CN110092418A - A kind of preparation method of the copper-based sulfide semiconductor nano material of ternary - Google Patents
A kind of preparation method of the copper-based sulfide semiconductor nano material of ternary Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01G30/00—Compounds of antimony
- C01G30/002—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A kind of copper-based sulfide semiconductor nano material of ternary is the nano-scale Ternary copper antimony sulfide that different metering ratios are prepared using solvent-thermal method, using inorganic mantoquita, inorganic antimonic salt and sulphur source as raw material, prepares ternary sulfide powder by the medium temperature single step reaction that pressurizes.Operation of the present invention is simple, step is less, raw material is cheap and easy to get, there is strong applicability to the selection of different material, preparation process product is easy to get, product cut size is tiny and crystal grain will not grow up, reaction process is not in that explosion causes preparation to fail, conducive to industrialization large-scale production, yield is high, up to 86.2%, product is mutually with high purity, impurity is few, purity may be up to 97.8%, universality is strong, process stabilizing, production stability is good, overcome the shortcomings that long-time high-temperature process is needed in traditional preparation methods, nano ternary antimonial copper glance material prepared by the present invention can be widely applied to lithium battery, thermoelectricity, the energy fields such as photoelectricity.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of copper-based sulfide semiconductor nano material of ternary
Preparation method.
Background technique
In face of fossil energy sources shortage and its bring problem of environmental pollution, exploitation uses new energy technology very urgent and must
It wants.Photoelectricity, thermoelectricity and lithium battery technology have extremely excellent performance and lower price among these, have it in energy market
There are very big universal potentiality.The basis that energy conversion and storge quality are promoted is material and suitable technology of preparing.Ternary is copper-based
Element contained by antimony sulfide (Cu-Sb-S is denoted as CAS) is cheap, stable, abundant, nontoxic, while there are four in CAS system
Stable ternary phase, CuSbS2(antimonial copper glance structure), Cu12Sb4S13(tetrahedrite structure), Cu3SbS4(famatinite structure)
And Cu3SbS3(cubic structure), different components and crystal structure assign its different physical property, have low intrinsic thermal conductivity
Rate (is lower than 1W/mK), and the excellent properties such as suitable bandwidth (0.8-1.4eV) and good absorbing properties are considered
The energy conversions storage art such as thermoelectricity, photoelectricity, lithium battery has a extensive future.
Due to containing 4 kinds of phases in CAS system, and high thermodynamic stability is all had, relatively narrow synthetic ingredient section makes
The problem of will appear multiphase coexistence or the removal of miscellaneous phase difficulty in general preparation method is obtained, for example phase is reinforced using traditional ball mill mixing
The method of sintering needs copper, antimony and sulphur simple substance powder by certain metering ratio after one hour of high-energy ball milling mixing, argon gas
800 DEG C of long-time solid-phase sinterings of high temperature, can just access CAS phase under protective atmosphere, and still will appear that object is mutually impure to be showed
As.These preparation methods need to introduce high-energy ball milling process, and the solid-phase sintering of (> 24 hours) for a long time, time-consuming energy consumption, cost
It is higher.Therefore it can be realized and the controllable simple preparation of copper antimony sulfide be necessary.
Meanwhile nano-sized materials possess the thermoelectricity and photoelectric properties better than block materials.Chen et al. utilizes heat injection
Method has synthesized Cu3SbS4Nanocrystal, and the thermoelectricity capability for promoting the copper-based sulfide of ternary is adulterated by nickel element, so that material
Thermoelectric figure of merit reach 0.37 at 250 DEG C, (Dongsheng Chen, Yan Zhao, Yani with good application prospect
Chen, Tingyu Lu, Yuanyuan Wang, Jun Zhou, Ziqi Liang, Adv. Electron. Mater.,
2016,2 (6): 1500473.).Nano particle is also considered as the very promising light absorption material applied to photoelectric device
Material, such as Cu12Sb4S13And Cu3SbS4Nanocrystal has stronger absorptivity in visible light and near-infrared, has reached 105cm-1,
Become preferable photovoltaic applications candidate materials.Cu3SbS4Nanocrystal is used as hole mobile material in perovskite battery,
Can be by inhibiting Carrier recombination to effectively improve hole injection, while the stability of battery is improved, the effect of perovskite battery
Rate reaches 8.7%(Zeng, Q., Di, Y., Huang, et al.J. Mater. Chem. C, 2018, 6(30),
7989.).The selection and experiment condition by control raw material such as Ramasamy, can be realized the synthesis (K. of all 4 CAS pure phases
Ramasamy, H. Sims, W. H. Butler and A. Gupta, Chem. Mater., 2014,26,2891.),
Injection method is warmed by height, under the protection of argon gas, sulfur powder is dissolved in 20 DEG C 18 dilute, and keep the temperature at 200 DEG C of high temperature
20 minutes, sulphur source solution is prepared.Then three necks burning is poured into copper acetate, antimony chloride, two mercaptan, oleic acid and 18 dilute mixing
Bottle keeps the temperature at 120 DEG C and carries out vacuumizing processing in 30 minutes.Sulphur source prepared above is rapidly injected in flask, temperature exists
200 DEG C of 1 hours of holding, and be stirred continuously.It is cooled to after room temperature, ethane and ethyl alcohol are added in flask, to mixed solution
Carry out ultrasound and centrifugal treating.Then the CAS powder of nanometric particles by standing three times with obtaining four kinds of pure phases after centrifugation.With
Upper synthetic method still has the problem of several aspects to need to solve: (1) complicated operation, needs just to be able to achieve by multiple steps
The recycling of particle；(2) yield is very low；(3) multiphase coexistence problem is difficult to resolve certainly, and finally multi-step is needed to handle；(4) it prepares
Process is unable to control, so that crystal grain is easy to grow up；(5) reaction process, which is easy explosion, causes preparation to fail；(6) product impurity is more,
Purity is low；(7) technique is unstable, and production stability is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the copper-based sulfide semiconductor nano material of ternary.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of the copper-based sulfide semiconductor nano material of ternary, which is characterized in that prepared not using solvent-thermal method
Nano-scale Ternary copper antimony sulfide with metering ratio is pressurizeed using inorganic mantoquita, inorganic antimonic salt and sulphur source as raw material by medium temperature
Single step reaction prepares ternary sulfide powder.
Further, the inorganic mantoquita is one of copper sulphate, copper acetate, copper chloride；The inorganic antimonic salt is acetic acid
One of antimony, antimony chloride；The sulphur source is one of thiocarbamide, sulphur powder.
Further, the inorganic mantoquita is preferably copper acetate, and the inorganic antimony is preferably antimony acetate, and the sulphur source is preferably
Thiocarbamide.
Further, the preparation in the antimony source is 20 ~ 25 DEG C of temperature under nitrogen protection, and antimonic salt powder is poured into glacial acetic acid
It in solution, is then ultrasonically treated 10 ~ 30 minutes, ultrasonic power 100W, dissolves antimony acetate powder all, obtain the second containing antimony
Acid solution；The nitrogen gas purity is 99.999%, and nitrogen pressure is 380 ~ 420pa.
Further, the preparation of the Ternary copper antimony sulfide nanoparticle, is dissolved in ethylene glycol first for inorganic mantoquita first
In ethereal solution, dissolve it all by stirring, speed of agitator is 250 ~ 300r/min, is then poured into diethanol amine above-mentioned molten
It in liquid and dissolves, then sulphur source is added in solution, and the acetic acid solution containing antimony is added, it is to be dissolved, it is subsequently placed in hydro-thermal reaction
In kettle, be that 1 DEG C/min is warming up to 150 ~ 240 DEG C with heating rate, keep the temperature 4 ~ 12 hours, after reaction kettle natural cooling is dropped
To 20 ~ 25 DEG C, mixed liquor is first used into alcohol washes, is then centrifuged for, outwelled supernatant, then cleaned with acetone, be then centrifuged for, it is described
Centrifugal rotational speed is 8000 ~ 12000r/min, and centrifugation time is 8 ~ 10 minutes, after centrifugation in the case where drying temperature is 60 ~ 85 DEG C
6 ~ 8 hours are dried to get Ternary copper antimony sulfide CAS is arrived.
Further, concentration of the inorganic antimonic salt in acetic acid solution is 0.1 ~ 0.3mol/L, the inorganic mantoquita, inorganic
The molar ratio of antimonic salt, sulphur source in reaction medium is 3:(1 ~ 3): (3 ~ 35).
A kind of Cu12Sb4S13The preparation method of semiconductor nano material, which comprises the steps of:
(1) under nitrogen protection, nitrogen gas purity 99.999%, pressure are 380 ~ 420pa, 20 ~ 25 DEG C of temperature are controlled, by acetic acid
Antimony powder end is poured into glacial acetic acid solvent as antimony source, by ultrasound 10 ~ 30 minutes, ultrasonic power 100W, realizes acetic acid antimony powder
The fully dissolved at end, obtains antimony acetate solution, and the concentration of the antimony acetate solution is 0.2mol/L；
(2) copper acetate is dissolved in ethylene glycol monomethyl ether solution first dissolves it all by stirring, and obtaining concentration is
Then diethanol amine is poured into above-mentioned solution and is dissolved, solution then is added in thiocarbamide by the copper acetate solution of 8.57mmol/L
In, and antimony acetate is added, mixes, copper acetate in configured solution, antimony acetate, thiocarbamide molar ratio be 3:1:3.4, be subsequently placed in
In hydrothermal reaction kettle, be that 1 DEG C/min is warming up to 150 ~ 240 DEG C with heating rate, keep the temperature 4 ~ 12 hours, after by reaction kettle from
20 ~ 25 DEG C so are cooled down to, mixed liquor is first used into alcohol washes, is then centrifuged for, outwells supernatant, then cleaned with acetone, then
Centrifugation, the centrifugal rotational speed are 8000 ~ 12000r/min, and centrifugation time is 8 ~ 10 minutes, are in drying temperature after centrifugation
6 ~ 8 hours are dried at 60 ~ 85 DEG C to get Cu is arrived12Sb4S13Semiconductor nano material.
A kind of Cu3SbS4The preparation method of semiconductor nano material, which is characterized in that it is to include the following steps:
(1) under nitrogen protection, nitrogen gas purity 99.999%, pressure are 380 ~ 420pa, 20 ~ 25 DEG C of temperature are controlled, by acetic acid
Antimony powder end is poured into glacial acetic acid solvent as antimony source, by ultrasound 10 ~ 30 minutes, ultrasonic power 100W, realizes acetic acid antimony powder
The fully dissolved at end, obtains antimony acetate solution, and the concentration of the antimony acetate solution is 0.2mol/L；
(2) copper acetate is dissolved in ethylene glycol monomethyl ether solution first dissolves it all by stirring, and obtaining concentration is 36mmol/
Then diethanol amine is poured into above-mentioned solution and is dissolved by the copper acetate solution of L, then thiocarbamide is added in solution, and is added
Antimony acetate mixes, copper acetate in configured solution, antimony acetate, thiocarbamide molar ratio be 3:1:35, be subsequently placed in hydrothermal reaction kettle
In, be that 1 DEG C/min is warming up to 150 ~ 240 DEG C with heating rate, keep the temperature 4 ~ 12 hours, after reaction kettle natural cooling is down to
20 ~ 25 DEG C, mixed liquor is first used into alcohol washes, is then centrifuged for, outwelled supernatant, then cleaned with acetone, be then centrifuged for, it is described from
Heart revolving speed is 8000 ~ 12000r/min, and centrifugation time is 8 ~ 10 minutes, is done at being 60 ~ 85 DEG C in drying temperature after centrifugation
Obtain Cu within dry 6 ~ 8 hours3SbS4Semiconductor nano material.
A kind of CuSbS2The preparation method of semiconductor nano material, which is characterized in that it is to include the following steps:
(1) under nitrogen protection, nitrogen gas purity 99.999%, pressure are 380 ~ 420pa, 20 ~ 25 DEG C of temperature are controlled, by acetic acid
Antimony powder end is poured into glacial acetic acid solvent as antimony source, by ultrasound 10 ~ 30 minutes, ultrasonic power 100W, realizes acetic acid antimony powder
The fully dissolved at end, obtains antimony acetate solution, and the concentration of the antimony acetate solution is 0.2mol/L；
(2) copper acetate is dissolved in ethylene glycol monomethyl ether solution first dissolves it all by stirring, and obtaining concentration is
Then diethanol amine is poured into above-mentioned solution and is dissolved, solution then is added in thiocarbamide by the copper acetate solution of 8.57mmol/L
In, and antimony acetate is added, mixes, copper acetate in configured solution, antimony acetate, thiocarbamide molar ratio be 1:1:2.5, be subsequently placed in
In hydrothermal reaction kettle, be 1 DEG C/minute with heating rate and be warming up to 150 ~ 240 DEG C, keep the temperature 4 ~ 12 hours, after by reaction kettle from
20 ~ 25 DEG C so are cooled down to, mixed liquor is first used into alcohol washes, is then centrifuged for, outwells supernatant, then cleaned with acetone, then
Centrifugation, the centrifugal rotational speed are 8000 ~ 12000r/min, and centrifugation time is 8 ~ 10 minutes, are in drying temperature after centrifugation
6 ~ 8 hours are dried at 60 ~ 85 DEG C to get CuSbS is arrived2Semiconductor nano material.
The invention has the following advantages:
A kind of preparation method of the copper-based sulfide semiconductor nano material of ternary of the present invention is easy to operate, and step is less, raw material valence
It is honest and clean to be easy to get, there is strong applicability to the selection of different material, preparation process product is easy to get, product cut size is tiny and crystal grain not
It can grow up, reaction process is not in that explosion causes preparation to fail, and is conducive to industrialization large-scale production, yield is high, up to
86.2%, product is mutually with high purity, and impurity is few, and purity may be up to 97.8%, and universality is strong, process stabilizing, and production stability is good, overcomes
The shortcomings that needing long-time high-temperature process in traditional preparation methods, nano ternary antimonial copper glance material prepared by the present invention can be extensive
Applied to energy fields such as lithium battery, thermoelectricity, photoelectricity.
Detailed description of the invention
Fig. 1 is synthesized Cu12Sb4S13The X ray diffracting spectrum of material.
Fig. 2 is synthesized nanometer Cu12Sb4S13The scanning electron microscope image of material.
Fig. 3 is synthesized nanometer Cu3SbS4The X ray diffracting spectrum of material.
Fig. 4 is synthesized nanometer Cu3SbS4The scanning electron microscope image of material.
Fig. 5 is synthesized CuS nanoparticles bS2The X ray diffracting spectrum of material.
Fig. 6 is synthesized CuS nanoparticles bS2The scanning electron microscope image of material.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1
It is a kind of to prepare nano ternary copper antimony sulfide (Cu12Sb4S13) particle method, include the following steps:
(1) it pours into using 3 mMs of antimony acetate powder as antimony source in 15 milliliters of glacial acetic acid solvent, was realized by ultrasound 30 minutes
The fully dissolved of antimony acetate powder obtains the antimony acetate solution of 0.2mol/L.
(2) 0.6 mM of two water acetic acid copper powders are poured into 70 milliliters of ethylene glycol monomethyl ether solution, it is made by stirring
All dissolutions.Then the diethanol amine of 0.5mL is poured into above-mentioned solution, solution colour becomes royal purple from bluish-green；Then by 0.68
MM thiocarbamide pours into above-mentioned solution, and solution colour becomes faint yellow；Then 1mL antimony acetate solution (1) is poured into above-mentioned molten
In liquid, solution becomes clear, colorless.The above-mentioned solution prepared is fitted into hydrothermal reaction kettle, hydrothermal reaction kettle is loaded into incubator
In, holding temperature is 240 DEG C, and heating and rate of temperature fall are 1 DEG C/min, keeps the temperature 8 hours, is then down to room temperature.Use ethyl alcohol
For cleaning solution, the solution that cleaning, centrifugal treating have obtained three times, the centrifugal rotational speed is 8000 ~ 12000r/min, when centrifugation
Between be 8 ~ 10 minutes, then 80 degrees Celsius drying 6 hours in vacuum tank, obtain Cu12Sb4S13Powder of nanometric particles.Nanometer
Grain yield is about 84.4%, and purity is about 97.8%.
All yields are the ratio calculations of the amount and raw material additive amount by final synthetic powder in the present invention, such as:
This example prepares Cu12Sb4S13Powder, the powder actually obtained in this example are 0.07g, can be according to mole of copper in compound
Quality calculates its yield=0.07/ Cu12Sb4S1312 ÷ 0.6=84.4% of molal weight *.
All purity are estimated by the adiabatic method in X-ray quantitative analysis method in the present invention, according to powder
The theoretical RIR value (reference intensity) of each phase in end, and the diffracted intensity of each phase is measured, to calculate the quality of object phase
Score.Such as: this example prepares Cu12Sb4S13Powder measures in this example Cu in X ray diffracting spectrum12Sb4S13Three strongest peak
Height and the Cu in its powder3SbS4The height of the three strongest peak of impurity phase is estimated according to peak height and the ratio of RIR value
Cu12Sb4S13The purity of phase.
Embodiment 2
It is a kind of to prepare nano ternary copper antimony sulfide (Cu3SbS4) particle method, include the following steps:
(1) it pours into using 3 mMs of antimony acetate powder as antimony source in 15 milliliters of glacial acetic acid solvent, was realized by ultrasound 30 minutes
The fully dissolved of antimony acetate powder obtains the antimony acetate solution of 0.2mol/L.
(2) 9 mMs of two water acetic acid copper powders are poured into 250 milliliters of ethylene glycol monomethyl ether solution, it is made by stirring
All dissolutions.Then the diethanol amine of 1mL is poured into above-mentioned solution, solution colour becomes royal purple from bluish-green；Then by 105 mmoles
You pour into above-mentioned solution thiocarbamide, and solution colour becomes faint yellow；Then 15mL antimony acetate solution (1) is poured into above-mentioned solution
In, solution becomes clear, colorless.The above-mentioned solution prepared is fitted into hydrothermal reaction kettle, hydrothermal reaction kettle is loaded into incubator
In, holding temperature is 240 DEG C, and heating and rate of temperature fall are 1 DEG C/min, keeps the temperature 8 hours, is then down to room temperature.Use ethyl alcohol
For cleaning solution, the solution that cleaning, centrifugal treating have obtained three times, the centrifugal rotational speed is 8000 ~ 12000r/min, when centrifugation
Between be 8 ~ 10 minutes, then 80 degrees Celsius drying 6 hours in vacuum tank, obtain Cu3SbS4Powder of nanometric particles.By embodiment 1
Calculation method, obtained Cu3SbS4Powder of nanometric particles yield is about 86.2%, and purity is about 93.8%.
Embodiment 3
It is a kind of to prepare nano ternary copper antimony sulfide (CuSbS2) particle method, include the following steps:
(1) it pours into using 3 mMs of antimony acetate powder as antimony source in 15 milliliters of glacial acetic acid solvent, was realized by ultrasound 30 minutes
The fully dissolved of antimony acetate powder obtains the antimony acetate solution of 0.2mol/L.
(2) 0.6 mM of two water acetic acid copper powders is poured into 70 milliliters of ethylene glycol monomethyl ether solution, keeps it complete by stirring
Portion's dissolution.Then 0.5 milliliter of diethanol amine is poured into above-mentioned solution, solution colour becomes royal purple from bluish-green；Then by 1.5 millis
Mole thiocarbamide pours into above-mentioned solution, and solution colour becomes faint yellow；Then 3 milliliters of antimony acetate solution (1) are poured into above-mentioned molten
In liquid, solution becomes clear, colorless.The above-mentioned solution prepared is poured into hydrothermal reaction kettle, hydrothermal reaction kettle is loaded into incubator
In, holding temperature is 150 DEG C, and heating and rate of temperature fall are 1 DEG C/min, keeps the temperature 12 hours, is then down to room temperature.Use ethyl alcohol
As cleaning solution, the solution that cleaning, centrifugal treating have obtained three times, and 80 degrees Celsius drying 6 hours in vacuum tank, it obtains
CuSbS2Powder of nanometric particles.By the calculation method of embodiment 1, obtained CuSbS2Powder of nanometric particles yield is about 85%,
Purity is about 90.2%.
Claims (6)
1. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary, which is characterized in that prepared using solvent-thermal method
The nano-scale Ternary copper antimony sulfide of difference metering ratios, using inorganic mantoquita, inorganic antimonic salt and sulphur source as raw material, by medium temperature plus
Pressure single step reaction prepares ternary sulfide powder.
2. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary as described in claim 1, which is characterized in that
The inorganic mantoquita is one of copper sulphate, copper acetate, copper chloride；The inorganic antimonic salt is antimony acetate, one in antimony chloride
Kind；The sulphur source is one of thiocarbamide, sulphur powder.
3. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary as claimed in claim 2, which is characterized in that
The inorganic mantoquita is preferably copper acetate, and the inorganic antimony is preferably antimony acetate, and the sulphur source is preferably thiocarbamide.
4. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary as claimed in claim 3, which is characterized in that
The preparation in the antimony source is under nitrogen protection, 20 ~ 25 DEG C of temperature, antimonic salt powder to be poured into glacial acetic acid solution, then ultrasonic
Processing 10 ~ 30 minutes, ultrasonic power 100W dissolves antimony acetate powder all, obtains the acetic acid solution containing antimony；The nitrogen
Purity is 99.999%, and nitrogen pressure is 380 ~ 420pa.
5. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary as claimed in claim 4, which is characterized in that
Inorganic mantoquita, is dissolved in ethylene glycol monomethyl ether solution, by stirring by the preparation of the Ternary copper antimony sulfide nanoparticle first
Mixing dissolves it all, and speed of agitator is 250 ~ 300r/min, and then diethanol amine is poured into above-mentioned solution and dissolved, then
Sulphur source is added in solution, and the acetic acid solution containing antimony is added, mixes, is subsequently placed in hydrothermal reaction kettle, with heating rate for 1
DEG C/min is warming up to 150 ~ 240 DEG C, keep the temperature 4 ~ 12 hours, after reaction kettle natural cooling is down to 20 ~ 25 DEG C, by mixed liquor
First use alcohol washes, be then centrifuged for, outwell supernatant, then cleaned with acetone, be then centrifuged for, the centrifugal rotational speed be 8000 ~
12000r/min, centrifugation time are 8 ~ 10 minutes, at being 60 ~ 85 DEG C in drying temperature after centrifugation dry 6 ~ 8 hours to get
To Ternary copper antimony sulfide CAS.
6. a kind of preparation method of the copper-based sulfide semiconductor nano material of ternary as claimed in claim 5, which is characterized in that
Concentration of the inorganic antimonic salt in acetic acid solution is 0.1 ~ 0.3mol/L, and the inorganic mantoquita, inorganic antimonic salt, sulphur source are being reacted
Molar ratio in medium is 3:(1 ~ 3): (3 ~ 35).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883640A (en) * | 2020-07-30 | 2020-11-03 | 河南理工大学 | Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof |
| CN112635593A (en) * | 2020-12-22 | 2021-04-09 | 东北电力大学 | All-antimony-based thin film solar cell and preparation method thereof |
| CN114031113A (en) * | 2021-12-10 | 2022-02-11 | 哈尔滨电机厂有限责任公司 | Hydrophobic Cu12Sb4S13Controllable preparation method of nanosheet |
| CN114452985A (en) * | 2022-02-14 | 2022-05-10 | 温州大学 | CuSbS for photocatalytic carbon dioxide2Method for preparing nanotube material |
| CN115367797A (en) * | 2022-07-12 | 2022-11-22 | 电子科技大学 | Ternary copper chalcogenide compound CuSbS 2 Preparation method of semiconductor nano material |
| CN115571912A (en) * | 2022-10-09 | 2023-01-06 | 重庆文理学院 | Preparation method of sulfide phase nano material |
| CN116409995A (en) * | 2023-04-13 | 2023-07-11 | 合肥工业大学 | High-purity Cu 12 Sb 4 S 13 Method for preparing thermoelectric material |
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2019
- 2019-06-10 CN CN201910497070.5A patent/CN110092418A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883640A (en) * | 2020-07-30 | 2020-11-03 | 河南理工大学 | Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof |
| CN112635593A (en) * | 2020-12-22 | 2021-04-09 | 东北电力大学 | All-antimony-based thin film solar cell and preparation method thereof |
| CN114031113A (en) * | 2021-12-10 | 2022-02-11 | 哈尔滨电机厂有限责任公司 | Hydrophobic Cu12Sb4S13Controllable preparation method of nanosheet |
| CN114452985A (en) * | 2022-02-14 | 2022-05-10 | 温州大学 | CuSbS for photocatalytic carbon dioxide2Method for preparing nanotube material |
| CN114452985B (en) * | 2022-02-14 | 2024-04-19 | 温州大学 | CuSbS for photocatalytic carbon dioxide2Method for preparing nano tube material |
| CN115367797A (en) * | 2022-07-12 | 2022-11-22 | 电子科技大学 | Ternary copper chalcogenide compound CuSbS 2 Preparation method of semiconductor nano material |
| CN115571912A (en) * | 2022-10-09 | 2023-01-06 | 重庆文理学院 | Preparation method of sulfide phase nano material |
| CN116409995A (en) * | 2023-04-13 | 2023-07-11 | 合肥工业大学 | High-purity Cu 12 Sb 4 S 13 Method for preparing thermoelectric material |
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