CN113603484A - Preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate - Google Patents

Preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate Download PDF

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CN113603484A
CN113603484A CN202110988660.5A CN202110988660A CN113603484A CN 113603484 A CN113603484 A CN 113603484A CN 202110988660 A CN202110988660 A CN 202110988660A CN 113603484 A CN113603484 A CN 113603484A
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CN113603484B (en
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王中旭
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Shaanxi Junpu Xinhang Technology Co ltd
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Abstract

The invention discloses a preparation method of negative temperature coefficient thermistor manganese titanate-lead niobate nickelate, which comprises the steps of ball-milling and mixing a lanthanum source, a manganese source and a titanium source, and presintering to obtain first powder; ball-milling and mixing a niobium source and a nickel source, and pre-sintering to obtain second powder; and mixing the first powder and the second powder, adding lead oxide, performing ball milling and mixing, granulating, sieving, tabletting and sintering to obtain the negative temperature coefficient thermistor lead manganese titanate-lead niobate. The NTC thermistor with the room temperature resistivity of 15 +/-3 omega-cm can be obtained, and the temperature drift is less than 5%.

Description

Preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate
Technical Field
The invention belongs to the technical field of preparation methods of electronic functional materials, and particularly relates to a preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate.
Background
Negative temperature coefficient thermistors (NTCR) are complex sintered oxides characterized by an exponential decrease in resistivity with increasing temperature. The characteristics of the negative temperature coefficient enable the NTCR to accurately measure the temperature change in the circuit, and the temperature can be regulated and controlled through temperature compensation. Therefore, the NTCR is widely used in various electronic information systems.
Generally, the core material of NTCR is a semiconductor functional ceramic, and its crystal structure usually has a spinel or perovskite type crystal structure. Lanthanum manganate (LaMnO) for NTCR of perovskite structure3) The derivative system NTCR of (A) is most common. LaMnO3Has good high-temperature stability, acid and alkali corrosion resistance, relatively stable crystal structure and capability of well keeping perovskite structure, however, LaMnO3As NTCR material, the material has low temperature sensitivity, low room temperature resistivity and poor sintering performance, and NTCR with high conductivity and wider use temperature range can be obtained by Ti doping modification, and lead nickel niobate (Pb (NiNb) O3PNNO) is a typical relaxor ferroelectric, also has a typical perovskite structure, can be well combined with lanthanum manganate to form a solid solution, and increases the conductivity and the temperature sensitivity of the lanthanum manganate.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a method for preparing negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the embodiment of the invention provides a preparation method of negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate nickelate, which comprises the following steps:
ball-milling and mixing a lanthanum source, a manganese source and a titanium source, and presintering to obtain first powder;
ball-milling and mixing a niobium source and a nickel source, and pre-sintering to obtain second powder;
and mixing the first powder and the second powder, adding lead oxide, performing ball milling and mixing, granulating, sieving, tabletting and sintering to obtain the negative temperature coefficient thermistor lead manganese titanate-lead niobate.
In the scheme, the lanthanum source, the manganese source and the titanium source respectively adopt MnCO3、La2O3And TiO2。
In the above scheme, the niobium source and the nickel source are respectivelyUsing Nb2O5And NiO.
In the scheme, the lanthanum source, the manganese source and the titanium source are mixed by ball milling, and are presintered to obtain first powder, and the method is realized by the following steps:
step 1.1, respectively adopting La as the lanthanum source, the manganese source and the titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 1.2, the mol ratio of La, Mn and Ti is 1: x: y, wherein x + y is 1, and x is not less than 0.7;
step 1.3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and step 1.4, drying the powder obtained in the step 1.3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 2-4 h, and naturally cooling to obtain first powder.
In the scheme, a niobium source and a nickel source are mixed by ball milling, and are presintered to obtain second powder, and the method is realized by the following steps:
step 2.1, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 2.2, the mol ratio of Nb to Ni is 0.4: 0.6-0.5: 0.5;
step 2.3 weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and 2.4, drying the powder obtained in the step 2.3, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid-phase reaction, preserving heat for 1-2 h, and naturally cooling to obtain second powder.
