CN1384079A - Prepn and application of Li and Ti doped nickel oxide-base ceramic - Google Patents
Prepn and application of Li and Ti doped nickel oxide-base ceramic Download PDFInfo
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- CN1384079A CN1384079A CN 02121437 CN02121437A CN1384079A CN 1384079 A CN1384079 A CN 1384079A CN 02121437 CN02121437 CN 02121437 CN 02121437 A CN02121437 A CN 02121437A CN 1384079 A CN1384079 A CN 1384079A
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Abstract
The Li and Ti doped NiO-base ceramic is prepared through a sol-gel process of preparing Li doped NiO precursor powder and subsequent mixing with TiO2 and sintering. The precursor powder prepared through sol-gel process has msll grain size and homogeneous chemical performance, and is easy to sintered and favorable to raising material performance. Regulating the doped Li and Ti amount can alter the dielectric performance of the ceramic material for different requirement. The ceramic has very high dielectric constant, greater than 10 to the power 4 at 1-10 MHz, and high temperature stability and may be used in thermoelectric electricity generation, thermoelectric refrigeration, producing high-density capacitor and other fields.
Description
Technical field
The present invention relates to a kind of oxide ceramic material, particularly a kind of Li and Ti doped nickel oxide-base ceramic preparation methods and application thereof belong to thermoelectric and dielectric materials technical field.
Background technology
People such as Palchik in its article (Nanostructured Materials.1999,11 (3), point out that 415-420) NiO is a kind of application material very widely, can be used for fields such as catalytic field, fuel cell electrode and gas sensor.People such as Woosuck Shin are at their article (Materials Letters.2000,45,302-306; Jpn.J.Appl.Phys.2000,39 (3), 145) point out that the NiO pottery of the NiO of lithium doping or lithium sodium codoped can also be as thermo-electric converting material in.
The dielectric substance of high-dielectric coefficient commonly used can be divided into following a few class substantially at present.One class be Tao Li etc. in its article (Materials Letters.2000,44, what 1-5) mention is the high dielectric oxide or the perovskite structure composite oxide of representative with titanium, niobium.It is hundreds of that its dielectric constant values can reach, and is porcelain and titanium magnesium group of the lanthanides porcelain etc. as rutile porcelain, calcium titanate ceramics, magnesium titanate porcelain, titanium zirconium.Another kind of what be that Sun Rizhen mentions in the book of " Dielectric Physics basis " (press of South China Science ﹠ Engineering University, 2000) is sulfide, selenide, the telluride of representative with copper, silver, mercury, thallium etc., and its dielectric coefficient is about tens.Also having a class material is ferroelectric ceramic(s).Lee marks in Rong Dengzai " inorganic dielectric " (HUST publishes, the 1995) book and mentions its dielectric coefficient up to 10
3～10
4, they mainly are barium titanate based ceramic and leaded ferroelectric system (PMN, PZN, PFW, PFN, PNN etc.).All there is significant disadvantages in above material: the specific inductivity of (1) preceding two class materials is less than normal, all less than 1000; (2) and the specific inductivity instability of ferroelectric material, with temperature generation considerable change; (3) ferroelectric material that specific inductivity is bigger is generally all for containing Pb material (PZN, PFW, PFN, PNN etc.), in preparation and use pollution very big, be unfavorable for environmental requirement.
In sum, about the application in the dielectric substance field yet there are no report to the adulterated pottery of NiO, it is a kind of novel dielectric substance.
As everyone knows, preparation technology is the basis of material technology, also can cause the character of material to change a lot even form identical, different preparation process.At present nickel oxide is mixed and generally adopt solid phase method preparation (Woosuck Shin, et al.Materials Letters.2000,45,302-306; Jpn.J.Appl.Phys.2000,39 (3), 145), this traditional method sintering time is long, and energy consumption is big, and the material homogeneity that obtains is poor, causes degradation.
Summary of the invention
The objective of the invention is problems at synthesizing blender nickel oxide pottery existence in the conventional solid-state method, a kind of Li and Ti doped nickel oxide-base ceramic material and preparation method thereof is provided, promptly adopt " sol-gel processing " to reduce temperature of reaction, shorten the reaction times, the gained material can not only be applied in thermoelectric field, and can be used as the dielectric substance application.
