CN110203962A - A kind of ZnSP nano-bar material and preparation method thereof for supercapacitor - Google Patents
A kind of ZnSP nano-bar material and preparation method thereof for supercapacitor Download PDFInfo
- Publication number
- CN110203962A CN110203962A CN201910335426.5A CN201910335426A CN110203962A CN 110203962 A CN110203962 A CN 110203962A CN 201910335426 A CN201910335426 A CN 201910335426A CN 110203962 A CN110203962 A CN 110203962A
- Authority
- CN
- China
- Prior art keywords
- znsp
- nano
- bar material
- supercapacitor
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 7
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 7
- 241000272814 Anser sp. Species 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000002073 nanorod Substances 0.000 abstract description 5
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000013589 supplement Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000010574 gas phase reaction 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
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007812 deficiency 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
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration 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
- 230000002195 synergetic effect Effects 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The ZnSP nano-bar material and preparation method thereof that the invention discloses a kind of for supercapacitor, the ZnSP nanorod diameter 30~90nm, 150~300nm of length；The molar ratio of Zn, S and P element is (0.47~0.49): (0.42~0.46): (0.07~0.09)；ZnSP nano-bar material is prepared using gas phase and hydro-thermal two-step method, is the source material of Zn with acetic acid zinc powder, and H2S is the source gas of S, and trbasic zinc phosphate is the source material of P and the supplement source material of Zn, using specific processing step and parameter, generation ZnSP nano-bar material；ZnSP nano-bar material is used for electrode of super capacitor, shows wild goose capacitance characteristic, and specific capacitance is 2300~2450F/g, and specific capacitance conservation rate is greater than 91.2% after circulation 10000 times.ZnSP nano-bar preparation method for material 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 50~150 F/g.This material is done
At 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 to reach certain energy
Density then needs very large component, occupies big quantity space, thus is applicable to the region of space license.To be led in military affairs
For the application in domain.According to the report, many countries are all developing this kind of directed energy weapon of laser gun, but volume and weight is excessive asks
Topic allows this weapon to be difficult to practice.Such as bulky U.S.'s Boeing YAL-1 airborne laser system is necessarily mounted at Boeing-747
On airliner, 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
The only supercapacitor of very huge energy is provided in short time, but current used carbon material is because of its energy density and function
Rate density is all lower, still needs the capacitor of bulkiness, some are even bigger than shipping container, it is difficult to meet practical need
It asking, people only find new electrode material, higher power density is made it have, while also there is high-energy density, thus
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 ZnSP nanometer for electrode of super capacitor
Bar material, and provide the preparation method and technique of the material.ZnSP nano-bar material has good chemical property.
The present invention provides a kind of ZnSP nano-bar material for supercapacitor, ZnSP nanorod diameter 30~
90nm, 150~300nm of length；ZnSP is a kind of new material formed by tri- kinds of elements of Zn, S and P, and Zn, S and P element are rubbed
You are than being (0.47~0.49): (0.42~0.46): (0.07~0.09)；ZnSP nano-bar material is used for super capacitor electrode
Pole shows wild goose capacitance characteristic, has very high specific capacitance, is 2300~2450F/g, specific capacitance is kept after circulation 10000 times
Rate is greater than 91.2%.
The present invention also provides the preparation methods for preparing the above-mentioned ZnSP nano-bar material for supercapacitor, specific to wrap
Include following steps:
1) using dual temperature area horizontal pipe furnace as growth apparatus；Quartz boat is placed in the downstream end of horizontal pipe furnace；Purity
99% or more zinc acetate (Zn (CH3COO) 22H2O) is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 2.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 850 DEG C, and substrate zone temperature is 450 DEG C；
3) H2S, 18~20sccm of gas flow are passed through by gas piping, react 30min；
4) power supply after reaction, is closed, maintains H2S in step 3) to be passed through situation, until furnace temperature is reduced to 200 DEG C；So
After close gas source, close vacuum pump, furnace temperature cooled to room temperature；Quartz boat is taken out, collection obtains primary product；
5) trbasic zinc phosphate (Zn3 (PO4) 22H2O) is dissolved into water, solution concentration 1.2mol/L is placed in hydrothermal reaction kettle
In；
6) product for being collected into step 4) is placed in the solution in step 5), the primary product in every 200mg step 4)
The solution being added in 100~110mL step 5) then heats 10 hours at 120 DEG C；
7) it after hydro-thermal reaction, is cooled to room temperature, filters, obtain product to get ZnSP nano-bar material.