In the scheme, the first powder and the second powder are mixed, lead oxide is added, and the negative temperature coefficient thermistor manganese titanate-lead niobate can be obtained by ball milling, mixing, granulating, sieving, tabletting and sintering, and the method is specifically realized by the following steps:
step 3.1, mixing the first powder and the second powder according to a molar ratio of 1.2-1.8: 1 to obtain mixed powder;
3.2, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.15-1.25 times of the sum of the molar amounts of Ni and Nb;
3.3, putting the powder obtained in the step 3.2 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
step 3.4, drying the powder obtained in the step 3.3, sieving the powder with a 300-mesh sieve, and adding 3-5 wt% of PVA for granulation;
step 3.5, compacting the powder obtained in the step 3.4 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 6-8 s, and then placing the powder into an aluminum oxide crucible with a cover;
3.6, putting the crucible in the step 3.5 into a muffle furnace, heating the muffle furnace to 650-950 ℃ at the speed of 2-3 ℃/min, preserving heat for 1-3 h, and then heating the muffle furnace to 1200-1250 ℃ at the speed of 4.5-5.5 ℃/min, preserving heat for 2 h;
and 3.7, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate.
Compared with the prior art, the NTC thermistor with the room-temperature resistivity of 15 +/-3 omega-cm can be obtained, and the temperature drift is less than 5%.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a resistance-temperature characteristic curve of a negative temperature coefficient thermistor LMTO-PNNO prepared by a preparation method of a negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate according to embodiment 1 of the present invention;
FIG. 2 is a resistance-temperature characteristic curve of a negative temperature coefficient thermistor LMTO-PNNO prepared by a preparation method of a negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate provided in embodiment 2 of the invention;
FIG. 3 is a resistance-temperature characteristic curve of a negative temperature coefficient thermistor LMTO-PNNO prepared by a preparation method of the negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate provided in embodiment 3 of the present invention;
fig. 4 is a resistance-temperature characteristic curve of the ntc thermistor LMTO-PNNO prepared by the method for preparing the ntc thermistor lanthanum manganite-lead niobate in embodiment 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, article, or apparatus that comprises the element.
The embodiment of the invention provides a preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate, which is realized by the following steps:
step 1, ball-milling and mixing a lanthanum source, a manganese source and a titanium source, and presintering to obtain first powder;
specifically, the lanthanum source, the manganese source and the titanium source respectively adopt MnCO3、La2O3And TiO2。
Step 2, performing ball milling and mixing on a niobium source and a nickel source, and pre-sintering to obtain second powder;
specifically, Nb is adopted as the niobium source and the nickel source respectively2O5And NiO.
And 3, mixing the first powder and the second powder, adding lead oxide, performing ball milling and mixing, granulating, sieving, tabletting and sintering to obtain the negative temperature coefficient thermistor lead manganese titanate-lead niobate nickelate.
Further, the lanthanum source, the manganese source and the titanium source are mixed in a ball milling mode, and after presintering, first powder is obtained, and the method is specifically realized through the following steps:
step 1.1, respectively adopting La as the lanthanum source, the manganese source and the titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 1.2, the mol ratio of La, Mn and Ti is 1: x: y, wherein x + y is 1, and x is not less than 0.7;
step 1.3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and step 1.4, drying the powder obtained in the step 1.3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 2-4 h, and naturally cooling to obtain first powder.
Further, the niobium source and the nickel source are mixed by ball milling, and after presintering, a second powder is obtained, and the method is specifically realized by the following steps:
step 2.1, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 2.2, the mol ratio of Nb to Ni is 0.4: 0.6-0.5: 0.5;
step 2.3 weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and 2.4, drying the powder obtained in the step 2.3, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid-phase reaction, preserving heat for 1-2 h, and naturally cooling to obtain second powder.
Further, the first powder and the second powder are mixed, lead oxide is added, and the negative temperature coefficient thermistor lead manganese titanate-lead niobate can be obtained by ball milling, mixing, granulating, sieving, tabletting and sintering, and the method is specifically realized by the following steps:
step 3.1, mixing the first powder and the second powder according to a molar ratio of 1.2-1.8: 1 to obtain mixed powder;
3.2, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.15-1.25 times of the sum of the molar amounts of Ni and Nb;
3.3, putting the powder obtained in the step 3.2 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
step 3.4, drying the powder obtained in the step 3.3, sieving the powder with a 300-mesh sieve, and adding 3-5 wt% of PVA for granulation;
step 3.5, compacting the powder obtained in the step 3.4 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 6-8 s, and then placing the powder into an aluminum oxide crucible with a cover;
3.6, putting the crucible in the step 3.5 into a muffle furnace, heating the muffle furnace to 650-950 ℃ at the speed of 2-3 ℃/min, preserving heat for 1-3 h, and then heating the muffle furnace to 1200-1250 ℃ at the speed of 4.5-5.5 ℃/min, preserving heat for 2 h;
and 3.7, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate.
In the preparation method, the titanium-doped lanthanum manganate LMTO is compounded with the relaxor ferroelectric lead niobate nickelate PNNO, so that the characteristic of high stability of the perovskite structure is kept, the room-temperature resistivity is reduced and the temperature sensitivity is improved by doping and solid solution sintering.
The invention is prepared by doping titanium with lanthanum manganate (LaMn)xTiyO3X + y is 1, x is not less than 0.7, LMTO) and lead nickelate niobate (PbNbzNivO3Z + v ═ 1, Nb: ni-0.4: 0.6-0.5: 0.5, PNNO) phase, and combining with a specific sintering process, the method for preparing the negative temperature coefficient thermistor lead manganese titanate-niobium nickelate (LMTO-PNNO) can be realized by a simple process, and the prepared negative temperature coefficient thermistor lead manganese titanate-niobium nickelate (LMTO-PNNO) can be realizedThe prepared thermistor has good electrical properties.
Example 1
The embodiment 1 of the invention provides a preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate, which is realized by the following steps:
step 1, respectively adopting La as lanthanum source, manganese source and titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 2, the mol of La, Mn and Ti is 1: 0.7: 0.3;
step 3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling the mixture for 4 hours at the rotating speed of 500 r/min;
step 4, drying the powder obtained in the step 3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 2 hours, and naturally cooling to obtain first powder;
step 5, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 6, the mol ratio of Nb to Ni is 0.4:0.6: 0.5;
step 7, weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4 hours at the rotating speed of 500 r/min;
step 8, drying the powder obtained in the step 7, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, keeping the temperature for 1h, and naturally cooling the obtained product to obtain second powder;
step 9, mixing the first powder and the second powder according to a molar ratio of 1.2:1 to obtain mixed powder;
step 10, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.15 times of the sum of the molar amounts of Ni and Nb;
step 11, putting the powder obtained in the step 10 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4 hours at the rotating speed of 500 r/min;
step 12, drying the powder obtained in the step 11, sieving the dried powder with a 300-mesh sieve, and adding 3 wt% of PVA (polyvinyl alcohol) for granulation;
step 13, compacting the powder obtained in the step 12 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 6s, and then placing the powder into an aluminum oxide crucible with a cover;
step 14, putting the crucible in the step 13 into a muffle furnace, heating the muffle furnace to 650 ℃ at the speed of 2 ℃/min, preserving heat for 1h, and then heating the muffle furnace to 1200 ℃ at the speed of 4.5 ℃/min, preserving heat for 2 h;
and step 15, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese titanate-lead niobate nickelate.
As shown in FIG. 1, it can be seen from the resistance-temperature characteristic curve of negative temperature coefficient thermistor LMTO-PNNO prepared by the method of example 1 of the present invention that the resistance of this example decreases with increasing temperature, has a significant negative temperature coefficient, and has a room temperature resistivity of 17.54. omega. cm.
Example 2
The embodiment 2 of the invention provides a preparation method of negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate, which is realized by the following steps:
step 1, respectively adopting La as lanthanum source, manganese source and titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 2, the mol of La, Mn and Ti is 1: 0.9: 0.1;
step 3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling the mixture for 8 hours at the rotating speed of 600 r/min;
step 4, drying the powder obtained in the step 3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 4 hours, and naturally cooling to obtain first powder;
step 5, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 6, the mol ratio of Nb to Ni is 0.4:0.5: 0.5;
step 7, weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 8 hours at the rotating speed of 600 r/min;
step 8, drying the powder obtained in the step 7, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, keeping the temperature for 2 hours, and naturally cooling the obtained product to obtain second powder;
step 9, mixing the first powder and the second powder according to a molar ratio of 1.8:1 to obtain mixed powder;
step 10, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.25 times of the sum of the molar amounts of Ni and Nb;
step 11, putting the powder obtained in the step 10 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 8 hours at the rotating speed of 600 r/min;
step 12, drying the powder obtained in the step 11, sieving the dried powder with a 300-mesh sieve, and adding 5 wt% of PVA (polyvinyl alcohol) for granulation;
step 13, compacting the powder obtained in the step 12 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 8s, and then placing the powder into an aluminum oxide crucible with a cover;
step 14, putting the crucible in the step 13 into a muffle furnace, heating the muffle furnace to 950 ℃ at the speed of 2-3 ℃/min, preserving heat for 3h, and then heating the muffle furnace to 1250 ℃ at the speed of 5.5 ℃/min, preserving heat for 2 h;
and step 15, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese titanate-lead niobate nickelate.
As shown in FIG. 2, it can be seen from the resistance-temperature characteristic curve of the negative temperature coefficient thermistor LMTO-PNNO prepared by the method of example 2 of the present invention that the resistance of this example decreases with increasing temperature, has a significant negative temperature coefficient, and has a room temperature resistivity of 12.01. omega. cm.
Example 3
Embodiment 3 of the present invention provides a method for preparing a negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate, which is implemented by the following steps:
step 1, respectively adopting La as lanthanum source, manganese source and titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 2, the mol of La, Mn and Ti is 1: 0.8: 0.2;
step 3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling the mixture for 6 hours at the rotating speed of 550 r/min;
step 4, drying the powder obtained in the step 3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 3 hours, and naturally cooling to obtain first powder;
step 5, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 6, the mol ratio of Nb to Ni is 0.4:0.55: 0.5;
step 7, weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 6 hours at the rotating speed of 550 r/min;
step 8, drying the powder obtained in the step 7, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, keeping the temperature for 1.5h, and naturally cooling the obtained product to obtain second powder;
step 9, mixing the first powder and the second powder according to a molar ratio of 1.5:1 to obtain mixed powder;
step 10, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.2 times of the sum of the molar amounts of Ni and Nb;
step 11, putting the powder obtained in the step 10 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 6 hours at the rotating speed of 550 r/min;
step 12, drying the powder obtained in the step 11, sieving the dried powder with a 300-mesh sieve, and adding 4 wt% of PVA (polyvinyl alcohol) for granulation;
step 13, compacting the powder obtained in the step 12 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 7s, and then placing the powder into an aluminum oxide crucible with a cover;
step 14, putting the crucible in the step 13 into a muffle furnace, heating the muffle furnace to 800 ℃ at the speed of 2-3 ℃/min, preserving heat for 2h, and then heating the muffle furnace to 1225 ℃ at the speed of 5 ℃/min, preserving heat for 2 h;
and step 15, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese titanate-lead niobate nickelate.
As shown in FIG. 3, it can be seen from the resistance-temperature characteristic curve of the negative temperature coefficient thermistor LMTO-PNNO prepared by the method of example 3 of the present invention that the resistance of this example decreases with increasing temperature, has a significant negative temperature coefficient, and has a room temperature resistivity of 16.55 Ω · cm.
Example 4
Embodiment 4 of the present invention provides a method for preparing a negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate, which is implemented by the following steps:
step 1, respectively adopting La as lanthanum source, manganese source and titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 2, the mol of La, Mn and Ti is 1: 0.95: 0.05;
step 3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 7 hours at the rotating speed of 580 r/min;
step 4, drying the powder obtained in the step 3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, keeping the temperature for 2.8 hours, and naturally cooling the obtained product to obtain first powder;
step 5, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 6, the mol ratio of Nb to Ni is 0.4:0.58: 0.5;
step 7, weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 7 hours at the rotating speed of 580 r/min;
step 8, drying the powder obtained in the step 7, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, keeping the temperature for 1.8h, and naturally cooling the obtained product to obtain second powder;
step 9, mixing the first powder and the second powder according to a molar ratio of 1.3:1 to obtain mixed powder;
step 10, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.23 times of the sum of the molar amounts of Ni and Nb;
step 11, putting the powder obtained in the step 10 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 7 hours at a rotating speed of 590 r/min;
step 12, drying the powder obtained in the step 11, sieving the dried powder with a 300-mesh sieve, and adding 4.5 wt% of PVA (polyvinyl alcohol) for granulation;
step 13, compacting the powder obtained in the step 12 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 7.5s, and then placing the powder into an aluminum oxide crucible with a cover;
step 14, putting the crucible in the step 13 into a muffle furnace, heating the muffle furnace to 900 ℃ at the speed of 2-3 ℃/min, preserving heat for 2.6 hours, and then heating the muffle furnace to 1240 ℃ at the speed of 4.5-5.5 ℃/min, preserving heat for 2 hours;
and step 15, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese titanate-lead niobate nickelate.
As shown in FIG. 4, it can be seen from the resistance-temperature characteristic curve of the negative temperature coefficient thermistor LMTO-PNNO prepared by the method of example 4 of the present invention that the resistance of this example decreases with increasing temperature, has a significant negative temperature coefficient, and has a room temperature resistivity of 14.22. omega. cm.
