CN104211395A - Leadless piezoelectric ceramic material applicable to energy collecting device and preparation method thereof - Google Patents
Leadless piezoelectric ceramic material applicable to energy collecting device and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a leadless piezoelectric ceramic material applicable to an energy collecting device and a preparation method thereof, belonging to the field of piezoelectric ceramic materials. The preparation method comprises the following steps: mixing Nb2O5 and KOH, calcining, dissolving in deionized water, titrating with nitric acid to obtain a white precipitate, and dissolving in oxalic acid to obtain soluble niobium; titrating with ammonia water until the pH value is 10-11, thus obtaining a white precipitate; dissolving in citric acid to obtain a solution A; dissolving K2CO3, Na2CO3 and Li2CO3 in water to form a solution B, and dissolving Mn(CH3COO)2 in the solution B; mixing the solution A and the solution B, heating to obtain a sol, drying, and performing heat treatment to obtain powder; and granulating and molding the powder, and sintering at 950-1050 DEG C to obtain a ceramic body. According to the invention, the method is simple and low in energy consumption; and the prepared leadless piezoelectric ceramic material has a high electro-mechanical transformation coefficient and meets the requirements of an energy collecting device.
Description
Technical field
The present invention relates to a kind of lead-free piezoceramic material and preparation method who is applied to collection of energy device, belong to piezoceramic material field.
Background technology
Growing along with wireless technology and micro-electromechanical technology, take chemical cell as main, needs the drawback of traditional energy-provision way of periodic replacement day by day to appear.Piezoelectric energy collector is a kind of novel environmental energy acquisition technology, the direct piezoelectric effect of this device based on piezoelectric, by in environment almost ubiquitous mechanical vibrational energy change into recycling electric energy, thereby realize micro electro mechanical device as the self-powered of wireless sensor node etc., therefore have broad application prospects.Therefore the acquisition of high-energy-density piezoelectric is the key of preparing piezoelectric energy collector, carries out the high-energy-density piezoelectric research that is suitable for energy harvester and is even more important.
The piezoceramic material that is widely used at present collection of energy device is mainly Pb-based lanthanumdoped zirconate titanates (PZT) matrix system.Along with the pay attention to day by day of countries in the world to environment protection and Sustainable development, the novel high-performance leadless piezoelectric ceramics that development substitutes poisonous and harmful plumbum-based material has become one of urgent task of various countries ceramic science man in recent years
In order to meet the requirement of piezoelectric energy collecting device, piezoelectric ceramics must have higher energy density μ,
μ＝1/2(d*g)(F/A)
2
D: piezoelectric strain constant g: piezoelectric field constant
F: reactive force A: area
By above formula, can be found out, for material itself, higher energy density should be decided by electromechanical conversion coefficient (d*g), again because g=d/ ε
tso the material require of high electromechanical conversion coefficient (d*g) possesses high piezoelectric constant d and low-k ε simultaneously
t.But the synthetic lead-free piezoceramic material of conventional liquid process is difficult to have high piezoelectric constant and low-k concurrently simultaneously, thereby can not meet the performance requriements of collection of energy device to material high-energy-density.For example, 2013, the people such as the In-Tae Seo of Korea University attempted adopting conventional liquid process preparation towards the potassium-sodium niobate KNN base lead-free (reference: In-Tae of piezoelectric energy collector application
chang-Hoi
daniel Song,
§min-Soo
bo-Yun
sahn
young-Sik Kim,
§tae-Hyun Sung,
‖and Hyun-Cheol
" Piezoelectric Properties of Lead-free Piezoelectric Ceramics and Their Energy Harvester Characteristics, " J.Am.Ceram.Soc., 96[4] 1024 – 1028 (2013)).Result shows, although material has higher mechanical quality factor Q
m(803) and lower dielectric loss tan δ (0.009), but transducing coefficient (dg) is very low by (4911 * 10
-15m
2/ N), cannot meet high-performance piezoelectric energy collector and manufacture needs.
The present invention organically combines sol gel process and doping techniques, by build Mn doping Na in liquid phase environment
0.46k
0.46li
0.08nbO
3colloid, realizing raw material mixes at the even of molecular state with hotchpotch, thereby synthetic high reactivity doping ultra-fine nano-powder under lower thermal treatment temp, and further sintering is prepared the high-energy-density lead-free ceramics material that meets the service requirements of piezoelectric energy collecting device.
Summary of the invention
The object of this invention is to provide a kind of be applied to collection of energy device there is lead-free piezoceramic material of high-energy-density and preparation method thereof.The Mn doping Na preparing in the present invention
0.46k
0.46li
0.08nbO
3piezoceramic material has higher energy density, can meet the performance requriements of collection of energy device.So-called energy density refers to the size of contained energy in unit space or quality, and specific to piezoceramic material, high-energy-density is mainly determined by large electromechanical conversion coefficient (d*g).
The above-mentioned lead-free piezoceramic material with high-energy-density of the present invention, is characterized in that, is Mn doping Na
0.46k
0.46li
0.08nbO
3, matrix chemical constitution is: Na
0.46k
0.46li
0.08nbO
3-x%Mn, the numerical value of x is 0.5～3.
The above-mentioned preparation method with the lead-free piezoceramic material nanometer powder of high-energy-density, is characterized in that obtaining by doped sol gel technology, specifically comprises the following steps:
(1) will after Niobium Pentxoxide and potassium hydroxide (preferably in molar ratio 1:10) mixed grinding, be positioned in platinum crucible through 350 ℃ of calcining 2～3h, products therefrom drips nitric acid to pH=2～3 after being dissolved in deionized water, obtain white precipitate, centrifugal collecting precipitation is also removed potassium ion for several times with deionized water washing precipitation; To be precipitated and dissolved in oxalic acid solution, heated and stirred, to clarification, is filtered and is obtained faint yellow transparent solubility niobium solution;
(2) get gained solubility niobium solution in step (1), drip ammoniacal liquor to pH=10～11, through centrifugation and deionized water wash, obtain white precipitate; Gained white precipitate is dissolved in the aqueous citric acid solution that concentration is 0.5～2mol/L, and heated and stirred obtains clear solution A, and the niobium in Niobium Pentxoxide is transferred in clear solution A substantially; By K
2cO
3, Na
2cO
3, Li
2cO
3after drying in loft drier according to Na
0.46k
0.46li
0.08nbO
3middle stoichiometric ratio, is dissolved in deionized water, makes solution B, according to Mn doping again Mn (CH
3cOO)
2be dissolved in solution B; Gained solution A is mixed with gained solution B, and 70～90 ℃ of heated and stirred 2～5h obtain vitreosol; Gained vitreosol is put into loft drier, and 100 ℃ dry, obtains transparent dry gel; Xerogel is processed at 350 ℃ to 2h removal organism and obtained intermediate product; After gained intermediate product is fully ground, at 500～700 ℃, calcine 3～6h, obtain Na
0.46k
0.46li
0.08nbO
3-x%Mn nano-powder.
Further Na
0.46k
0.46li
0.08nbO
3-x%Mn powder can obtain fine and close ceramic body through firing, and its processing method is characterised in that: adopt polyvinyl alcohol water solution (run-of-the-mill concentration is 5%) as binding agent by Na
0.46k
0.46li
0.08nbO
3-x%Mn powder carries out granulation, depresses (as pressure 100Mpa) moulding adding, in 2 hours binder removals of 560 ℃ of insulations.Adopt two sealed crucibles, and add Na
0.46k
0.46li
0.08nbO
3-x%Mn ceramic powder make its under sintering temperature as protective atmosphere, firing temperature is 950 ℃～1050 ℃, soaking time is 2～4h.According to above-mentioned processing method, can obtain fine and close pottery uniformly.Ceramic plate is by upper silver electrode, in 150 ℃ of silicone oil, and 40kVcm
-1voltage under the 30min that polarizes, then sample is carried out to electric performance test.
Generally preferred: the amount that strength of solution and step (2) volume of getting by step (1) can calculate niobium in clear solution A.
Above-mentioned materials of the present invention is applied to collection of energy device.Wherein, best sample is: Na
0.46k
0.46li
0.08nbO
3-2%Mn, i.e. Mn (CH
3cOO)
2when the Mn doping quality percentage composition that consumption makes is 2%, its best performance, d
33=220pc/N, ε
t=550, g
33=45.20, d
33g
33=9944 * 10
-15m
2/ N, meets the performance requriements of collection of energy device.
Compare with other invention technology, the present invention has following remarkable advantage:
(1) the method is converted into solubility niobium salt by simple chemical conversion by low price, the Niobium Pentxoxide that is easy to obtain, the expensive problem of niobium alkoxides used when having solved to a great extent sol-gel method and preparing niobate powder.Gained powder granularity is even, and sintering activity is large, for preparing at a lower temperature fine and close sintered compact, provides possibility.
(2) the method is under liquid phase environment, to make raw material more evenly mix, and has avoided utilizing solid phase method doped element that raw material is mixed uneven, thereby has caused the shortcomings such as performance degradation.Present method preparation technology is simple, and cost is low, and prepared lead-free piezoceramic material Environmental Safety has higher electromechanical conversion coefficient (d
33g
33), can be applicable to collection of energy device, there is potential society and economic implications.
When Mn content is 0.5%～3%, electromechanical conversion coefficient remains on 6500～10000 * 10
-15m
2within the scope of/N, meet the requirement of collection of energy device.
Accompanying drawing explanation
Fig. 1: the powder x-ray diffraction of different products (XRD) collection of illustrative plates, wherein, each diffraction curve is respectively the resulting Na by embodiment 1～4
0.46k
0.46li
0.08nbO
3the XRD figure spectrum of-x%Mn powder;
The morphology microstructure transmission electron microscope picture that Fig. 2: embodiment 1 obtains;
The Na that Fig. 3: embodiment 3 obtains
0.46k
0.46li
0.08nbO
3the scanning electron microscope (SEM) photograph of-2%Mn pottery;
Embodiment
Below by embodiment, further illustrate substantive distinguishing features of the present invention and remarkable advantage, but the present invention is never only confined to following examples.
Embodiment 1
(1) by Niobium Pentxoxide and potassium hydroxide in molar ratio 1:10 mix and fully grind after be positioned in platinum crucible through 360 ℃ of calcining 3h, obtain product and be dissolved in deionized water; With nitric acid, be titrated to pH=2, obtain a large amount of white precipitates, white precipitate is collected by centrifuging and for several times, be dissolved in oxalic acid solution with deionized water wash, heated and stirred is to resolution of precipitate, after finally filtering, obtain faint yellow transparent solubility niobium solution, utilize ICP fluorescent spectrometry to record Nb in solution
5+concentration;
(2) with measuring tank, measure gained solubility niobium solution in quantitative step (1), drip ammoniacal liquor to pH=10～11, through centrifugation and deionized water wash, obtain white precipitate; Gained white precipitate is dissolved in the aqueous citric acid solution that concentration is 0.5～2mol/L, and heated and stirred obtains clear solution A, and the niobium in Niobium Pentxoxide is transferred in clear solution A substantially; By K
2cO
3, Na
2cO
3, Li
2cO
3after drying in loft drier according to Na
0.46k
0.46li
0.08nbO
3middle stoichiometric ratio, is dissolved in a small amount of deionized water, makes solution B, by the doping of Mn 0.5% again Mn (CH
3cOO)
2be dissolved in solution B; Gained solution A is mixed with gained solution B, and 70～90 ℃ of heated and stirred 2～5h obtain vitreosol; Gained vitreosol is put into loft drier, and 100 ℃ of dry 48h, obtain transparent dry gel; Xerogel is processed at 350 ℃ to 2h removal organism and obtained intermediate product; After gained intermediate product is fully ground, at 500 ℃, calcine 5h, obtain Na
0.46k
0.46li
0.08nbO
3-0.5%Mn nano-powder.
(3) Na
0.46k
0.46li
0.08nbO
3-0.5%Mn powder can obtain fine and close ceramic body through firing, and its processing method is characterised in that: adopt polyvinyl alcohol water solution that mass concentration is 5% as binding agent by Na
0.46k
0.46li
0.08nbO
3-0.5%Mn powder carries out granulation, at 100Mpa forming under the pressure, in 2 hours binder removals of 560 ℃ of insulations.Adopt two sealed crucibles, and add Na
0.46k
0.46li
0.08nbO
3-0.5%Mn ceramic powder make its under sintering temperature as protective atmosphere, obtain ceramic of compact be incubated 2h at 1020 ℃ of firing temperatures after.
Embodiment 2
In step (2), by the Mn (CH of doping 1%
3cOO)
2be dissolved in solution B, ceramic sintering temperature is 1000 ℃, and all the other are with embodiment 1.
Embodiment 3
In step (2), by the doping of Mn 2% by Mn (CH
3cOO)
2be dissolved in solution B, ceramic sintering temperature is 980 ℃, and all the other are with embodiment 1.
Embodiment 4
In step (2), by the doping of Mn 3% by Mn (CH
3cOO)
2be dissolved in solution B, ceramic sintering temperature is 960 ℃, and all the other are with embodiment 1.
Above-described embodiment performance comparison table
Claims (6)
1. the lead-free piezoceramic material with high-energy-density, is characterized in that, is Mn doping Na
0.46k
0.46li
0.08nbO
3, matrix chemical constitution is: Na
0.46k
0.46li
0.08nbO
3-x%Mn, the numerical value of x is 0.5～3.