Technical scheme of the present invention is as follows:
A kind of Li and Ti doped nickel oxide-base ceramic material is characterized in that having following chemical formula:
Li
ATi
BNi
CO
Wherein: A is 0.05～0.3
B is 0.02～0.05
C should satisfy: 1-A-B
Above-mentioned Li and Ti doped nickel oxide-base ceramic material can be prepared as follows:
(1). weighing is 0.93～0.65: 0.05～0.3: 0.02～0.05 Ni (NO in molar ratio respectively
3)
2, LiNO
3And TiO
2
(2). earlier with Ni (NO
3)
2And LiNO
aBe dissolved in the deionized water, forming concentration is the clear solution of 0.5～1mol/L, adds 1.3～2 times again to adding inorganic salt Ni (NO
3)
2The citric acid of molar weight is 70 ℃～80 ℃ stirrings, till forming transparent heavy-gravity colloidal sol;
(3). colloidal sol is made gel in 110 ℃～130 ℃ following dryings, take out xerogel, grind,, obtain black Li-Ni-O precursor powder 400 ℃～600 ℃ pre-burnings 1 hour～2 hours;
(4). with Li-Ni-O precursor powder and the load weighted TiO that makes in the step (3)
2The powder ball milling mixes, and is dry-pressing formed under 4Mpa～6Mpa, and 1100 ℃～1300 ℃ sintering 4 hours～8 hours obtain block Li-Ti-Ni-O base ceramic material.
The Li and Ti doped nickel oxide series stupalith that the present invention is prepared can be used as dielectric substance and uses.
The present invention is owing to adopted solution chemical processes (sol-gel processing), reduce temperature of reaction, shortened the reaction times, and obtain the uniform nano level lead compound of chemical ingredients, the precursor powder particle diameter is little, the chemistry homogeneity is good, and temperature of reaction is low, and the time is short, sintering process can be carried out under lower temperature, thereby has saved the energy.By nickel oxide being carried out Li and Ti doped (Li-Ti-Ni-O) base ceramic material that obtains, this material has unusual high specific inductivity (ε＞10
4,=10～10MHz), and temperature stability is good, all is better than the dielectric substance and the ferroelectric material of conventional perovskite structure, is lead-free systems; The doping that changes lithium and titanium can obviously change the dielectric properties of material, also can change the spectrum signature and the temperature dependency of material dielectric constant, makes it satisfy different industrial service requirements (as the X7R characteristic), is a kind of novel unleaded dielectric substance.The application of institute's synthetic Li and Ti doped nickel oxide stupalith of the present invention aspect engineering is very extensive.In thermoelectric field, can be used for thermo-electric generation (used heat utilization) and thermoelectric refrigeration system; In the dielectric medium field, except that can be used for making the high energy storage density electrical condenser, can also be used for aspects such as laser, demonstration, solid detection.
Description of drawings
Fig. 1: the XRD figure spectrum of different lithium and titanium doped content sample.
Fig. 2: typical powder TEM figure.
Fig. 3: Li
0.05Ti
0.02Ni
0.93The SEM figure of O sample.
Fig. 4: Li
0.1Ti
0.02Ni
0.88The SEM figure of O sample.
Fig. 5: Li
0.2Ti
0.04Ni
0.76The SEM figure of O sample.
Fig. 6: Li
0.3Ti
0.02Ni
0.68The SEM figure of O sample.
Fig. 7: Li
0.1Ti
0.05Ni
0.85The SEM figure of O sample.
Fig. 8: under the differing temps, relative permittivity is with the variation (Li of frequency
0.1Ti
0.05Ni
0.85O).
Fig. 9: under the fixed frequency, relative permittivity is with variation of temperature (Li
0.1Ti
0.05Ni
0.85O).
Figure 10: under the fixed frequency, relative permittivity is with variation of temperature (Li
0.05Ti
0.02Ni
0.93O).
Figure 11: under the differing temps, relative permittivity is with the variation (Li of frequency
0.05Ti
0.02Ni
0.93O).
Figure 12: under the room temperature, relative permittivity is with the variation (Li of frequency
0.1Ti
0.02Ni
0.88O).
Figure 13: under the room temperature, relative permittivity is with the variation (Li of frequency
0.2Ti
0.04Ni
0.76O).
Figure 14: under the room temperature, relative permittivity is with the variation (Li of frequency
0.3Ti
0.02Ni
0.68O).
Figure 15: the doping of lithium (left side, titanium content are 0.02) and titanium (right side, lithium content are 0.1) is to the influence of material dielectric constant.
Embodiment
All chemical are commercially available analytical pure, without being further purified.
