CN109485419A - A kind of processing method of high-stability nano superlattices thermo electric material - Google Patents
A kind of processing method of high-stability nano superlattices thermo electric material Download PDFInfo
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Abstract
The invention discloses a kind of processing methods of high-stability nano superlattices thermo electric material, include the following steps: the preparation of (1) composite additive, (2) premix preparation, the preparation of (3) finished product.The present invention provides a kind of processing methods of thermo electric material, simple process, and rationally, easy to promote and utilize, the thermoelectricity capability of nano super-lattice thermo electric material obtained is good for step collocation, and stability in use is high, and the service life is long, the great market competitiveness.
Description
Technical field
The invention belongs to material working process technical fields, and in particular to a kind of high-stability nano superlattices thermo electric material
Processing method.
Background technique
Fossil energy its non-renewable bring energy crisis and was used as current main energy sources source
Greenhouse effects caused by carbon dioxide are discharged in journey to cause more and more to pay close attention to.According to statistics, about 2/3rds fossil
The energy of the energy is wasted in the form of waste heat in use；If can be recycled to this part waste heat, it is clear that alleviation
Energy crisis and solution greenhouse effects all have a very important significance；In this context, thermoelectric material conduct can be real
The functional material that existing thermal energy and electric energy directly convert, received higher and higher attention in recent years.
All the time, what is be used widely is mostly with the alloy thermoelectric material compared with high zt, such as Bi2Ti3, PbTe etc.；
But alloy material there is toxic, raw material shortcoming, thermo-chemical stability is poor the problems such as, be not suitable for large-scale application；In view of
This, in recent years, oxide material starts the attention and attention that cause thermoelectric material researcher.
People have carried out a large amount of experimental study to oxide pyroelectric material at present, although the material of a variety of types has been made
Material, but its carry out attachment film forming when, multilist it is existing between substrate combination strength it is bad, will affect the stability used and
Service life, to reduce the competitiveness in market.In addition, the electrical property of material itself, which is also required to further enhance, to be improved.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of adding for high-stability nano superlattices thermo electric material is provided
Work method.
The present invention is achieved by the following technical solutions:
A kind of processing method of high-stability nano superlattices thermo electric material, includes the following steps:
(1) prepared by composite additive:
A. potassium-sodium niobate powder and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtained after being stirred continuously 6 ~ 8min of processing
Mixed liquor A is spare；
B. pyrroles and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtain mixed liquid B after being stirred continuously 8 ~ 10min of processing
It is spare；
C. ammonium peroxydisulfate and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtained after being stirred continuously 10 ~ 12min of processing
Mixed liquor C is spare；
D. graphene, sodium pyrophosphate, dodecyl trimethyl ammonium bromide, disodium ethylene diamine tetraacetate, deionized water correspondence are pressed
Be mixed according to 14 ~ 18:4 of weight ratio ~ 7:2 ~ 5:0.5 ~ 1:75 ~ 80, be stirred continuously after 1 ~ 1.5h of processing mixed liquor D is standby
With；
E. mixed liquid B made from mixed liquor A made from operation a and operation b is mixed jointly and is put into reaction kettle, is stirred continuously
Handle 35 ~ 40min after, then by operation c made from mixed liquor C be slowly dropped in reaction kettle, after the completion heating keep reaction kettle
Interior temperature is 45 ~ 50 DEG C, after being stirred continuously 9 ~ 12h of processing, then mixed liquor D made from operation d is added in reaction kettle, is surpassed
Centrifugal filtration is carried out after 1.5 ~ 2h of sonication, and composite additive is obtained after finally successively cleaning one time with deionized water and dehydrated alcohol
It is spare；
(2) prepared by premix:
A. neodymium oxide, lithia, titanium dioxide mixing is carried out according to 4 ~ 5:2 of weight ratio ~ 3:1 ~ 2 to put into ball mill
Carry out ball-milling treatment, take out after 40 ~ 50min mixture E is spare；
B. the resulting mixture E of a will be operated to be put into calcining furnace, it is 1250 ~ 1300 DEG C that heating, which keeps the temperature in calcining furnace,
Heat preservation 5 ~ 7h of calcination processing after take out mixture F is spare；
C. will operate the resulting mixture F of b put into grinder taken out after ground 2000 mesh premix is spare；
(3) prepared by finished product:
The resulting premix of step (2) and step (1) resulting composite additive are mixed according to 6 ~ 7:1 of weight ratio, so
After put into crucible, keep crucible in be argon gas protection environment, and heat keep crucible in temperature be 1350 ~ 1380 DEG C, 10 ~
Material is got product after material in crucible is taken out cooled to room temperature after 12h.
