CN110371936A - A kind of preparation method and applications of interlamellar spacing adjustable sodium-ion battery copper selenide nano-chip arrays - Google Patents
A kind of preparation method and applications of interlamellar spacing adjustable sodium-ion battery copper selenide nano-chip arrays Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and applications of interlamellar spacing adjustable sodium-ion battery copper selenide nano-chip arrays, the copper selenide nano-chip arrays are using high-purity copper foil, selenium source, sodium hydroxide, strong reductant, intercalator as raw material, it takes water as a solvent, 0.5~4 h is reacted at 20~80 DEG C, obtains a kind of adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing.Outstanding feature of the invention is to realize the regulation of copper selenide interlamellar spacing with lower temperature, and the material preparation method is simple, and low energy consumption, is easy to industrialization large-scale production；Secondly copper selenide nano-chip arrays arrangement consistency is good, morphology controllable, specific surface area with higher.When the material is used as anode material of lithium-ion battery, the superior advantage of specific capacity height, good rate capability, cycle performance is shown.Therefore the material is expected in sodium-ion battery and otheralkali metal ion battery, and the fields such as thermoelectric material obtain extensive use.
Description
Technical field
The present invention relates to the preparation fields of anode material of lithium-ion battery, and in particular to a kind of adjustable sodium ion of interlamellar spacing
The preparation method and applications of battery copper selenide nano-chip arrays.
Background technique
The energy and environment are two significant problems that mankind nowadays existence must cope with social development, with coal oil
The exhaustion of equal fossil resources and the worsening of environment, develop the renewable energy such as solar energy, wind energy and water energy and have become entirely
Ball trend.As renewable energy and distributed energy largely access power grid, in order to overcome wind energy or solar power generation not to advise
Then with interrupted output characteristic, energy-storage battery is widely used in power generation, power transmission and distribution and uses electrical domain.
Although lithium ion battery has many advantages, such as that voltage is high, has extended cycle life, self discharge is small and memory-less effect, lithium
Ion battery battery higher cost (positive electrode, electrolyte, diaphragm are expensive), while lithium ion battery is faced with lithium resource
The problems such as shortage, recycling is difficult.From the viewpoint of economy, high-cost lithium ion battery is not appropriate for leading in extensive energy storage
Domain application.Sodium element and elemental lithium have similar physicochemical property, and its is from a wealth of sources, rich reserves, with the related compounds of sodium
Object is that the secondary cell system of raw material has great advantage in cost, and therefore, sodium-ion battery is in extensive energy storage field
Great application potential.
As the important component of battery, the negative electrode material with height ratio capacity and long-life cycle characteristics is for improving
The overall energy storage density of battery is most important.Negative electrode material based on electrochemical reaction mechanism is divided into three classes: insertion type, alloy
Change type and conversion type.
Conversion hysteria negative electrode material with polyelectron reaction can provide height ratio capacity, this will be that a kind of sodium-ion battery is non-
Normal promising material.Compared with Intercalation material, transistion metal compound can be reduced to metal by conversion reaction completely
State is to make material have higher theoretical capacity.For example, Zhao Dongyuan seminar, Fudan University is by the mesoporous Fe of highly crystalline3O4
It is encapsulated in the hollow Nano carbon balls of N doping, is used for high-capacity and long-life sodium-ion battery, the material is in 160 mA g-1Electricity
There are 372 mAh g under current density-1High discharge capacity, and by 800 circulations, material capacity gradually increases and is maintained at
522 mAh g-1, in 1200 mA g-1Current density under capacity be 196 mAh g-1With high coulomb efficiency (~ 100%), show
Excellent high rate performance and cyclical stability (Nano Energy, 2019,56,426).In addition, conversion hysteria negative electrode material
Reaction potential can be adjusted by combining different transition-metal cation and anionic species, this can be effectively ensured that
The safety of battery.Meanwhile many transformant anode material such as Fe3O4And FeS2To be naturally occurring, there is extremely low production
Cost.
Although conversion hysteria negative electrode material has many advantages, due to their ion/electron conducting low, charge and discharge
Material volume changes the problems such as relatively large and electrolyte decomposes in journey, and there are still many to choose for the material functionization of this type
War.Low conductivity will lead to poor dynamics and reduce material high rate performance.Large volume expansion crushes electrode material, causes
Battery capacity rapid decay.In addition, electrolyte decomposes the resistance increase that may cause electrode, the electrochemistry of electrode material is influenced
Energy.Therefore, there is still a need for making many effort to make conversion hysteria negative electrode material become the practical alternative materials of sodium-ion battery.
For the disadvantage for overcoming conversion hysteria material intrinsic, researcher has used various optimisation strategies to improve transformant
The storage sodium performance of cathode material, including nano-structure design, carbon material is compound and molecule intercalation.Hollow/hole nanostructure by
It is proved to be a kind of promising strategy for improving electrode sodium storge quality.Li et al. people reports with core-shell hollow microsphere knot
The mesoporous CoS C composite of structure is down to 55 mAh g through 5 circulation volumes with not optimized CoS(-1) compare, CoS@
C composite is in 0.2 A g-1Still there are 532 mAh g after lower circulation 100 times-1Height ratio capacity, CoS@C composite
Excellent electrochemical performance have benefited from mesoporous CoS core and alveolar shape carbon shell structure synergistic effect (Nano Energy, 2017,
41, 109).Compound carbon material is the conductivity and mechanical stability for improving electrode, improves its multiplying power speed characteristic and circulation longevity
Another effective ways of life.Ren et al. is reported prepares ultra-thin MoS on flexible carbon cloth2Nanometer sheet@metal organic framework
(MOF) N derived from adulterates carbon nanowalls composite material, and uses them as anode material of lithium-ion battery, shows Fabrication of High Specific Capacitance
Amount is (in 200 mA g-1It is down 653.9 mA h g-1, 100 times circulation after be 619.2 mA h g-1), excellent high rate performance and
Long circulation life stability is (in 1 A g-1When 1000 times circulation after be 265 mA h g-1) (Adv. Funct. Mater,
2017, 27, 1702116).The surfactant intercalated interlamellar spacing that can increase material is with padded coaming in charge and discharge process
Volume expansion, secondly biggish interlamellar spacing is conducive to the quick transmission of sodium ion, improves the high rate performance of material；Last surface
Activating agent can prevent metallic particles from further growth and ensuring the high circulation stability of electrode in conversion reaction.
Copper selenide exists with different stoichiometric forms, their complicated structures and valence state lead to some unique optics
And electrical properties.Copper selenide is a kind of important p-type semiconductor, solar battery, catalysis, energy storage, optical filter,
There is extensive potential application in the fields such as nanotube switch, thermoelectricity and opto-electronic transformers and superconductor.For example, the Chinese Academy of Sciences
The chemical palace institute Zhu Qing, Han Buxing study group have found that copper selenide nanocatalyst produces methanol in Carbon dioxide electrochemical reduction method
Outstanding performance in the process, under the low overvoltage of 285 mV, current density may be up to 41.5 mA cm-2And faradic efficiency
For 77.6% (Nature Communications, 2019,10,677).Copper selenide is used for aluminium ion for the first time by Jiang et al.
Battery cathode, selenizing copper electrode show high reversible capacity and outstanding cyclical stability, in 200 mA g-1High current density
Under, the specific discharge capacity in initial cycle is 241 mA h g-1, and 100 mA h g are maintained at after 100 circulations-1, library
Logical sequence efficiency is 96.1%, show good capacity retention ratio (ACS Appl. Mater. Interfaces, 2018,10,
21, 17942-17949).Chen Lidong teaches seminar by utilizing chemical interaction special between Ni metal and multi wall CNTs
Power is successfully realized and grows Cu in CNTs surface in situ2Se is nanocrystalline, and is assembled into a series of Cu2Se/CNTs hybrid material.
Cu2The monodispersed molecular level CNTs of Se crystal boundary internal height, greatly reduces lattice thermal conductivity and carrier concentration, to make heat
The electric figure of merit in 1000 k up to 2.4 (Energ. Environ. Sci., 2017,10 (9): 1928-1935).
In addition, there is similar patent of invention as follows: Hu Zhixiang etc. (CN103449385A) is synthesized using the method for vacuum calcining
Berzeline powder.Plum bright equal (CN104016313A) uses hydro-thermal method, is 100~160 DEG C in hydrothermal temperature, when reaction
Between be 1 ~ 4 h, synthesized a kind of six side's copper selenide nanometer sheets.Chen Gang etc. (CN103879974A) is with copper acetate, sodium selenite etc.
For raw material, selenizing copper nano-wire has been made through microwave hydrothermal.Xue Ming Zhe etc. (CN1889291) passes through reactive pulse laser deposition
Method is prepared for Berzeline film, and is used as negative electrode of lithium ion battery.The preparation process of these same type of material all refers to big
Highly energy-consuming and complicated equipment are measured, high production cost, the period is long and is not suitable for large-scale production.Therefore find it is simple and easy, it is green
Colour circle protect and be capable of large-scale production synthetic method it is significant.
Summary of the invention
The present invention provides a kind of preparation method of adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing, closes
It is simple at method, it is low in cost, it can be used for large-scale industrial production.The adjustable sodium-ion battery selenium of obtained interlamellar spacing
Change specifically a kind of stable structure of copper nano-chip arrays, specific capacity height, the sodium with superior cyclical stability and high rate capability
Ion battery cathode material.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of interlamellar spacing adjustable sodium-ion battery preparation method of copper selenide nano-chip arrays, steps are as follows:
(1) by high-purity copper foil respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water supersound washing to be to remove copper foil table
The organic matter and oxide in face, then 60 DEG C of 5 h of drying of vacuum.
(2) a certain amount of sodium hydroxide is dissolved in aqueous intercalant, then sequentially adds selenium source, strong reductant,
20~80 DEG C are quickly stirred 10-120 min and raw material are made to be completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 0.5~4 h is reacted at a temperature of 20~80 DEG C,
Take out copper foil, it is multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum be acquisition the adjustable sodium of interlamellar spacing from
Sub- battery copper selenide nano-chip arrays.
Further, the selenium source in the step (2) is simple substance selenium powder, selenium dioxide, sodium selenite, selenous acid, selenic acid, four
Selenium chloride.
Further, the strong reductant in the step (2) is hydrazine hydrate, sodium borohydride, potassium borohydride.
Further, the intercalator in the step (2) is cetyl trimethylammonium bromide, lauryl sodium sulfate, ten
Dialkyl benzene sulfonic acids sodium, polyvinylpyrrolidone, dodecyl benzyl dimethyl ammonium chloride or hexadecyltrimethylammonium chloride.
Further, the substance withdrawl syndrome of the intercalator molecule aqueous solution in the step (2) is 0.001~0.05 mol
L-1, in mixed solution, the substance withdrawl syndrome of sodium hydroxide is 1-5 mol L-1, the solubility of strong reductant is 0.05-0.2
mol L-1, the solubility of selenium source is 0.01-0.05 mol L-1。
Copper selenide nano-chip arrays arrangement produced by the present invention is consistent, morphology controllable；Nanometer sheet thickness is 20~40 nm,
Array heights are 1~4 μm.
Utilize the adjustable sodium-ion battery of interlamellar spacing made from preparation method of the present invention copper selenide nanometer sheet battle array
The application being listed in anode material of lithium-ion battery.
The beneficial effects of the present invention are: 1, the present invention using have excellent electron conductivity selenizing copper product as sodium from
Sub- cell negative electrode material improves the specific surface of material by the two kinds of means combinations of nano-structure design and intercalator molecule intercalation
Long-pending and interlamellar spacing is finally obtained the sodium-ion battery cathode of function admirable with the volume expansion in padded coaming charge and discharge process
Material.
2, copper selenide nano-chip arrays of the invention arrangement consistency is good, morphology controllable, specific surface area with higher, electricity
Chemical activity is high, is conducive to sodium ion and is embedded in and deviates from, and it directly grows in copper foil surface, has the advantages that without being coated with, can
To reduce production cost well.
3, the present invention realizes the copper foil growth in situ of copper selenide nano-chip arrays and the regulation of interlamellar spacing at normal temperature, is not necessarily to
The high-temperature high-pressure apparatus of conventional hydrothermal reaction, preparation method is simple, and the reaction time is short, almost Non-energy-consumption, is easy to industrialize big
Large-scale production has green relatively and economic advantage.
4, copper selenide nano-chip arrays preparation process of the invention is easy to operate, and yield is high, at low cost, environmental-friendly, sodium
Ion battery charging and discharging capacity is high, good cycling stability, and high rate performance is excellent.As the negative electrode material of sodium-ion battery
It uses, obtained sodium-ion battery is in 0.1 A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0 A g-1、5.0 A g-1、10.0 A g-1Current density under specific capacity be respectively 432.76,421.62,420.37,407.49,
403.82,387.48,358.74,320.36 mAh g-1, show higher high rate performance.With 2 A g-1Current density into
500 cyclical stability tests of row, specific capacity conservation rate is 88.70 %, shows excellent cyclical stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the XRD spectrum of 1 copper selenide nano-chip arrays of the embodiment of the present invention.
Fig. 2 is the scanning electron microscope (SEM) of 1 copper selenide nano-chip arrays of the embodiment of the present invention.
Fig. 3 is constant current charge-discharge curve of the 1 copper selenide nano-chip arrays of embodiment under different current densities.
Fig. 4 is the high rate performance curve of 1 copper selenide nano-chip arrays of embodiment.
Fig. 5 is the stable circulation linearity curve of 1 copper selenide nano-chip arrays of embodiment.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under that premise of not paying creative labor
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of interlamellar spacing of the present embodiment adjustable sodium-ion battery copper selenide nano-chip arrays the preparation method is as follows:
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 4 g sodium hydroxides are dissolved in 100 ml, 0.001 mol L-1Lauryl sodium sulfate aqueous solution in, then
Sequentially add 0.110 g (0.001 mol) selenium dioxide, 0.189 g (0.005 mol) sodium borohydride, in 20 DEG C of quickly stirrings
10 min make raw material be completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 4 h are reacted at a temperature of 20 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
The XRD spectrum of the copper selenide nano-chip arrays is consistent with standard card PDF#29-0575 as shown in Figure 1, and map
There is diffraction maximum appearance at 7.6 ° and (111) crystal face deviates 5.4 ° to low-angle direction, causes material for the insertion of intercalation agent molecule
It is in addition to this diffraction maximum of copper (PDF#04-0836) substrate caused by interlamellar spacing expands.
Fig. 2 can be seen that the copper selenide nano-chip arrays are made of the sheet of 40-100 nm, marshalling.
Fig. 3 from right to left, successively in 0.1 A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0
A g-1、5.0 A g-1、10.0 A g-1Current density under, the charging and discharging curve that measures.In this process, charging and discharging curve is not
Significant change occurs, shows that the copper selenide nano-chip arrays have excellent stabilization in anode material of lithium-ion battery application
Property.
Fig. 4 is the high rate performance curve of the copper selenide nano-chip arrays of embodiment 1.From left to right, it is followed successively by close in electric current
Spend 0.1 A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0 A g-1、5.0 A g-1、10.0 A g-1
Under the conditions of, the specific discharge capacity data measured, in 0.1 A g-1Current density under specific capacity be 432.75 mAh g-1, work as electricity
Current density increases to 10 A g-1When, specific capacity is still 320.64 mAh g-1.And in 10 A g-1It is carried out five times under current density
After circulation, when current density is converted to 0.1 A g-1When, specific capacity has preferable high rate performance and circulation almost without decaying
Stability.
Fig. 5 is in 2 A g-1Current density under carry out the charge and discharge data that measure of 500 charge and discharge cycles, initial specific volume
Amount is 372.69 mAh g-1, 329.96 mAh g are decayed to after 500 charge and discharge cycles-1, specific capacity conservation rate is
88.53%.Show overlength cyclical stability.
Using the copper selenide nano-chip arrays of preparation as the negative electrode material of sodium-ion battery, electrolyte is 1 mol L-1Three
Methyl fluoride sodium sulfonate (CF3SO3Na), solvent is diethylene glycol dimethyl ether (DEGDME).
Embodiment 2
A kind of interlamellar spacing of the present embodiment adjustable sodium-ion battery copper selenide nano-array the preparation method is as follows:
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 8 g sodium hydroxides are dissolved in 100 ml, 0.005 mol L-1Aqueous povidone solution, then according to
Secondary addition 0.346 g (0.002 mol) sodium selenite, 0.378 g (0.01 mol) sodium borohydride, in 30 DEG C of quickly stirrings 30
Min makes raw material be completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 4 h are reacted at a temperature of 30 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
In the example, XRD spectrum shows Cu2Se (111) crystal face deviates 5.6 ° to low-angle direction, is offset to by 13.0 °
7.4 °, caused by causing interlamellar spacing to expand for surfactant insertion, interlamellar spacing is expanded to 1.2 by 0.68 initial nm at this time
nm.Battery assembly technique is with example 1, in 0.1 A g-1Current density under specific discharge capacity be 410.68 mAh g-1, 2
A g-1Current density under carry out 500 charge and discharge cycles, capacity retention ratio 89.2%.
Embodiment 3
A kind of interlamellar spacing of the present embodiment adjustable sodium-ion battery copper selenide nano-array the preparation method is as follows:
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 10 g sodium hydroxides are dissolved in 100 ml, 0.01 mol L-1Sodium dodecyl benzene sulfonate aqueous solution, then
0.237 g (0.003 mol) selenium powder, 0.81 g (0.015 mol) potassium borohydride are sequentially added, in 40 DEG C of quickly stirrings 60
Min makes raw material be completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 3 h are reacted at a temperature of 40 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
In the example, XRD spectrum shows Cu2Se (111) crystal face deviates 5.1 ° to low-angle direction, is offset to by 13.0 °
7.9 °, caused by causing interlamellar spacing to expand for surfactant insertion, interlamellar spacing is expanded to 1.12 by 0.68 initial nm at this time
nm.Battery assembly technique is with example 1, in 0.1 A g-1Current density under specific discharge capacity be 422.74 mAh g-1, 2
A g-1Current density under carry out 500 charge and discharge cycles, capacity retention ratio 85.4%.
Embodiment 4
A kind of interlamellar spacing of the present embodiment adjustable sodium-ion battery copper selenide nano-array the preparation method is as follows:
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 12 g sodium hydroxides are dissolved in 100 ml, 0.02 mol L-1Dodecyl benzyl dimethyl ammonium chloride it is water-soluble
Then liquid sequentially adds 0.516 g (0.004 mol) selenous acid, 1.08 g (0.02 mol) potassium borohydride, quickly at 50 DEG C
Stirring 60 min makes raw material be completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 2 h are reacted at a temperature of 50 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
In the example, XRD spectrum shows Cu2Se (111) crystal face deviates 4.7 ° to low-angle direction, is offset to by 13.0 °
8.3 °, caused by causing interlamellar spacing to expand for surfactant insertion, interlamellar spacing is expanded to 1.06 by 0.68 initial nm at this time
nm.Battery assembly technique is with example 1, in 0.1 A g-1Current density under specific discharge capacity be 397.92 mAh g-1, 2
A g-1Current density under carry out 500 charge and discharge cycles, capacity retention ratio 83.9%.
Embodiment 5
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 16 g sodium hydroxides are dissolved in 100 ml, 0.05 mol L-1Cetyl trimethylammonium bromide aqueous solution,
Then 0.725 g (0.001 mol) selenic acid, 8 ml hydrazine hydrates are sequentially added, quickly stirring 90 min at 60 DEG C keeps raw material complete
Dissolution obtains solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 1 h is reacted at a temperature of 60 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
In the example, XRD spectrum shows Cu2Se (111) crystal face deviates 5.5 ° to low-angle direction, is offset to by 13.0 °
7.5 °, caused by causing interlamellar spacing to expand for surfactant insertion, interlamellar spacing is expanded to 1.17 by 0.68 initial nm at this time
nm.Battery assembly technique is with example 1, in 0.1 A g-1Current density under specific discharge capacity be 427.25 mAh g-1, 2
A g-1Current density under carry out 500 charge and discharge cycles, capacity retention ratio 87.5%.
Embodiment 6
A kind of interlamellar spacing of the present embodiment adjustable sodium-ion battery preparation method of copper selenide nano-array, steps are as follows:
(1) high-purity copper foil is cut out as the cm size of 1 cm × 1, respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water
Supersound washing is to remove the organic matter and oxide of copper foil surface, then 60 DEG C of 5 h of drying of vacuum.
(2) 20 g sodium hydroxides are dissolved in 100 ml, 0.01 mol L-1Hexadecyltrimethylammonium chloride aqueous solution,
Then 1.100 g (0.005 mol) selenic chloride, 8 ml hydrazine hydrates are sequentially added, quickly stirring 120 min at 60 DEG C makes original
Material is completely dissolved to obtain solution A.
(3) it will be placed in solution A through step (1) processed copper foil, 1 h is reacted at a temperature of 60 DEG C, and take out copper foil,
Multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium-ion battery of interlamellar spacing and use
Copper selenide nano-chip arrays.
In the example, XRD spectrum shows Cu2Se (111) crystal face deviates 5.3 ° to low-angle direction, is offset to by 13.0 °
7.7 °, caused by causing interlamellar spacing to expand for surfactant insertion, interlamellar spacing is expanded to 1.15 by 0.68 initial nm at this time
nm.Battery assembly technique is with example 1, in 0.1 A g-1Current density under specific discharge capacity be 415.03 mAh g-1, 2
A g-1Current density under carry out 500 charge and discharge cycles, capacity retention ratio 86.8%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of interlamellar spacing adjustable sodium-ion battery copper selenide nano-chip arrays, it is characterised in that step is such as
Under:
(1) by high-purity copper foil respectively through acetone, 1 mol L-1Hydrochloric acid solution, deionized water supersound washing to be to remove copper foil surface
Organic matter and oxide, then 60 DEG C of 5 h of drying of vacuum；
(2) a certain amount of sodium hydroxide is dissolved in the aqueous solution there are also intercalation agent molecule, then sequentially adds selenium source, reduction
Agent, quickly stirring 10-120 min at 20~80 DEG C makes raw material be completely dissolved to obtain mixed solution；
(3) it will be placed in mixed solution through step (1) processed copper foil, 0.5~4 h is reacted at a temperature of 20~80 DEG C, is taken
Copper foil out, multiple with deionized water and ethanol washing, 60 DEG C of 10 h of drying of subsequent vacuum obtain the adjustable sodium ion of interlamellar spacing
Battery copper selenide nano-chip arrays.
2. a kind of preparation side of the adjustable sodium-ion battery copper selenide nano-array of interlamellar spacing according to claim 1
Method, it is characterised in that: the selenium source in the step (2) is simple substance selenium powder, selenium dioxide, sodium selenite, selenous acid, selenic acid, four
Selenium chloride.
3. a kind of preparation side of the adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing according to claim 1
Method, it is characterised in that: the strong reductant in the step (2) is hydrazine hydrate, sodium borohydride, potassium borohydride.
4. a kind of preparation side of the adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing according to claim 1
Method, it is characterised in that: the intercalator in the step (2) is cetyl trimethylammonium bromide, lauryl sodium sulfate, 12
Sodium alkyl benzene sulfonate, polyvinylpyrrolidone, dodecyl benzyl dimethyl ammonium chloride or hexadecyltrimethylammonium chloride.
5. a kind of preparation side of the adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing according to claim 1
Method, it is characterised in that: the substance withdrawl syndrome of the intercalator molecule aqueous solution in the step (2) is 0.001~0.05 mol
L-1, in mixed solution, the substance withdrawl syndrome of sodium hydroxide is 1-5 mol L-1, the solubility of strong reductant is 0.05-0.2
mol L-1, the solubility of selenium source is 0.01-0.05 mol L-1。
6. a kind of preparation side of the adjustable sodium-ion battery copper selenide nano-chip arrays of interlamellar spacing according to claim 1
Method, it is characterised in that: copper selenide nano-chip arrays arrangement obtained is consistent, morphology controllable；Nanometer sheet thickness is 20~40 nm,
Array heights are 1~4 μm.
7. the adjustable sodium-ion battery of interlamellar spacing made from -6 any preparation methods is received with copper selenide according to claim 1
Application of the rice chip arrays in anode material of lithium-ion battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421115A (en) * | 2020-09-14 | 2021-02-26 | 上海大学 | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof |
| CN114122388A (en) * | 2021-11-16 | 2022-03-01 | 信阳师范学院 | CuSe nano material for sodium ion battery and preparation method thereof |
| CN114314528A (en) * | 2021-12-20 | 2022-04-12 | 深圳大学 | Two-dimensional layered nanosheet and preparation method and application thereof |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN116282020A (en) * | 2023-02-27 | 2023-06-23 | 昆明理工大学 | New application of copper selenide catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016313A (en) * | 2014-06-10 | 2014-09-03 | 郑州轻工业学院 | Preparation method of hexagonal copper selenide nanosheets |
| CN108423705A (en) * | 2018-02-28 | 2018-08-21 | 郑州轻工业学院 | A kind of interlamellar spacing, the preparation method of pore volume adjustable sodium-ion battery level copper sulfide micro-sphere material |
| CN110015645A (en) * | 2019-05-13 | 2019-07-16 | 东华大学 | A kind of self-supporting grid shape Cu2-xThe preparation method of Se nano material |
-
2019
- 2019-07-30 CN CN201910694802.XA patent/CN110371936B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016313A (en) * | 2014-06-10 | 2014-09-03 | 郑州轻工业学院 | Preparation method of hexagonal copper selenide nanosheets |
| CN108423705A (en) * | 2018-02-28 | 2018-08-21 | 郑州轻工业学院 | A kind of interlamellar spacing, the preparation method of pore volume adjustable sodium-ion battery level copper sulfide micro-sphere material |
| CN110015645A (en) * | 2019-05-13 | 2019-07-16 | 东华大学 | A kind of self-supporting grid shape Cu2-xThe preparation method of Se nano material |
Non-Patent Citations (2)
| Title |
|---|
| HONGLIANG CAO ET AL.: "Conversion of Cu2O nanocrystals into hollow Cu2-xSe nanocages with the preservation of morphologies", 《CHEMICAL COMMUNICATIONS》 * |
| 赵彦星: "硒化铜膜与二氧化钛纳米管阵列的制备及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421115A (en) * | 2020-09-14 | 2021-02-26 | 上海大学 | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof |
| CN112421115B (en) * | 2020-09-14 | 2022-11-18 | 上海大学 | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN114512729B (en) * | 2020-11-16 | 2023-07-14 | 比亚迪股份有限公司 | Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN114122388A (en) * | 2021-11-16 | 2022-03-01 | 信阳师范学院 | CuSe nano material for sodium ion battery and preparation method thereof |
| CN114122388B (en) * | 2021-11-16 | 2024-04-02 | 信阳师范学院 | CuSe nano material for sodium ion battery and preparation method thereof |
| CN114314528A (en) * | 2021-12-20 | 2022-04-12 | 深圳大学 | Two-dimensional layered nanosheet and preparation method and application thereof |
| CN116282020A (en) * | 2023-02-27 | 2023-06-23 | 昆明理工大学 | New application of copper selenide catalyst |
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