2. the method for the nanometer powder of the preparation lead-free piezoceramic material with high-energy-density claimed in claim 1, is characterized in that, by doped sol gel technology, obtains, and specifically comprises the following steps:
(1) will after Niobium Pentxoxide and potassium hydroxide mixed grinding, be positioned in platinum crucible through 350 ℃ of calcining 2～3h, products therefrom drips nitric acid to pH=2～3 after being dissolved in deionized water, obtain white precipitate, centrifugal collecting precipitation is also removed potassium ion for several times with deionized water washing precipitation; To be precipitated and dissolved in oxalic acid solution, heated and stirred, to clarification, is filtered and is obtained faint yellow transparent solubility niobium solution;
(2) get gained solubility niobium solution in step (1), drip ammoniacal liquor to pH=10～11, through centrifugation and deionized water wash, obtain white precipitate; Gained white precipitate is dissolved in the aqueous citric acid solution that concentration is 0.5～2mol/L, and heated and stirred obtains clear solution A, and the niobium in Niobium Pentxoxide is transferred in clear solution A substantially; By K
2cO
3, Na
2cO
3, Li
2cO
3after drying in loft drier according to Na
0.46k
0.46li
0.08nbO
3middle stoichiometric ratio, is dissolved in deionized water, makes solution B, according to Mn doping again Mn (CH
3cOO)
2be dissolved in solution B; Gained solution A is mixed with gained solution B, and 70～90 ℃ of heated and stirred 2～5h obtain vitreosol; Gained vitreosol is put into loft drier, and 100 ℃ dry, obtains transparent dry gel; Xerogel is processed at 350 ℃ to 2h removal organism and obtained intermediate product; After gained intermediate product is fully ground, at 500～700 ℃, calcine 3～6h, obtain Na
0.46k
0.46li
0.08nbO
3-x%Mn nano-powder.
3. according to the method for claim 2, it is characterized in that step (1) Niobium Pentxoxide and potassium hydroxide mol ratio 1:10.
4. the method for the ceramic body of the preparation lead-free piezoceramic material with high-energy-density claimed in claim 1, is characterized in that Na
0.46k
0.46li
0.08nbO
3-x%Mn powder can obtain fine and close ceramic body through firing, and its technique side comprises as follows: employing polyvinyl alcohol water solution as binding agent by Na
0.46k
0.46li
0.08nbO
3-x%Mn nano-powder carries out granulation, at pressurization compacted under, in 2 hours binder removals of 560 ℃ of insulations; Adopt two sealed crucibles, and add Na
0.46k
0.46li
0.08nbO
3-x%Mn ceramic powder make its under sintering temperature as protective atmosphere, firing temperature is 950 ℃～1050 ℃, soaking time is 2～4h, can obtain fine and close pottery uniformly.
5. according to the method for claim 4, it is characterized in that, add the pressure 100Mpa depressing.
6. material claimed in claim 1 is applied to collection of energy device.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689709A (en) * | 2018-05-17 | 2018-10-23 | 韶关学院 | A kind of preparation method of niobic acid titanium copper giant dielectric ceramics |
| CN112807852A (en) * | 2020-12-31 | 2021-05-18 | 广东春夏新材料科技股份有限公司 | Nano-filtration filter element material and production process and application thereof |
| CN115947600A (en) * | 2022-10-11 | 2023-04-11 | 电子科技大学 | Li-Mg-Mo-based single-phase ultralow-temperature ceramic material and preparation method thereof |
-
2014
- 2014-09-10 CN CN201410459529.XA patent/CN104211395B/en not_active Expired - Fee Related
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| KE WANG ET AL.: "Low-Temperature Sintering of Li-Modified (K，Na)NbO3 Lead-Free Ceramics:Sintering Behavior,Microstructure,and Electrical Properties", 《J.AM.CERAM.SOC》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689709A (en) * | 2018-05-17 | 2018-10-23 | 韶关学院 | A kind of preparation method of niobic acid titanium copper giant dielectric ceramics |
| CN108689709B (en) * | 2018-05-17 | 2021-04-16 | 韶关学院 | Preparation method of titanium copper niobate giant dielectric ceramic |
| CN112807852A (en) * | 2020-12-31 | 2021-05-18 | 广东春夏新材料科技股份有限公司 | Nano-filtration filter element material and production process and application thereof |
| CN115947600A (en) * | 2022-10-11 | 2023-04-11 | 电子科技大学 | Li-Mg-Mo-based single-phase ultralow-temperature ceramic material and preparation method thereof |
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