In above-mentioned gas phase reaction and hydro-thermal reaction growing method, the sequencing and its parameter of each technique are by multiple
It is obtained after experiment, needs accurately to control, you can't get ZnSP nano-bar materials beyond the range, with less above-mentioned knot
It is configured looks and chemical property.
The beneficial effects of the present invention are:
(1) the ZnSP nano-bar material obtained by the present invention is a kind of new ternary nano material, contains tri- kinds of Zn, S, P
Element, and Zn:(S+P) stoichiometric ratio close to 1:1.
(2) in ZnSP nano-bar material, nanometer rods size in nanometer scale, has very high specific surface area and active sites
Point is conducive to the infiltration 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) this patent is successfully made using the two-stage process of gas phase reaction and hydro-thermal reaction using the synergistic effect of S and P
S is reacted with Zn jointly with P generates ZnSP, is a kind of novel material, it is expected to have unique chemical property.
(4) it in hydro-thermal reaction, uses trbasic zinc phosphate for the source material of P, and can further replenish Zn in hydro-thermal reaction
Loss, to obtain Zn:(S+P) stoichiometric ratio close to 1:1 high quality ZnSP nano-bar material.
(5) ZnSP nano-bar material is used for electrode of super capacitor, has very excellent performance, and specific capacitance may be up to
2400F/g, and there is high cyclical stability, it is a kind of excellent electrode material for super capacitor.
(6) preparation method provided by the present invention, gas phase reaction and hydro-thermal reaction are method capable of being industrialized, equipment
Simply, raw materials used 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 ZnSP nano-bar material made from embodiment 1.
Fig. 2 is the specific capacitance cyclical stability curve graph of ZnSP nano-bar 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；Quartz boat is placed in the downstream end of horizontal pipe furnace；Purity
99% or more zinc acetate (Zn (CH3COO) 22H2O) is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 2.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 850 DEG C, and substrate zone temperature is 450 DEG C；
3) H2S, gas flow 20sccm are passed through by gas piping, react 30min；
4) power supply after reaction, is closed, maintains H2S in step 3) to be passed through situation, until furnace temperature is reduced to 200 DEG C；So
After close gas source, close vacuum pump, furnace temperature cooled to room temperature；Quartz boat is taken out, collection obtains primary product；
5) trbasic zinc phosphate (Zn3 (PO4) 22H2O) is dissolved into water, solution concentration 1.2mol/L is placed in hydrothermal reaction kettle
In；
6) product for being collected into step 4) is placed in the solution in step 5), the primary product in every 200mg step 4)
The solution being added in 100mL step 5) then heats 10 hours at 120 DEG C；
7) it after hydro-thermal reaction, is cooled to room temperature, filters, obtain product to get ZnSP nano-bar material.
Attached drawing 1 is the SEM figure of ZnSP nano-bar material made from embodiment 1, and ZnSP 30~90nm of nanorod diameter is long
Spend 150~300nm.
ZnSP nano-bar material made from embodiment 1 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSP nanometers
The molar ratio of Zn, S and P element is 0.47:0.46:0.07 in bar material.
Show that the electro-chemical test of ZnSP nano-bar material: ZnSP shows as fake capacitance characteristic, under 1A/g current density
Specific capacitance be 2300F/g, the specific capacitance under 10A/g current density is 1870F/g, has good high rate performance.
Attached drawing 2 is specific capacitance cyclical stability of the ZnSP nano-bar material under 1A/g current density made from embodiment 1
Curve graph, ZnSP nano-bar material is as electrode, and specific capacitance conservation rate is 91.7% after recycling 10000 times.
Embodiment 2
1) using dual temperature area horizontal pipe furnace as growth apparatus；Quartz boat is placed in the downstream end of horizontal pipe furnace；Purity
99% or more zinc acetate (Zn (CH3COO) 22H2O) is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 2.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 850 DEG C, and substrate zone temperature is 450 DEG C；
3) H2S, gas flow 19sccm are passed through by gas piping, react 30min；
4) power supply after reaction, is closed, maintains H2S in step 3) to be passed through situation, until furnace temperature is reduced to 200 DEG C；So
After close gas source, close vacuum pump, furnace temperature cooled to room temperature；Quartz boat is taken out, collection obtains primary product；
5) trbasic zinc phosphate (Zn3 (PO4) 22H2O) is dissolved into water, solution concentration 1.2mol/L is placed in hydrothermal reaction kettle
In；
6) product for being collected into step 4) is placed in the solution in step 5), the primary product in every 200mg step 4)
The solution being added in 105mL step 5) then heats 10 hours at 120 DEG C；
7) it after hydro-thermal reaction, is cooled to room temperature, filters, obtain product to get ZnSP nano-bar material.
