CN110148526A - A kind of ZnSN nano-material and preparation method thereof for supercapacitor - Google Patents
A kind of ZnSN nano-material and preparation method thereof for supercapacitor Download PDFInfo
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- CN110148526A CN110148526A CN201910335436.9A CN201910335436A CN110148526A CN 110148526 A CN110148526 A CN 110148526A CN 201910335436 A CN201910335436 A CN 201910335436A CN 110148526 A CN110148526 A CN 110148526A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 230000009977 dual effect Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 241000272814 Anser sp. Species 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims 1
- 239000002070 nanowire Substances 0.000 abstract description 10
- 239000003990 capacitor Substances 0.000 abstract description 9
- 238000010574 gas phase reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 239000007772 electrode material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The ZnSN nano-material and preparation method thereof that the invention discloses a kind of for supercapacitor, 10~30nm of the ZnSN nanowire diameter, 1.5~3 μm of length, collimation arrangement；The molar ratio of Zn, S and N element is (0.51~0.54): (0.35~0.37): (0.11~0.12)；ZnSN nano-material is prepared using dual temperature area horizontal pipe furnace, and using ZnO powder as raw material, H2S and NH3 are reaction gas, and using specific processing step and parameter, gas phase reaction generates ZnSN nano-material；ZnSN nano-material is used for electrode of super capacitor, shows wild goose capacitance characteristic, and specific capacitance is 2100~2300F/g, and conservation rate is greater than 93% after circulation 10000 times.ZnSN nano-material preparation method is at low cost, easily operated, it can be achieved that large-scale production.
Description
Technical field
The present invention relates to the field of electrode material for super capacitor, in particular to a kind of metallization for supercapacitor
Close object electrode material and preparation method thereof.
Background technique
With the continuous consumption of the fossil energies such as petroleum, natural gas, environmental pollution is increasingly severe, solar energy, tide energy,
The clean energy resourcies such as wind energy are of increasing concern.The efficient application of clean energy resource, other than the device of energy production, energy storage device
Part is also increasingly important.In practice, for this intermittent clean energy resource, energy stores are to restrict its widely applied ring collar
Section.In energy storage device, supercapacitor is a kind of novel storage of performance between traditional capacitor and secondary cell
Energy device, with power density is high, charge/discharge speed is fast, temperature range is wide, has extended cycle life, is almost non-maintaining, environmentally protective
The advantages that, thus the application field particularly suitable for clean energy resource.In addition, supercapacitor new-energy automobile, consumer electronics,
The numerous areas such as heavy-duty machinery, military affairs also have a wide range of applications.
The electrode material of supercapacitor commercialization at present is substantially activated carbon.The remarkable advantage of carbon material is: circulation is steady
Qualitative length up to million times, but has a significant deficiency, i.e., specific capacitance is not high, only 50~150F/g.This material is made into
Supercapacitor, be suitable for three typical fields: first, to the lower occasion of energy requirement；Second, substantially non-maintaining
Occasion, such as desert, forest, deep-sea depopulated zone；Third, the supercapacitor of carbon material production is close to reach certain energy
Degree, then need very large component, occupy big quantity space, thus is applicable to the region of space license.In military field
Application for.According to the report, many countries are all developing this kind of directed energy weapon of laser gun, but the problem that volume and weight is excessive
This weapon is allowed to be difficult to practice.Such as to be necessarily mounted at Boeing-747 big for bulky U.S.'s Boeing YAL-1 airborne laser system
On type passenger plane, power can only but shoot down a frame small drone, this project was finally cancelled in 2012.Although nowadays laser
Weapon can be contracted to suitcase size, but huge energy supply demand makes still surprising huge of whole system.It can be in short-term
It is interior offer very huge energy only supercapacitor, but at present used in carbon material because its energy density and power it is close
Degree is all lower, still needs the capacitor of bulkiness, some are even bigger than shipping container, it is difficult to meet actual demand,
People only find new electrode material, make it have higher power density, while also having high-energy density, to realize
This target.
Carbon material is a kind of this typical electric double layer capacitance material.In order to improve the energy density of supercapacitor, people
Increasingly pay close attention to some fake capacitance materials.Relative to electric double layer capacitance material, wild goose capacitance material has higher specific capacitance, thus
Under identical volume and quality, there can be more excellent comprehensive performance.Currently, pseudocapacitors electrode material mainly includes leading
Electric polymer, transition metal oxide, transition metal hydroxide, transient metal sulfide etc..In order to promote supercapacitor
Wider practical application, developing novel electrode material for super capacitor is still the target that people pursue always.
Summary of the invention
The present invention is directed to the application demand of high-efficiency energy-storage, provides a kind of ZnSN nano wire for electrode of super capacitor
Material, and provide the preparation method and technique of the material.ZnSN nano-material has good chemical property.
