CN113725439A - Porous copper nitride nanowire array and preparation method and application thereof - Google Patents
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- 239000002070 nanowire Substances 0.000 title claims abstract description 102
- 239000010949 copper Substances 0.000 title claims abstract description 93
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- -1 copper nitride Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000011889 copper foil Substances 0.000 claims abstract description 45
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- 239000005750 Copper hydroxide Substances 0.000 description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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Abstract
The invention provides a porous copper nitride nanowire array and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving sodium hydroxide and ammonium persulfate in water to prepare a mixed solution, placing copper foil in the mixed solution, standing for reaction, washing and drying to obtain a precursor Cu (OH)2A nanowire array; the precursor Cu (OH)2And calcining the nanowire array under a preset condition to obtain the porous copper nitride nanowire array. The size of the porous copper nitride nanowire array provided by the invention is controllable, the porous copper nitride nanowire array has good stability at normal temperature, and the porous copper nitride nanowire array can be used for assembling a full cell without a negative current collector, inhibiting the growth of lithium dendrites and improving the cycling stability; the preparation method has simple and convenient flow, simple operation and lower energy consumption, and is beneficial to market popularization.
Description
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to a porous copper nitride nanowire array and a preparation method and application thereof.
Background
Lithium metal is considered to be the ultimate choice for the negative electrode of high specific energy secondary batteries by virtue of its extremely high specific capacity (3860mAh/g) and lowest redox potential (-3.04Vvs standard hydrogen electrode). However, lithium itself has problems such as low coulombic efficiency and dendritic growth. In order to apply metallic lithium as a negative electrode material, researchers have proposed many effective modification strategies. These strategies, however, tend to be based on thick lithium sheets (> 200 μm) and the use of excess lithium source may mask the problem of negative electrodes in full cells and also greatly reduce the energy density of the cell. And the battery structure without a lithium negative electrode (the negative electrode does not contain a lithium source and an active material) is adopted, so that the effectiveness of a modification strategy can be more clearly known, and the improvement of the energy density of the whole battery is facilitated.
The copper current collector is the most commonly used current collector of the negative electrode at present, but the problems of poor affinity with lithium metal, incapability of inhibiting the growth of lithium dendrite and the like easily occur in the use process. Therefore, how to reduce the generation of lithium dendrites and increase the safety of the battery when the copper current collector is modified to be applied to a lithium sulfur full battery without a lithium cathode is still a problem to be solved.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects of the prior art, and provides a porous copper nitride nanowire array, a preparation method thereof and an application thereof, so as to solve the problems that the existing lithium-free negative electrode lithium-sulfur full battery is easy to generate lithium dendrite and has poor cycle performance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a porous copper nitride nanowire array comprises the following steps:
s1, dissolving sodium hydroxide and ammonium persulfate in water to prepare a mixed solution, placing the copper foil in the mixed solution, standing for reaction, washing and drying to obtain a precursor Cu (OH)2A nanowire array;
s2, mixing the precursor Cu (OH)2And calcining the nanowire array under a preset condition to obtain the porous copper nitride nanowire array.
Optionally, in the mixed solution in step S1, the mass ratio of the sodium hydroxide to the ammonium persulfate is 3: 1 to 5: 1, in the range of.
Alternatively, the conditions of the standing reaction in step S1 include a reaction temperature in the range of 20 ℃ to 30 ℃ and a reaction time in the range of 6min to 60 min.
Optionally, the copper foil of step S1 is pretreated, and the pretreatment step includes washing the copper foil with an acidic solution or an organic solution.
Optionally, the preset condition in step S2 includes: the calcination temperature is within the range of 300 ℃ to 500 ℃, the calcination time is within the range of 3h to 5h, and the temperature rise rate of the tube furnace is within the range of 5 ℃/min to 10 ℃/min.
The invention also aims to provide a porous copper nitride nanowire array, which is prepared by adopting the preparation method of the porous copper nitride nanowire array.