SEM test is carried out to ZnSP nano-bar material made from embodiment 2, shows ZnSP 30~90nm of nanorod diameter,
150~300nm of length, it is similar to ZnSP nano-bar material pattern obtained by embodiment 1.
ZnSP nano-bar material made from embodiment 2 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSP nanometers
The molar ratio of Zn, S and P element is 0.48:0.44:0.08 in bar material.
Show the electro-chemical test of ZnSP nano-bar material: ZnSP shows as fake capacitance characteristic；Under 1A/g current density
Specific capacitance be 2370F/g, the specific capacitance under 10A/g current density is 1905F/g, has good high rate performance；In 1A/g
Under current density, specific capacitance conservation rate is 91.2% after circulation 10000 times.
Embodiment 3
1) using dual temperature area horizontal pipe furnace as growth apparatus；Quartz boat is placed in the downstream end of horizontal pipe furnace；Purity
99% or more zinc acetate (Zn (CH3COO) 22H2O) is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 2.5Pa, then by horizontal tube stove heating, raw material area
Temperature is 850 DEG C, and substrate zone temperature is 450 DEG C；
3) H2S, gas flow 18sccm are passed through by gas piping, react 30min；
4) power supply after reaction, is closed, maintains H2S in step 3) to be passed through situation, until furnace temperature is reduced to 200 DEG C；So
After close gas source, close vacuum pump, furnace temperature cooled to room temperature；Quartz boat is taken out, collection obtains primary product；
5) trbasic zinc phosphate (Zn3 (PO4) 22H2O) is dissolved into water, solution concentration 1.2mol/L is placed in hydrothermal reaction kettle
In；
6) product for being collected into step 4) is placed in the solution in step 5), the primary product in every 200mg step 4)
The solution being added in 110mL step 5) then heats 10 hours at 120 DEG C；
7) it after hydro-thermal reaction, is cooled to room temperature, filters, obtain product to get ZnSP nano-bar material.
SEM test is carried out to ZnSP nano-bar material made from embodiment 3, shows ZnSP 30~90nm of nanorod diameter,
150~300nm of length, it is similar to ZnSP nano-bar material pattern obtained by embodiment 1.
ZnSP nano-bar material made from embodiment 3 is obtained by energy disperse spectroscopy (EDS) test, as shown in table 1, ZnSP nanometers
The molar ratio of Zn, S and P element is 0.49:0.42:0.09 in bar material.
Show the electro-chemical test of ZnSP nano-bar material: ZnSP shows as fake capacitance characteristic；Under 1A/g current density
Specific capacitance be 2450F/g, the specific capacitance under 10A/g current density is 1975F/g, has good high rate performance；In 1A/g
Under current density, specific capacitance conservation rate is 91.5% after circulation 10000 times.
The each component content and ratio of ZnSP nano-bar material made from 1 Examples 1 to 3 of table
| Embodiment | Zn content (mol.%) | S content (mol.%) | P content (mol.%) | Zn:S:P molar ratio |
| Embodiment 1 | 47 | 46 | 7 | 47:46:7 |
| Embodiment 2 | 48 | 44 | 8 | 48:44:8 |
| Embodiment 3 | 49 | 42 | 9 | 49:42:9 |
Claims (3)
1. a kind of ZnSP nano-bar material and preparation method thereof for supercapacitor, it is characterised in that the ZnSP nanometer
Stick 30~90nm of diameter, 150~300nm of length；ZnSP is a kind of new material formed by tri- kinds of elements of Zn, S and P, Zn, S and P
The molar ratio of element is (0.47~0.49): (0.42~0.46): (0.07~0.09).