Further, mass volume ratio when potassium-sodium niobate powder described in step (1) operation a and hydrochloric acid solution mix
For the mL of 1g:180 ~ 200；The concentration of the hydrochloric acid solution is 0.1 ~ 0.15mol/L.
Further, mass volume ratio when pyrroles and hydrochloric acid solution described in step (1) operation b mix be 1g:35 ~
40 mL；The concentration of the hydrochloric acid solution is 0.1 ~ 0.15mol/L.
Further, mass volume ratio when ammonium peroxydisulfate and hydrochloric acid solution described in step (1) operation c mix is
The mL of 1g:20 ~ 25；The concentration of the hydrochloric acid solution is 0.15 ~ 0.2mol/L.
Further, mixed liquor A made from operation a described in step (1) operation e and mixed liquid B made from operation b are total
Corresponding mass ratio is 1 ~ 1.2:1 when with mixing；The gross mass that mixed liquor C made from the operation c is added dropwise is that operation b is made
0.8 ~ 1 times of mixed liquid B gross mass；The additional amount of mixed liquor D made from the operation d is mixed liquid B made from operation b
1.4 ~ 1.6 times of gross mass.
Further, the frequency of ultrasonic wave is 600 ~ 650kHz when ultrasonic treatment described in step (1) operation e.
The present invention has carried out special improvement to the processing method of thermo electric material and has handled, wherein being first prepared for a kind of compound add
Feed ingredient, to enhance the electrical property and processing characteristics of thermo electric material entirety.First mixed liquor A, the mixed liquid B and mixed to prepare
It closes liquid C and carries out hybrid process, generate a large amount of polypyrrole/potassium-sodium niobate complex microsphere, then add the ingredients such as graphene
Carry out compound, under the action of auxiliary element, polypyrrole/potassium-sodium niobate complex microsphere is effectively inserted and fixed on graphene,
On the one hand it is able to ascend whole specific surface area and electrical property, on the other hand can enhance whole surface reaction activity and energy again
Power promotes material and the combination being attached between substrate strength, it is carried out hybrid process molding with premix obtained again later,
Obtained a kind of material uniformly, micro-nano phase interface links up, and zero defect, thermoelectricity capability are good, strength is big with substrate ining conjunction with, process use
The good thermo electric material of quality.
The present invention has the advantage that compared with prior art
The present invention provides a kind of processing method of thermo electric material, simple process, step collocation is rationally, easy to promote and utilize,
The thermoelectricity capability of nano super-lattice thermo electric material obtained is good, and stability in use is high, and the service life is long, the great market competitiveness.
Specific embodiment
Embodiment 1
A kind of processing method of high-stability nano superlattices thermo electric material, includes the following steps:
(1) prepared by composite additive:
A. potassium-sodium niobate powder and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 6min
It is spare to close liquid A；
B. pyrroles and hydrochloric acid solution are mixed jointly and are put into three-neck flask, be stirred continuously processing 8min after mixed liquid B it is standby
With；
C. ammonium peroxydisulfate and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 10min
It is spare to close liquid C；
D. graphene, sodium pyrophosphate, dodecyl trimethyl ammonium bromide, disodium ethylene diamine tetraacetate, deionized water correspondence are pressed
Be mixed according to weight ratio 14:4:2:0.5:75, be stirred continuously processing 1h after mixed liquor D it is spare；
E. mixed liquid B made from mixed liquor A made from operation a and operation b is mixed jointly and is put into reaction kettle, is stirred continuously
Handle 35min after, then by operation c made from mixed liquor C be slowly dropped in reaction kettle, after the completion heating keep reaction kettle in
Temperature is 45 DEG C, is stirred continuously after handling 9h, then mixed liquor D made from operation d is added in reaction kettle, is ultrasonically treated 1.5h
After carry out centrifugal filtration, after finally successively cleaning one time with deionized water and dehydrated alcohol composite additive it is spare；
(2) prepared by premix:
A. neodymium oxide, lithia, titanium dioxide are carried out mixing to put into carrying out ball in ball mill according to weight ratio 4:2:1
Mill processing, take out after 40min mixture E is spare；
B. the resulting mixture E of a will be operated to be put into calcining furnace, it is 1250 DEG C that heating, which keeps the temperature in calcining furnace, heat preservation
Taken out after calcination processing 5h mixture F is spare；
C. will operate the resulting mixture F of b put into grinder taken out after ground 2000 mesh premix is spare；
(3) prepared by finished product:
The resulting premix of step (2) and step (1) resulting composite additive are mixed according to weight ratio 6:1, then
It puts into crucible, keeps being argon gas protection environment in crucible, and heating temperature in holding crucible is 1350 DEG C, by earthenware after 10h
Material gets product material after taking out cooled to room temperature in crucible.