The present invention provides a kind of ZnSN nano-material for supercapacitor, ZnSN nanowire diameter 10~
30nm, 1.5~3 μm of length, and collimate arrangement；ZnSN is a kind of new material formed by tri- kinds of elements of Zn, S and N, Zn, S and N
The molar ratio of element is (0.51~0.54): (0.35~0.37): (0.11~0.12)；ZnSN nano material is used for super capacitor
Device electrode shows wild goose capacitance characteristic, has very high specific capacitance, is 2100~2300F/g, specific capacitance after circulation 10000 times
Conservation rate is greater than 93%.
The present invention also provides the preparation methods for preparing the above-mentioned ZnSN nano-material for supercapacitor, specific to wrap
Include following steps:
1) using dual temperature area horizontal pipe furnace as growth apparatus；Using quartz as substrate, it is placed in the downstream end of horizontal pipe furnace；
The ZnO powder of 99.99% or more purity is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 1.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 900 DEG C, and substrate zone temperature is 500 DEG C；
3) it first passes through a gas-guide pipeline and is passed through H2S, 12~16sccm of gas flow, react 5min；Then it is passed through again
NH3,12~16sccm of gas flow keep H2S in step 2) to be passed through while being passed through NH3, and NH3 gas flow and step
It is rapid 2) in H2S gas flow it is identical, react 20min in H2S-NH3 mixed atmosphere；
4) power supply after reaction, is closed, maintains H2S-NH3 in step 3) to be passed through situation, until furnace temperature is reduced to 150
℃；It is then shut off gas source, continuing to vacuumize remains pressure in tube furnace no more than 3Pa, and furnace temperature is cooled to room temperature；It takes out
Substrate collects product to get ZnSN nano-material.
In above-mentioned gas phase reaction growing method, the sequencing and its parameter of each technique are obtained after many experiments
, it needs accurately to control, beyond the range, you can't get ZnSN nano-materials, with less above-mentioned structure and morphology and electricity
Chemical property.
The beneficial effects of the present invention are:
(1) the ZnSN nano-material obtained by the present invention is a kind of new ternary nano material, contains tri- kinds of Zn, S, N
Element, and the content of N can reach 10% or more.
(2) in ZnSN nano-material, nanowire diameter is in 30nm hereinafter, having very high specific surface area and active sites
Point is conducive to the immersion of electrolyte, is conducive to the transmission of ion and electronics, is conducive to the electric conductivity for promoting electrode material, favorably
In pattern and structural stability of the maintenance nano material in electrochemical process.
(3) Zn, which is difficult to react with N, generates compound, and the present invention uses the mixing source method of H2S and NH3, and uses
The method for being passed through H2S vulcanization in advance is acted on using the concerted catalysis of S, is reacted S with Zn jointly with N and is generated ZnSN, is
A kind of novel material, it is expected to which there is unique chemical property.
(4) ZnSN nano-material is used for electrode of super capacitor, has very excellent performance, and specific capacitance may be up to
2300F/g, and there is high cyclical stability, it is a kind of excellent electrode material for super capacitor.
(5) preparation method provided by the present invention a step can be completed in horizontal pipe furnace, and equipment is simple, raw materials used
It is inexpensive, it is easily operated, and yield is larger, it can be achieved that large-scale industrial production.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of ZnSN nano-material made from embodiment 1.
Fig. 2 is the specific capacitance cyclical stability curve graph of ZnSN nano-material made from embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
1) using dual temperature area horizontal pipe furnace as growth apparatus；Using quartz as substrate, it is placed in the downstream end of horizontal pipe furnace；
The ZnO powder of 99.99% or more purity is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 1.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 900 DEG C, and substrate zone temperature is 500 DEG C；
3) it first passes through a gas-guide pipeline and is passed through H2S, gas flow 12sccm, react 5min；Then it is passed through NH3, gas again
Body flow 12sccm keeps H2S in step 2) to be passed through while being passed through NH3, and in NH3 gas flow and step 2)
H2S gas flow is identical, reacts 20min in H2S-NH3 mixed atmosphere；
4) power supply after reaction, is closed, maintains H2S-NH3 in step 3) to be passed through situation, until furnace temperature is reduced to 150
℃；It is then shut off gas source, continuing to vacuumize remains pressure in tube furnace no more than 3Pa, and furnace temperature is cooled to room temperature；It takes out
Substrate collects product to get ZnSN nano-material.
Attached drawing 1 is the SEM figure of ZnSN nano-material made from embodiment 1, ZnSN 10~30nm of nanowire diameter, length
1.5~3 μm, and collimate arrangement.
ZnSN nano-material made from embodiment 1 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSN nano wire
The molar ratio of Zn, S and N element is 0.54:0.35:0.11 in material.
Show that the electro-chemical test of ZnSN nano-material: ZnSN shows as fake capacitance characteristic, under 1A/g current density
Specific capacitance be 2100F/g, the specific capacitance under 10A/g current density is 1600F/g, has good high rate performance.
Attached drawing 2 is specific capacitance cyclical stability of the ZnSN nano-material under 1A/g current density made from embodiment 1
Curve graph, ZnSN nano-material is as electrode, and specific capacitance conservation rate is 94.5% after recycling 10000 times.
Embodiment 2
1) using dual temperature area horizontal pipe furnace as growth apparatus；Using quartz as substrate, it is placed in the downstream end of horizontal pipe furnace；
The ZnO powder of 99.99% or more purity is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 1.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 900 DEG C, and substrate zone temperature is 500 DEG C；
3) it first passes through a gas-guide pipeline and is passed through H2S, gas flow 14sccm, react 5min；Then it is passed through NH3, gas again
Body flow 14sccm keeps H2S in step 2) to be passed through while being passed through NH3, and in NH3 gas flow and step 2)
H2S gas flow is identical, reacts 20min in H2S-NH3 mixed atmosphere；
4) power supply after reaction, is closed, maintains H2S-NH3 in step 3) to be passed through situation, until furnace temperature is reduced to 150
℃；It is then shut off gas source, continuing to vacuumize remains pressure in tube furnace no more than 3Pa, and furnace temperature is cooled to room temperature；It takes out
Substrate collects product to get ZnSN nano-material.
SEM test is carried out to ZnSN nano-material made from embodiment 2, shows ZnSN 10~30nm of nanowire diameter,
1.5~3 μm of length, and arrangement is collimated, it is similar to ZnSN nano-material pattern obtained by embodiment 1.
ZnSN nano-material made from embodiment 2 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSN nano wire
The molar ratio of Zn, S and N element is 0.53:0.36:0.11 in material.
Show the electro-chemical test of ZnSN nano-material: ZnSN shows as fake capacitance characteristic；Under 1A/g current density
Specific capacitance be 2210F/g, the specific capacitance under 10A/g current density is 1700F/g, has good high rate performance；In 1A/g
Under current density, specific capacitance conservation rate is 94.1% after circulation 10000 times.
Embodiment 3
1) using dual temperature area horizontal pipe furnace as growth apparatus；Using quartz as substrate, it is placed in the downstream end of horizontal pipe furnace；
The ZnO powder of 99.99% or more purity is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 1.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 900 DEG C, and substrate zone temperature is 500 DEG C；
3) it first passes through a gas-guide pipeline and is passed through H2S, gas flow 16sccm, react 5min；Then it is passed through NH3, gas again
Body flow 16sccm keeps H2S in step 2) to be passed through while being passed through NH3, and in NH3 gas flow and step 2)
H2S gas flow is identical, reacts 20min in H2S-NH3 mixed atmosphere；
4) power supply after reaction, is closed, maintains H2S-NH3 in step 3) to be passed through situation, until furnace temperature is reduced to 150
℃；It is then shut off gas source, continuing to vacuumize remains pressure in tube furnace no more than 3Pa, and furnace temperature is cooled to room temperature；It takes out
Substrate collects product to get ZnSN nano-material.
SEM test is carried out to ZnSN nano-material made from embodiment 3, shows ZnSN 10~30nm of nanowire diameter,
1.5~3 μm of length, and arrangement is collimated, it is similar to ZnSN nano-material pattern obtained by embodiment 1.
ZnSN nano-material made from embodiment 3 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSN nano wire
The molar ratio of Zn, S and N element is 0.51:0.37:0.12 in material.
Show the electro-chemical test of ZnSN nano-material: ZnSN shows as fake capacitance characteristic；Under 1A/g current density
Specific capacitance be 2300F/g, the specific capacitance under 10A/g current density is 1850F/g, has good high rate performance；In 1A/g
Under current density, specific capacitance conservation rate is 93.0% after circulation 10000 times.
The each component content and ratio of ZnSN nano-material made from 1 Examples 1 to 3 of table
| Embodiment | Zn content (mol.%) | S content (mol.%) | N content (mol.%) | Zn:S:N molar ratio |
| Embodiment 1 | 54 | 35 | 11 | 54:35:11 |
| Embodiment 2 | 53 | 36 | 11 | 53:36:11 |
| Embodiment 3 | 51 | 37 | 12 | 51:37:12 |
Claims (3)
1. a kind of ZnSN nano-material and preparation method thereof for supercapacitor, it is characterised in that the ZnSN nanometer
10~30nm of linear diameter, 1.5~3 μm of length, and collimate arrangement；ZnSN is a kind of green wood formed by tri- kinds of elements of Zn, S and N
The molar ratio of material, Zn, S and N element is (0.51~0.54): (0.35~0.37): (0.11~0.12).
2. a kind of preparation method of the ZnSN nano-material for supercapacitor as described in claim 1, feature exist
In including the following steps:
1) using dual temperature area horizontal pipe furnace as growth apparatus；Using quartz as substrate, it is placed in the downstream end of horizontal pipe furnace；Purity
99.99% or more ZnO powder is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 1.5Pa, then by horizontal tube stove heating, raw material area temperature
It is 900 DEG C, substrate zone temperature is 500 DEG C；
3) it first passes through a gas-guide pipeline and is passed through H2S, 12~16sccm of gas flow, react 5min；Then it is passed through NH3, gas again
Body 12~16sccm of flow keeps H2S in step 2) to be passed through while being passed through NH3, and in NH3 gas flow and step 2)
H2S gas flow it is identical, react 20min in H2S-NH3 mixed atmosphere；
4) power supply after reaction, is closed, maintains H2S-NH3 in step 3) to be passed through situation, until furnace temperature is reduced to 150 DEG C；So
After close gas source, continuing to vacuumize remains pressure in tube furnace no more than 3Pa, and furnace temperature is cooled to room temperature；Substrate is taken out,
Product is collected to get ZnSN nano-material.
3. a kind of ZnSN nano-material for supercapacitor according to claim 1 or 2 is used for supercapacitor
Electrode shows wild goose capacitance characteristic, has very high specific capacitance, is 2100~2300 F/g, specific capacitance is protected after circulation 10000 times
Holdup is greater than 93%.
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|---|---|---|---|---|
| JPH03266406A (en) * | 1990-03-15 | 1991-11-27 | Murata Mfg Co Ltd | Film capacitor |
| CN102593198A (en) * | 2012-03-02 | 2012-07-18 | 合肥工业大学 | II-VI group laminating integrated nano photovoltaic device and manufacturing method thereof |
| CN103390590A (en) * | 2013-06-28 | 2013-11-13 | 合肥工业大学 | Storage manufacturing method based on P-type ZnSe/ N-type Si core shell nanowire heterojunction |
| CN105304729A (en) * | 2015-09-08 | 2016-02-03 | 安阳师范学院 | Flexible optoelectronic device based on graphene and II-VI group semiconductor axial p-n junction nanowire array and preparation method thereof |
| CN106315659A (en) * | 2016-08-09 | 2017-01-11 | 吕冬梅 | CuCS nano-rod material used for superconductor and preparation method thereof |
| CN107057701A (en) * | 2017-05-15 | 2017-08-18 | 合肥工业大学 | A kind of β NaYF4:Yb/Tm@ZnxCd1‑xS core-shell nanospheres and preparation method thereof |
| CN108529675A (en) * | 2018-05-14 | 2018-09-14 | 合肥工业大学 | A kind of rodlike bismuth sulfide hollow nanospheres and preparation method thereof |
| CN109585842A (en) * | 2018-10-08 | 2019-04-05 | 北京大学 | A kind of hybrid electrochemical energy storage system based on absorption counterfeit potential and embedded reactive |
-
2019
- 2019-04-24 CN CN201910335436.9A patent/CN110148526B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03266406A (en) * | 1990-03-15 | 1991-11-27 | Murata Mfg Co Ltd | Film capacitor |
| CN102593198A (en) * | 2012-03-02 | 2012-07-18 | 合肥工业大学 | II-VI group laminating integrated nano photovoltaic device and manufacturing method thereof |
| CN103390590A (en) * | 2013-06-28 | 2013-11-13 | 合肥工业大学 | Storage manufacturing method based on P-type ZnSe/ N-type Si core shell nanowire heterojunction |
| CN105304729A (en) * | 2015-09-08 | 2016-02-03 | 安阳师范学院 | Flexible optoelectronic device based on graphene and II-VI group semiconductor axial p-n junction nanowire array and preparation method thereof |
| CN106315659A (en) * | 2016-08-09 | 2017-01-11 | 吕冬梅 | CuCS nano-rod material used for superconductor and preparation method thereof |
| CN107057701A (en) * | 2017-05-15 | 2017-08-18 | 合肥工业大学 | A kind of β NaYF4:Yb/Tm@ZnxCd1‑xS core-shell nanospheres and preparation method thereof |
| CN108529675A (en) * | 2018-05-14 | 2018-09-14 | 合肥工业大学 | A kind of rodlike bismuth sulfide hollow nanospheres and preparation method thereof |
| CN109585842A (en) * | 2018-10-08 | 2019-04-05 | 北京大学 | A kind of hybrid electrochemical energy storage system based on absorption counterfeit potential and embedded reactive |
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| CN110148526B (en) | 2021-05-04 |
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