2. a kind of preparation method of the ZnSP nano-bar 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；Quartz boat is placed in the downstream end of horizontal pipe furnace；Purity 99%
Above zinc acetate (Zn (CH3COO) 22H2O) is raw material, is placed in the upstream end of horizontal pipe furnace；
2) horizontal pipe furnace is evacuated to background vacuum lower than 2.5Pa, then by horizontal tube stove heating, raw material area temperature
It is 850 DEG C, substrate zone temperature is 450 DEG C；
3) H2S, 18~20sccm of gas flow are passed through by gas piping, react 30min；
4) power supply after reaction, is closed, maintains H2S in step 3) to be passed through situation, until furnace temperature is reduced to 200 DEG C；Then it closes
It holds one's breath source, closes vacuum pump, furnace temperature cooled to room temperature；Quartz boat is taken out, collection obtains primary product；
5) trbasic zinc phosphate (Zn3 (PO4) 22H2O) is dissolved into water, solution concentration 1.2mol/L is placed in hydrothermal reaction kettle；
6) product for being collected into step 4) is placed in the solution in step 5), and the primary product in every 200mg step 4) is added
To the solution in 100~110mL step 5), then heated 10 hours at 120 DEG C；
7) it after hydro-thermal reaction, is cooled to room temperature, filters, obtain product to get ZnSP nano-bar material.
3. a kind of ZnSP nano-bar 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 2300~2450 F/g, specific capacitance is protected after circulation 10000 times
Holdup is greater than 91.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910335426.5A CN110203962B (en) | 2019-04-24 | 2019-04-24 | ZnSP nanorod material for super capacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910335426.5A CN110203962B (en) | 2019-04-24 | 2019-04-24 | ZnSP nanorod material for super capacitor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110203962A true CN110203962A (en) | 2019-09-06 |
| CN110203962B CN110203962B (en) | 2021-08-03 |
Family
ID=67786265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910335426.5A Active CN110203962B (en) | 2019-04-24 | 2019-04-24 | ZnSP nanorod material for super capacitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110203962B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320662A (en) * | 2001-02-26 | 2001-11-07 | 中国科学院长春应用化学研究所 | Process for preparing doped nm powder of zine sulfide |
| CN101508461A (en) * | 2009-03-31 | 2009-08-19 | 北京科技大学 | Method for producing nano-zinc sulfide and doped zinc sulfide with low-temperature solid-phase method |
| CN101575117A (en) * | 2009-05-26 | 2009-11-11 | 陕西师范大学 | Method for thermally preparing solvent of high-orientating diameter adjustable ZnS nano-rod array |
| CN102097206A (en) * | 2009-12-09 | 2011-06-15 | 吉林师范大学 | Low temperature growth method for wurtzite zinc sulfide base diluted magnetic semiconductor nanorod |
| US20110280796A1 (en) * | 2010-05-12 | 2011-11-17 | National Chung Cheng University | Zinc Oxide Nanorod Thin Film and Method for Making Same |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
| CN102602984A (en) * | 2012-03-22 | 2012-07-25 | 合肥工业大学 | P type doped ZnSxSe1-x nano material and preparation method thereof |
| WO2014092167A1 (en) * | 2012-12-14 | 2014-06-19 | 日本碍子株式会社 | Surface light-emission element using zinc oxide substrate |
| CN106315659A (en) * | 2016-08-09 | 2017-01-11 | 吕冬梅 | CuCS nano-rod material used for superconductor and preparation method thereof |
| CN107619026A (en) * | 2017-10-19 | 2018-01-23 | 暨南大学 | A kind of nano wire p n hetero-junctions and preparation method thereof |
| CN109243836A (en) * | 2018-08-31 | 2019-01-18 | 浙江大学 | Cu as electrode material for super capacitor2Se nano material and preparation method thereof |
-
2019
- 2019-04-24 CN CN201910335426.5A patent/CN110203962B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320662A (en) * | 2001-02-26 | 2001-11-07 | 中国科学院长春应用化学研究所 | Process for preparing doped nm powder of zine sulfide |
| CN101508461A (en) * | 2009-03-31 | 2009-08-19 | 北京科技大学 | Method for producing nano-zinc sulfide and doped zinc sulfide with low-temperature solid-phase method |
| CN101575117A (en) * | 2009-05-26 | 2009-11-11 | 陕西师范大学 | Method for thermally preparing solvent of high-orientating diameter adjustable ZnS nano-rod array |
| CN102097206A (en) * | 2009-12-09 | 2011-06-15 | 吉林师范大学 | Low temperature growth method for wurtzite zinc sulfide base diluted magnetic semiconductor nanorod |