Optionally, the porous copper nitride nanowire array comprises a copper foil and copper nitride nanowires, and the copper nitride nanowires are distributed on the surface of the copper foil in a vertical array.
Optionally, the copper nitride nanowires have a length in the range of 10 μm to 30 μm and a diameter in the range of 100nm to 300 nm.
The third purpose of the present invention is to provide an application of the porous copper nitride nanowire array in the lithium-negative-electrode-free lithium-sulfur full cell field, wherein the lithium-negative-electrode-free lithium-sulfur full cell is assembled by using the porous copper nitride nanowire array as a negative electrode current collector and using lithium sulfide as a lithium source.
Compared with the prior art, the porous copper nitride nanowire array and the preparation method and application thereof provided by the invention have the following advantages:
(1) the porous copper nitride nanowire array provided by the invention has controllable size, good stability at normal temperature, simple and convenient preparation method flow, simple operation and low energy consumption, and the product is favorable for marketization popularization.
(2) The porous copper nitride nanowire array provided by the invention can be used for assembling a full battery without a negative current collector, inhibiting the growth of lithium dendrites and improving the cycling stability.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 shows Cu (OH) according to example 1 of the present invention2Elemental distribution and TEM images of nanowire arrays;
FIG. 2 is a TEM image and elemental distribution of a porous copper nitride nanowire array according to an embodiment of the present invention;
fig. 3 is a graph of cycle performance of the assembled lithium-free negative electrode full cell in example 1 of the present invention;
FIG. 4 shows Cu (OH) according to example 2 of the present invention2SEM images of nanowire arrays;
FIG. 5 shows Cu (OH) according to example 3 of the present invention2SEM images of nanowire arrays;
FIG. 6 shows Cu (OH) according to example 4 of the present invention2SEM images of nanowire arrays;
FIG. 7 is an SEM image of an array of porous copper nitride nanowires of example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the description of the present invention, it should be noted that the terms "first" and "second" mentioned in the embodiments of the present invention are only used for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In the description of embodiments of the present application, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
It should be noted that the term "in.
The embodiment of the invention provides a preparation method of a porous copper nitride nanowire array, which comprises the following steps:
s1, dissolving sodium hydroxide and ammonium persulfate in water to prepare a mixed solution, placing the copper foil in the mixed solution, standing for reaction, washing and drying to obtain a precursor Cu (OH)2A nanowire array;
s2, mixing the precursor Cu (OH)2And calcining the nanowire array under a preset condition to obtain the porous copper nitride nanowire array.
The invention grows porous Cu on the copper foil in situ3The N nanowire array can ensure that the whole array of nanowires is in close contact with the copper current collector, and the effective current density of the electrode is reduced, so that the uniform deposition of lithium metal is realized, and the growth of lithium dendrites is inhibited. In addition, the size of the porous copper nitride nanowire array is controllable, the porous copper nitride nanowire array has good stability at normal temperature, the preparation method is simple and convenient in process, simple to operate and low in energy consumption, and the product is favorable for marketization popularization.
Specifically, in the mixed liquid in step S1, the mass ratio of sodium hydroxide to ammonium persulfate is 3: 1 to 5: 1, in the range of. Preferably, the mass ratio of sodium hydroxide to ammonium persulfate is 5: 1, i.e., 2mg of sodium hydroxide was uniformly mixed with 0.4mg of ammonium persulfate in the aqueous solution.
The conditions of the standing reaction in the copper foil re-mixed liquid comprise: the reaction temperature is in the range of 20 ℃ to 30 ℃ and the reaction time is in the range of 6min to 60 min. Preferably, the reaction temperature is room temperature and the reaction time is 10 min.
Wherein, before the standing reaction, the copper foil is pretreated, and the pretreatment step comprises the step of cleaning the copper foil by using an acid solution or an organic solution. Preferably, the acidic solution is a hydrochloric acid solution and the organic solution is acetone.
The length, width and thickness of the copper foil are (2-4) cm x 5 μm, and the copper foil in the embodiment of the invention is preferably 2cm x 5 μm.