Further, mass volume ratio when potassium-sodium niobate powder described in step (1) operation a and hydrochloric acid solution mix
For 1g:180 mL；The concentration of the hydrochloric acid solution is 0.1mol/L.
Further, mass volume ratio when pyrroles described in step (1) operation b and hydrochloric acid solution mix is 1g:
35mL；The concentration of the hydrochloric acid solution is 0.1mol/L.
Further, mass volume ratio when ammonium peroxydisulfate and hydrochloric acid solution described in step (1) operation c mix is
1g:20mL；The concentration of the hydrochloric acid solution is 0.15mol/L.
Further, mixed liquor A made from operation a described in step (1) operation e and mixed liquid B made from operation b are total
Corresponding mass ratio is 1:1 when with mixing；The gross mass that mixed liquor C made from the operation c is added dropwise is mixed made from operation b
0.8 times for closing liquid B gross mass；The additional amount of mixed liquor D made from the operation d is mixed liquid B gross mass made from operation b
1.4 times.
Further, the frequency of ultrasonic wave is 600kHz when ultrasonic treatment described in step (1) operation e.
Embodiment 2
A kind of processing method of high-stability nano superlattices thermo electric material, includes the following steps:
(1) prepared by composite additive:
A. potassium-sodium niobate powder and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 7min
It is spare to close liquid A；
B. pyrroles and hydrochloric acid solution are mixed jointly and are put into three-neck flask, be stirred continuously processing 9min after mixed liquid B it is standby
With；
C. ammonium peroxydisulfate and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 11min
It is spare to close liquid C；
D. graphene, sodium pyrophosphate, dodecyl trimethyl ammonium bromide, disodium ethylene diamine tetraacetate, deionized water correspondence are pressed
Be mixed according to weight ratio 16:6:4:0.8:77, be stirred continuously processing 1.3h after mixed liquor D it is spare；
E. mixed liquid B made from mixed liquor A made from operation a and operation b is mixed jointly and is put into reaction kettle, is stirred continuously
Handle 38min after, then by operation c made from mixed liquor C be slowly dropped in reaction kettle, after the completion heating keep reaction kettle in
Temperature is 47 DEG C, is stirred continuously after handling 11h, then mixed liquor D made from operation d is added in reaction kettle, is ultrasonically treated
Centrifugal filtration is carried out after 1.6h, and it is spare that composite additive is obtained after finally successively cleaning one time with deionized water and dehydrated alcohol；
(2) prepared by premix:
A. neodymium oxide, lithia, titanium dioxide mixing is carried out according to weight ratio 4.4:2.5:1.6 to put into ball mill
Carry out ball-milling treatment, take out after 45min mixture E is spare；
B. the resulting mixture E of a will be operated to be put into calcining furnace, it is 1280 DEG C that heating, which keeps the temperature in calcining furnace, heat preservation
Taken out after calcination processing 6h mixture F is spare；
C. will operate the resulting mixture F of b put into grinder taken out after ground 2000 mesh premix is spare；
(3) prepared by finished product:
The resulting premix of step (2) and step (1) resulting composite additive are mixed according to weight ratio 6.5:1, so
After put into crucible, keep crucible in be argon gas protection environment, and heat keep crucible in temperature be 1370 DEG C, after 11h will
Material gets product material after taking out cooled to room temperature in crucible.
Further, mass volume ratio when potassium-sodium niobate powder described in step (1) operation a and hydrochloric acid solution mix
For 1g:190 mL；The concentration of the hydrochloric acid solution is 0.13mol/L.
Further, mass volume ratio when pyrroles described in step (1) operation b and hydrochloric acid solution mix is 1g:37
mL；The concentration of the hydrochloric acid solution is 0.12mol/L.
Further, mass volume ratio when ammonium peroxydisulfate and hydrochloric acid solution described in step (1) operation c mix is
1g:22 mL；The concentration of the hydrochloric acid solution is 0.18mol/L.
Further, mixed liquor A made from operation a described in step (1) operation e and mixed liquid B made from operation b are total
Corresponding mass ratio is 1.1:1 when with mixing；The gross mass that mixed liquor C made from the operation c is added dropwise is made from operation b
0.9 times of mixed liquid B gross mass；The additional amount of mixed liquor D made from the operation d is the total matter of mixed liquid B made from operation b
1.5 times of amount.
Further, the frequency of ultrasonic wave is 630kHz when ultrasonic treatment described in step (1) operation e.
Embodiment 3
A kind of processing method of high-stability nano superlattices thermo electric material, includes the following steps:
(1) prepared by composite additive:
A. potassium-sodium niobate powder and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 8min
It is spare to close liquid A；
B. pyrroles and hydrochloric acid solution are mixed jointly and are put into three-neck flask, be stirred continuously processing 10min after mixed liquid B it is standby
With；
C. ammonium peroxydisulfate and hydrochloric acid solution are mixed jointly and is put into three-neck flask, must mixed after being stirred continuously processing 12min
It is spare to close liquid C；
D. graphene, sodium pyrophosphate, dodecyl trimethyl ammonium bromide, disodium ethylene diamine tetraacetate, deionized water correspondence are pressed
Be mixed according to weight ratio 18:7:5:1:80, be stirred continuously processing 1.5h after mixed liquor D it is spare；
E. mixed liquid B made from mixed liquor A made from operation a and operation b is mixed jointly and is put into reaction kettle, is stirred continuously
Handle 40min after, then by operation c made from mixed liquor C be slowly dropped in reaction kettle, after the completion heating keep reaction kettle in
Temperature is 50 DEG C, is stirred continuously after handling 12h, then mixed liquor D made from operation d is added in reaction kettle, is ultrasonically treated 2h
After carry out centrifugal filtration, after finally successively cleaning one time with deionized water and dehydrated alcohol composite additive it is spare；
(2) prepared by premix:
A. neodymium oxide, lithia, titanium dioxide are carried out mixing to put into carrying out ball in ball mill according to weight ratio 5:3:2
Mill processing, take out after 50min mixture E is spare；
B. the resulting mixture E of a will be operated to be put into calcining furnace, it is 1300 DEG C that heating, which keeps the temperature in calcining furnace, heat preservation
Taken out after calcination processing 7h mixture F is spare；
C. will operate the resulting mixture F of b put into grinder taken out after ground 2000 mesh premix is spare；
(3) prepared by finished product:
The resulting premix of step (2) and step (1) resulting composite additive are mixed according to weight ratio 7:1, then
It puts into crucible, keeps being argon gas protection environment in crucible, and heating temperature in holding crucible is 1380 DEG C, by earthenware after 12h
Material gets product material after taking out cooled to room temperature in crucible.
Further, mass volume ratio when potassium-sodium niobate powder described in step (1) operation a and hydrochloric acid solution mix
For 1g:200 mL；The concentration of the hydrochloric acid solution is 0.15mol/L.
Further, mass volume ratio when pyrroles described in step (1) operation b and hydrochloric acid solution mix is 1g:40
mL；The concentration of the hydrochloric acid solution is 0.15mol/L.
Further, mass volume ratio when ammonium peroxydisulfate and hydrochloric acid solution described in step (1) operation c mix is
1g:25 mL；The concentration of the hydrochloric acid solution is 0.2mol/L.
Further, mixed liquor A made from operation a described in step (1) operation e and mixed liquid B made from operation b are total
Corresponding mass ratio is 1.2:1 when with mixing；The gross mass that mixed liquor C made from the operation c is added dropwise is made from operation b
1 times of mixed liquid B gross mass；The additional amount of mixed liquor D made from the operation d is mixed liquid B gross mass made from operation b
1.6 times.
Further, the frequency of ultrasonic wave is 650kHz when ultrasonic treatment described in step (1) operation e.
Comparative example 1
This comparative example 1 compared with Example 2, in the preparation of step (1) composite additive, eliminates the processing of operation d, and
The use of subsequent mixed liquor D, method and step in addition to this are all the same.
Comparative example 2
This comparative example 2 compared with Example 2, step (3) finished product preparation in, with etc. mass parts graphene step of replacing
(1) resulting composite additive ingredient, method and step in addition to this are all the same.
It is corresponding obtained to above-described embodiment 2, comparative example 1,2 method of comparative example in order to compare effect of the present invention
Thermo electric material be tested for the property, it is specific that first this material is attached on ceramic base material with vapor deposition method again, then carry out
Performance test, specific correlation data are as shown in table 1 below:
Table 1
Note: adhesive force described in upper table 1 is referring to " the scratch of the vapor deposition film and matrix adhesive force examination of JB/T8554-1997
Test method " related request carry out adhesive force test, specifically tested using the automatic scratching instrument of WS-2005 type coating adhesion,
Test method are as follows: the test of sound emission measurement method, loading speed 5N/min, scratch rate 2mm/min；The Seebeck system
The device model used when several and conductivity performance test is RZ-2001K(Ozawa Scientific Corporation)；Institute
The zero dimension thermoelectric figure of merit ZT stated is to test and obtain under the conditions of 500 DEG C.
The thermoelectricity capability of the combination strength and material of material and substrate made from the method for the present invention it can be seen from upper table 1
There is significant enhancing, service life and stability are obviously improved, the great market competitiveness and production and application value.
Claims (6)
1. a kind of processing method of high-stability nano superlattices thermo electric material, which comprises the steps of:
(1) prepared by composite additive:
A. potassium-sodium niobate powder and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtained after being stirred continuously 6 ~ 8min of processing
Mixed liquor A is spare；
B. pyrroles and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtain mixed liquid B after being stirred continuously 8 ~ 10min of processing
It is spare；
C. ammonium peroxydisulfate and hydrochloric acid solution are mixed jointly and is put into three-neck flask, obtained after being stirred continuously 10 ~ 12min of processing
Mixed liquor C is spare；
D. graphene, sodium pyrophosphate, dodecyl trimethyl ammonium bromide, disodium ethylene diamine tetraacetate, deionized water correspondence are pressed
Be mixed according to 14 ~ 18:4 of weight ratio ~ 7:2 ~ 5:0.5 ~ 1:75 ~ 80, be stirred continuously after 1 ~ 1.5h of processing mixed liquor D is standby
With；
E. mixed liquid B made from mixed liquor A made from operation a and operation b is mixed jointly and is put into reaction kettle, is stirred continuously
Handle 35 ~ 40min after, then by operation c made from mixed liquor C be slowly dropped in reaction kettle, after the completion heating keep reaction kettle
Interior temperature is 45 ~ 50 DEG C, after being stirred continuously 9 ~ 12h of processing, then mixed liquor D made from operation d is added in reaction kettle, is surpassed
Centrifugal filtration is carried out after 1.5 ~ 2h of sonication, and composite additive is obtained after finally successively cleaning one time with deionized water and dehydrated alcohol
It is spare；
(2) prepared by premix:
A. neodymium oxide, lithia, titanium dioxide mixing is carried out according to 4 ~ 5:2 of weight ratio ~ 3:1 ~ 2 to put into ball mill
Carry out ball-milling treatment, take out after 40 ~ 50min mixture E is spare；
B. the resulting mixture E of a will be operated to be put into calcining furnace, it is 1250 ~ 1300 DEG C that heating, which keeps the temperature in calcining furnace,
Heat preservation 5 ~ 7h of calcination processing after take out mixture F is spare；
C. will operate the resulting mixture F of b put into grinder taken out after ground 2000 mesh premix is spare；
(3) prepared by finished product:
The resulting premix of step (2) and step (1) resulting composite additive are mixed according to 6 ~ 7:1 of weight ratio, so
After put into crucible, keep crucible in be argon gas protection environment, and heat keep crucible in temperature be 1350 ~ 1380 DEG C, 10 ~
Material is got product after material in crucible is taken out cooled to room temperature after 12h.
2. a kind of processing method of high-stability nano superlattices thermo electric material according to claim 1, which is characterized in that
Mass volume ratio when potassium-sodium niobate powder described in step (1) operation a and hydrochloric acid solution mix is the mL of 1g:180 ~ 200；
The concentration of the hydrochloric acid solution is 0.1 ~ 0.15mol/L.
3. a kind of processing method of high-stability nano superlattices thermo electric material according to claim 1, feature exist
In mass volume ratio when pyrroles described in step (1) operation b and hydrochloric acid solution mix is the mL of 1g:35 ~ 40；The salt
The concentration of acid solution is 0.1 ~ 0.15mol/L.
4. a kind of processing method of high-stability nano superlattices thermo electric material according to claim 1, feature exist
In mass volume ratio when ammonium peroxydisulfate described in step (1) operation c and hydrochloric acid solution mix is the mL of 1g:20 ~ 25；Institute
The concentration for the hydrochloric acid solution stated is 0.15 ~ 0.2mol/L.
5. a kind of processing method of high-stability nano superlattices thermo electric material according to claim 1, which is characterized in that
Corresponding matter when being mixed jointly with mixed liquid B made from operation b of mixed liquor A made from operation a described in step (1) operation e
Amount is than being 1 ~ 1.2:1；The gross mass that mixed liquor C made from the operation c is added dropwise is mixed liquid B gross mass made from operation b
0.8 ~ 1 times；The additional amount of mixed liquor D made from the operation d is operate mixed liquid B gross mass made from b 1.4 ~ 1.6
Times.
6. a kind of processing method of high-stability nano superlattices thermo electric material according to claim 1, which is characterized in that
The frequency of ultrasonic wave is 600 ~ 650kHz when step (1) operates ultrasonic treatment described in e.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276158A (en) * | 2011-05-17 | 2011-12-14 | 太原理工大学 | Preparation method of metavanadate nano crystal / polymer composite fluorescent screen |
| WO2012032518A2 (en) * | 2010-09-07 | 2012-03-15 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd | A process for the formation of metal oxide nanoparticles coating of a solid substrate |
| CN104810530A (en) * | 2015-03-26 | 2015-07-29 | 桂林电子科技大学 | Preparation method and application of graphene-Pt (platinum) nanoparticle-polypyrrole composite material |
| US20160079001A1 (en) * | 2014-09-12 | 2016-03-17 | Yi-Jun Lin | Graphene Electrode Based Ceramic Capacitor |
| CN106495559A (en) * | 2016-10-19 | 2017-03-15 | 北京恒通绿建节能科技有限公司 | A kind of 03 type composite piezoelectric materials and preparation method thereof and device |
| CN107551275A (en) * | 2017-09-12 | 2018-01-09 | 山西大学 | A kind of preparation of magnetic nano drug and its method for load doxorubicin hydrochloride |
| CN107727858A (en) * | 2017-09-30 | 2018-02-23 | 山东理工大学 | A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors |
| CN108183039A (en) * | 2017-12-11 | 2018-06-19 | 中国科学院过程工程研究所 | Preparation method, carbon modification titanium niobate material, lithium-ion capacitor and its negative electrode slurry of carbon modification titanium niobate material |
-
2018
- 2018-10-26 CN CN201811255824.8A patent/CN109485419A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012032518A2 (en) * | 2010-09-07 | 2012-03-15 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd | A process for the formation of metal oxide nanoparticles coating of a solid substrate |
| CN102276158A (en) * | 2011-05-17 | 2011-12-14 | 太原理工大学 | Preparation method of metavanadate nano crystal / polymer composite fluorescent screen |
| US20160079001A1 (en) * | 2014-09-12 | 2016-03-17 | Yi-Jun Lin | Graphene Electrode Based Ceramic Capacitor |
| CN104810530A (en) * | 2015-03-26 | 2015-07-29 | 桂林电子科技大学 | Preparation method and application of graphene-Pt (platinum) nanoparticle-polypyrrole composite material |
| CN106495559A (en) * | 2016-10-19 | 2017-03-15 | 北京恒通绿建节能科技有限公司 | A kind of 03 type composite piezoelectric materials and preparation method thereof and device |
| CN107551275A (en) * | 2017-09-12 | 2018-01-09 | 山西大学 | A kind of preparation of magnetic nano drug and its method for load doxorubicin hydrochloride |
| CN107727858A (en) * | 2017-09-30 | 2018-02-23 | 山东理工大学 | A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors |
| CN108183039A (en) * | 2017-12-11 | 2018-06-19 | 中国科学院过程工程研究所 | Preparation method, carbon modification titanium niobate material, lithium-ion capacitor and its negative electrode slurry of carbon modification titanium niobate material |
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