| US20110280796A1 (en) * | 2010-05-12 | 2011-11-17 | National Chung Cheng University | Zinc Oxide Nanorod Thin Film and Method for Making Same |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
| CN102602984A (en) * | 2012-03-22 | 2012-07-25 | 合肥工业大学 | P type doped ZnSxSe1-x nano material and preparation method thereof |
| WO2014092167A1 (en) * | 2012-12-14 | 2014-06-19 | 日本碍子株式会社 | Surface light-emission element using zinc oxide substrate |
| CN106315659A (en) * | 2016-08-09 | 2017-01-11 | 吕冬梅 | CuCS nano-rod material used for superconductor and preparation method thereof |
| CN107619026A (en) * | 2017-10-19 | 2018-01-23 | 暨南大学 | A kind of nano wire p n hetero-junctions and preparation method thereof |
| CN109243836A (en) * | 2018-08-31 | 2019-01-18 | 浙江大学 | Cu as electrode material for super capacitor2Se nano material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| S. LOCMELIS ET AL.: "Der Chemische Transport von ZnS und CdS mit Phosphor - die Mischphase ZnS:P", 《Z. ANORG. ALLG. CHEM.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110203962B (en) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107403698B (en) | A kind of application preparing the method for activated carbon and its active carbon of preparation using biomass | |
| CN110510689B (en) | Photo-thermal seawater desalination material with multi-stage structure and preparation method and application thereof | |
| CN108383098B (en) | Hollow porous carbon material co-doped with various heteroatoms, and preparation method and application thereof | |
| CN106848494B (en) | A kind of simple preparation method of carbon auto-dope nano carbon nitride film electrode | |
| JP2016538709A (en) | Titanium oxide-based supercapacitor electrode material and manufacturing method thereof | |
| CN106111161B (en) | A kind of ZnO/ZnS/CdS composite material and preparation method of porous core-shell structure | |
| CN103682340B (en) | A kind of iron-based fluoride nano material with hierarchy and its preparation method and application | |
| CN108682791B (en) | Method for preparing inorganic perovskite negative electrode material with layered structure by vapor phase method | |
| Wang et al. | A salt-free superhydrophilic metal-organic framework photothermal textile for portable and efficient solar evaporator | |
| CN110205634A (en) | A kind of ZnO/ZnS/CdS photo-anode film and preparation method thereof | |
| CN103318943B (en) | A kind of preparation method of flower-shaped ZnO nanorod cluster | |
| CN103274451A (en) | Synthesis and application of nanometer composite material with stannic oxide/zinc oxide core-shell structure | |
| Liu et al. | Ti3C2T x MXenes-based flexible materials for electrochemical energy storage and solar energy conversion | |
| CN203222497U (en) | Cold, heat, power and water poly-generation system for comprehensively utilizing wind energy and seawater heat energy | |
| CN104961159B (en) | A kind of nanometer tungsten oxide and one step vapour phase reduction preparation method and application | |
| CN103570013B (en) | A kind of method preparing graphene-inorganic nanometer composite material continuously fast | |
| CN102671590A (en) | Preparation method of carbon coated magnetic nano-spherical iron sulfide | |
| CN102389828B (en) | Preparation and application of high-dispersity ZnO/GaN solid solution | |
| CN107522266B (en) | Preparation method of hierarchical porous carbon material capacitive desalination electrode material | |
| CN107857308B (en) | Nickel-cobalt composite hydroxide ultra-long nanobelt, nickel-cobalt composite oxide ultra-long nanobelt and preparation method thereof | |
| Qian et al. | Conductive Metal–Organic Framework Nanosheets Constructed Hierarchical Water Transport Biological Channel for High‐Performance Interfacial Seawater Evaporation | |
| CN110203962A (en) | A kind of ZnSP nano-bar material and preparation method thereof for supercapacitor | |
| Yang et al. | A hierarchical strategy for fabricating synergistic 3D network bio-based porous carbon and 0D niobium-based bimetallic oxides as counter electrodes for I-and Cu-mediated dye-sensitized solar cells with N719 and Y123 dyes | |
| CN105314688B (en) | A kind of preparation method and applications of nickel oxide nano piece | |
| CN110820010A (en) | Self-supporting Ni2P/Ni @ C composite cathode hydrogen evolution material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |