.
3. The method for preparing a high aspect ratio and high whiteness conductive material according to claim 1, wherein: the total concentration of the stannic chloride and the stannous chloride in the step (2) is 1.0-2.5 mol/L, and the mol ratio of the stannous chloride to the stannic chloride in the solution is 0.1-0.3:1; the tin dioxide and the fibrous silicate mineral material are added according to the mass ratio of 0.32-0.86:1 based on the mass of the tin dioxide generated by the complete reaction of the tin tetrachloride and the stannous chloride.
4. The method for preparing a high aspect ratio and high whiteness conductive material according to claim 1, wherein: and (3) the ratio of the mole number of ammonium phosphate to the total mole number of titanium tin is 0.05-0.2:1.
5. The method for preparing a high aspect ratio and high whiteness conductive material according to claim 1, wherein: and (3) the heat treatment temperature is 400-700 ℃ and the heat treatment temperature is 1-6 hours.
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| US5350448A (en) * | 1992-04-25 | 1994-09-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Electrically conductive pigments |
| CN102580713A (en) * | 2012-01-18 | 2012-07-18 | 常州大学 | Method for preparing titanium dioxide/silicate mineral nano composites |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN107128940A (en) * | 2017-04-25 | 2017-09-05 | 安徽博硕科技有限公司 | A kind of preparation method of the composite modified attapulgite insulating unit material of nano strontium titanate/nano tin dioxide/nano-zinc sulfide |
| CN109338454A (en) * | 2018-09-26 | 2019-02-15 | 浙江凯色丽科技发展有限公司 | The preparation method of the siliceous titanium dioxide crystal whisker of rutile-type |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5350448A (en) * | 1992-04-25 | 1994-09-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Electrically conductive pigments |
| CN102580713A (en) * | 2012-01-18 | 2012-07-18 | 常州大学 | Method for preparing titanium dioxide/silicate mineral nano composites |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN107128940A (en) * | 2017-04-25 | 2017-09-05 | 安徽博硕科技有限公司 | A kind of preparation method of the composite modified attapulgite insulating unit material of nano strontium titanate/nano tin dioxide/nano-zinc sulfide |
| CN109338454A (en) * | 2018-09-26 | 2019-02-15 | 浙江凯色丽科技发展有限公司 | The preparation method of the siliceous titanium dioxide crystal whisker of rutile-type |
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