Ni (NO
3)
2(0.093mol) and LiNO
3(0.005mol) be dissolved in the 250ml deionized water, stirring obtains clear solution, the 0.121mol citric acid is dissolved in above-mentioned solution, and 70 ℃ of stir abouts 3 hours obtain thickness colloidal sol, colloidal sol is put into baking oven, about 12 hours of 110 ℃ of dryings obtain xerogel, grind, 400 ℃ of pre-burnings 2 hours obtain black Li-Ni-O precursor powder.With this powder and TiO
2(0.002mol) powder mixes, ball milling, drying, dry-pressing formed under 4Mpa, 1300 ℃ of sintering 4 hours obtain block Li
0.05Ti
0.02Ni
0.93The O stupalith.At room temperature, relative permittivity ε=12190 (10000Hz).The sign of material and performance are seen Fig. 1, Fig. 3, Figure 10 and Figure 11; Presoma is a spheroidal particle, the about 30 nanometer (see figure 2)s of size.
Ni (NO
3)
2(0.088mol) and LiNO
3(0.01mol) be dissolved in the 250ml deionized water, stirring obtains clear solution, the 0.176mol citric acid is dissolved in above-mentioned solution, and 80 ℃ of stir abouts 3 hours obtain thickness colloidal sol, colloidal sol is put into baking oven, about 12 hours of 130 ℃ of dryings obtain xerogel, grind, 600 ℃ of pre-burnings 1 hour obtain black Li-Ni-O precursor powder.With this powder and TiO
2(0.002mol) powder mixes, ball milling, drying, dry-pressing formed under 5MPa, about 1100 ℃ of sintering 8 hours, obtain block Li
0.1Ti
0.02Ni
0.88The O stupalith.At room temperature, relative permittivity ε=52280 (10000Hz).The sign of material and performance are seen Fig. 1, Fig. 4 and Figure 12.
Ni (NO
3)
2(0.076mol) and LiNO
3(0.02mol) be dissolved in the 250ml deionized water, stirring obtains clear solution, the 0.128mol citric acid is dissolved in above-mentioned solution, and 70 ℃ of stir abouts 3 hours obtain thickness colloidal sol, colloidal sol is put into baking oven, about 12 hours of 120 ℃ of dryings obtain xerogel, grind, 450 ℃ of pre-burnings 1 hour obtain the black precursor powder.With this powder and TiO
2(0.004mol) powder mixes, ball milling, drying, dry-pressing formed under 5MPa, about 1280 ℃ of sintering 6 hours, obtain block Li
0.2Ti
0.04Ni
0.76The O stupalith.At room temperature, relative permittivity ε=200850 (10000Hz).The sign of material and performance are seen Fig. 1, Fig. 5 and Figure 13.
Ni (NO
3)
2(0.068mol) and LiNO
3(0.03mol) be dissolved in the 250ml deionized water, stirring obtains clear solution, the 0.126mol citric acid is dissolved in above-mentioned solution, and 60 ℃ of stir abouts 3 hours obtain thickness colloidal sol, colloidal sol is put into baking oven, about 12 hours of 110 ℃ of dryings obtain xerogel, grind, 450 ℃ of pre-burnings 1 hour obtain black LiNiO precursor powder.With LiNiO powder and TiO
2(0.002mol) powder mixes, ball milling, drying, dry-pressing formed under 4MPa, 1280 ℃ of sintering 4 hours, obtain block Li
0.3Ti
0.02Ni
0.68The O stupalith.At room temperature, relative permittivity ε=559800 (10000Hz).The sign of material and performance are seen Fig. 1, Fig. 6 and Figure 14.
Embodiment 5
Ni (NO
3)
2(0.085mol) and LiNO
3(0.01mol) be dissolved in the 250ml deionized water, stirring obtains clear solution, the 0.130mol citric acid is dissolved in above-mentioned solution, and 70 ℃ of stir abouts 3 hours obtain thickness colloidal sol, colloidal sol is put into baking oven, about 12 hours of 120 ℃ of dryings obtain xerogel, grind, 500 ℃ of pre-burnings 1 hour obtain black LiNiO precursor powder.With LiNiO powder and TiO
2(0.005mol) powder mixes, ball milling, drying, dry-pressing formed under 5Mpa, 1280 ℃ of sintering 8 hours obtain block Li
0.1Ti
0.05Ni
0.85The O stupalith.At room temperature, relative permittivity ε=9329 (10000Hz).The sign of material and performance are seen Fig. 1, Fig. 7, Fig. 8 and Fig. 9.
The doping of lithium and titanium is seen shown in Figure 15 to the influence of material dielectric constant.
Claims (3)
1. Li and Ti doped nickel oxide-base ceramic material is characterized in that having following chemical formula:
Li
ATi
BNi
CO
Wherein: A is 0.05～0.3
B is 0.02～0.05
C should satisfy: 1-A-B
2. prepare the method for Li and Ti doped according to claim 1 nickel oxide-base ceramic material, this method is carried out as follows:
(1) weighing is 0.93～0.65: 0.05～0.3: 0.02～0.05 Ni (NO in molar ratio respectively
3)
2, LiNO
3And TiO
2
(2) earlier with Ni (NO
3)
2And LiNO
3Be dissolved in the deionized water, forming concentration is the clear solution of 0.5～1mol/L, adds 1.3～2 times again to adding inorganic salt Ni (NO
3)
2The citric acid of molar weight is 70 ℃～80 ℃ stirrings, till forming transparent heavy-gravity colloidal sol;
(3) colloidal sol is made gel in 110 ℃～130 ℃ following dryings, take out xerogel, grind,, obtain presoma black Li-Ni-O powder 400 ℃～600 ℃ pre-burnings 1 hour～2 hours;
(4) with the presoma Li-Ni-O powder that makes in the step (3) and the TiO of weighing
2The powder ball milling mixes, and is dry-pressing formed under 4Mpa～6Mpa, and 1100 ℃～1300 ℃ sintering 4 hours～8 hours obtain block Li-Ti-Ni-O stupalith.
3. a kind of Li and Ti doped nickel oxide-base ceramic material as claimed in claim 1 is characterized in that using as dielectric substance.
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| CN1159256C CN1159256C (en) | 2004-07-28 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101292310B (en) * | 2005-10-17 | 2011-05-18 | 富士重工业株式会社 | Lithium ion capacitor |
| CN102157724A (en) * | 2011-03-09 | 2011-08-17 | 北京工业大学 | Method for claddingLiMn2O4 with Sn based on self-segregation cladding |
| CN102340185A (en) * | 2010-05-12 | 2012-02-01 | 通用电气公司 | Dielectric materials for power transfer system |
| CN102653863A (en) * | 2012-05-10 | 2012-09-05 | 东北大学 | Preparation method of Ru-Li codoped nickel oxide film |
| US8968603B2 (en) | 2010-05-12 | 2015-03-03 | General Electric Company | Dielectric materials |
| US9174876B2 (en) | 2010-05-12 | 2015-11-03 | General Electric Company | Dielectric materials for power transfer system |
| CN106747606A (en) * | 2017-01-04 | 2017-05-31 | 姚月祥 | A kind of method that template prepares Na doping carbon dioxide absorber ceramics |
| US9954580B2 (en) | 2011-07-28 | 2018-04-24 | General Electric Company | Dielectric materials for power transfer systems |
| CN111410526A (en) * | 2020-03-27 | 2020-07-14 | 广东风华高新科技股份有限公司 | Perovskite-doped barium stannate material and preparation method and application thereof |
-
2002
- 2002-06-21 CN CNB021214379A patent/CN1159256C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101292310B (en) * | 2005-10-17 | 2011-05-18 | 富士重工业株式会社 | Lithium ion capacitor |
| CN102340185A (en) * | 2010-05-12 | 2012-02-01 | 通用电气公司 | Dielectric materials for power transfer system |
| US8968603B2 (en) | 2010-05-12 | 2015-03-03 | General Electric Company | Dielectric materials |
| US8968609B2 (en) | 2010-05-12 | 2015-03-03 | General Electric Company | Dielectric materials for power transfer system |
| CN102340185B (en) * | 2010-05-12 | 2015-05-20 | 通用电气公司 | Dielectric materials for power transfer system |
| US9174876B2 (en) | 2010-05-12 | 2015-11-03 | General Electric Company | Dielectric materials for power transfer system |
| CN102157724A (en) * | 2011-03-09 | 2011-08-17 | 北京工业大学 | Method for claddingLiMn2O4 with Sn based on self-segregation cladding |
| CN102157724B (en) * | 2011-03-09 | 2014-08-20 | 北京工业大学 | Method for claddingLiMn2O4 with Sn based on self-segregation cladding |
| US9954580B2 (en) | 2011-07-28 | 2018-04-24 | General Electric Company | Dielectric materials for power transfer systems |
| CN102653863A (en) * | 2012-05-10 | 2012-09-05 | 东北大学 | Preparation method of Ru-Li codoped nickel oxide film |
| CN106747606A (en) * | 2017-01-04 | 2017-05-31 | 姚月祥 | A kind of method that template prepares Na doping carbon dioxide absorber ceramics |
| CN111410526A (en) * | 2020-03-27 | 2020-07-14 | 广东风华高新科技股份有限公司 | Perovskite-doped barium stannate material and preparation method and application thereof |
| CN111410526B (en) * | 2020-03-27 | 2020-12-29 | 广东风华高新科技股份有限公司 | Perovskite-doped barium stannate material and preparation method and application thereof |
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| CN1159256C (en) | 2004-07-28 |
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