The specific data of the performance parameters of the negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate nickelate prepared in examples 1 to 4 are shown in table 1:
Figure BDA0003231704930000111
therefore, the negative temperature coefficient thermistor LMTO-PNNO prepared by the preparation method has the NTC thermistor with the room temperature resistivity of 15 +/-3 omega cm, the temperature drift is less than 5 percent, and great economic benefit is achieved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.

Claims (6)

1. A preparation method of negative temperature coefficient thermistor manganese titanate-lead niobate nickelate is characterized by comprising the following steps:
ball-milling and mixing a lanthanum source, a manganese source and a titanium source, and presintering to obtain first powder;
ball-milling and mixing a niobium source and a nickel source, and pre-sintering to obtain second powder;
and mixing the first powder and the second powder, adding lead oxide, performing ball milling and mixing, granulating, sieving, tabletting and sintering to obtain the negative temperature coefficient thermistor lead manganese titanate-lead niobate.
2. The method of claim 1, wherein the lanthanum source, the manganese source, and the titanium source are MnCO, respectively3、La2O3And TiO2。
3. The method of claim 2, wherein the niobium source and the nickel source are Nb and Ni, respectively2O5And NiO.
4. The preparation method of the negative temperature coefficient thermistor lead manganese titanate-lead niobate according to any one of claims 1 to 3, wherein the lanthanum source, the manganese source and the titanium source are mixed by ball milling, and then subjected to presintering to obtain a first powder, and the preparation method specifically comprises the following steps:
step 1.1, respectively adopting La as the lanthanum source, the manganese source and the titanium source2O3、MnCO3And TiO2The purity requirement is analytically pure AR;
step 1.2, the mol ratio of La, Mn and Ti is 1: x: y, wherein x + y is 1, and x is not less than 0.7;
step 1.3, weighing La2O3、MnCO3And TiO2Putting the mixture into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and step 1.4, drying the powder obtained in the step 1.3, placing the dried powder in an alumina crucible, heating the dried powder to 1000 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid phase reaction, preserving heat for 2-4 h, and naturally cooling to obtain first powder.
5. The preparation method of the negative temperature coefficient thermistor lanthanum manganese titanate-lead niobate nickelate according to claim 4, characterized in that a niobium source and a nickel source are mixed by ball milling and are presintered to obtain a second powder, and the preparation method specifically comprises the following steps:
step 2.1, respectively adopting Nb for the niobium source and the nickel source2O5NiO, the purity requirement is analytically pure AR;
step 2.2, the mol ratio of Nb to Ni is 0.4: 0.6-0.5: 0.5;
step 2.3 weighing Nb2O5Putting NiO and the NiO into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
and 2.4, drying the powder obtained in the step 2.3, placing the dried powder in an alumina crucible, heating the dried powder to 1100 ℃ at a speed of 4 ℃/min in a muffle furnace, carrying out solid-phase reaction, preserving heat for 1-2 h, and naturally cooling to obtain second powder.
6. The method for preparing the negative temperature coefficient thermistor lead lanthanum manganese titanate-lead niobate according to claim 5, wherein the method comprises the following steps of mixing the first powder and the second powder, adding lead oxide, performing ball milling, mixing, granulating, sieving, tabletting and sintering to obtain the negative temperature coefficient thermistor lead lanthanum manganese titanate-lead niobate, and specifically comprises the following steps:
step 3.1, mixing the first powder and the second powder according to a molar ratio of 1.2-1.8: 1 to obtain mixed powder;
3.2, adding lead oxide PbO into the mixed powder, wherein the addition amount of the lead oxide PbO is 1.15-1.25 times of the sum of the molar amounts of Ni and Nb;
3.3, putting the powder obtained in the step 3.2 into a polytetrafluoroethylene ball milling tank, adding deionized water, and ball milling for 4-8 hours at the rotating speed of 500-600 r/min;
step 3.4, drying the powder obtained in the step 3.3, sieving the powder with a 300-mesh sieve, and adding 3-5 wt% of PVA for granulation;
step 3.5, compacting the powder obtained in the step 3.4 by using a manual tablet press, wherein the pressure is about 5Mpa, the pressure maintaining time is 6-8 s, and then placing the powder into an aluminum oxide crucible with a cover;
3.6, putting the crucible in the step 3.5 into a muffle furnace, heating the muffle furnace to 650-950 ℃ at the speed of 2-3 ℃/min, preserving heat for 1-3 h, and then heating the muffle furnace to 1200-1250 ℃ at the speed of 4.5-5.5 ℃/min, preserving heat for 2 h;
and 3.7, naturally cooling the muffle furnace to obtain the negative temperature coefficient thermistor manganese lanthanum titanate-lead niobate nickelate.
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