Specifically, in step S2, the precursor Cu (OH)2The preset conditions for calcining the nanowire array comprise: the calcination temperature is within the range of 300 ℃ to 500 ℃, the calcination time is within the range of 3h to 5h, and the temperature rise rate of the tube furnace is within the range of 5 ℃/min to 10 ℃/min. Preferably, in the embodiment of the invention, the heating rate is 5 ℃/min, the calcining temperature is 350 ℃, and the calcining time is 4 h.
The invention also provides a porous copper nitride nanowire array, which is prepared by the preparation method of the porous copper nitride nanowire array.
Specifically, the porous copper nitride nanowire array comprises a copper foil and copper nitride nanowires, wherein the copper nitride nanowires are distributed on the surface of the copper foil in a vertical array. The copper nitride nanowires have a length in the range of 10 to 30 μm and a diameter in the range of 100 to 300 nm.
The porous copper nitride nanowire array provided by the embodiment of the invention has controllable size and good stability at normal temperature, and the lithium metal cathode prepared by the copper current collector modified by the porous copper nitride nanowire can inhibit the growth of lithium dendrite and effectively improve the coulombic efficiency, the cycling stability and the safety of a battery.
The invention also provides an application of the porous copper nitride nanowire array in the field of lithium-sulfur full batteries with lithium-free cathodes, wherein the porous copper nitride nanowire array is used as a cathode current collector, and lithium sulfide Li is used as the cathode current collector2And S is used as a lithium source to assemble the lithium-sulfur full battery without the lithium cathode.
On the basis of the above embodiments, the present invention provides the following specific examples of the preparation method of the porous copper nitride nanowire array, and further illustrates the present invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method and application of a porous copper nitride nanowire array, which comprises the following steps:
1) taking a copper foil with the length of 2cm, the width of 2cm and the thickness of 5 microns, putting the copper foil into a proper amount of hydrochloric acid solution for soaking and taking out, washing the copper foil cleanly by deionized water, putting the copper foil into a proper amount of acetone solution, carrying out ultrasonic cleaning, and then putting the copper foil into a proper amount of absolute ethyl alcohol solution for ultrasonic cleaning;
2) weighing 2.0mg of flaky sodium hydroxide, pouring deionized water, fully stirring to dissolve the flaky sodium hydroxide uniformly, weighing 0.4mg of ammonium persulfate powder, pouring the ammonium persulfate powder into the completely dissolved sodium hydroxide solution, and quickly stirring to obtain a mixed solution;
3) putting the copper foil for standby cleaning into the mixed solution for reaction for 10min, taking out the copper foil, rinsing for 3 times by using deionized water and absolute ethyl alcohol respectively, drying in the air, and obtaining an intermediate Cu (OH) on the surface of the copper foil2A nanowire array;
4) mixing Cu (OH)2And (3) putting the nanowire array into a tube furnace, introducing flowing ammonia gas, raising the temperature at the rate of 5 ℃/min, calcining at the temperature of 350 ℃, keeping the temperature for 4h, and naturally cooling to obtain the porous copper nitride nanowire array growing compactly on the surface of the copper foil.
5) Taking the porous copper nitride nanowire array as a negative current collector, and dropwise adding Li2And (3) taking the self-assembled rGO of the S as a positive electrode to assemble the lithium-free negative electrode full battery.
The Cu (OH) prepared in step 2) of this example 12And (3) carrying out structural and morphological characterization on the nanowire array through XRD, SEM and TEM to obtain a result graph as shown in figure 1. FIG. 1 shows Cu (OH)2The element distribution and TEM image of the nanowire array can be seen from FIG. 1, the material contains Cu element and O element, the lattice stripe spacing of the material is 0.259nm, and the nanowire can be determined to be a copper hydroxide nanowire.
The porous copper nitride nanowire array prepared in step 4) of this example 1 is characterized in structure and morphology by XRD, SEM and TEM, and result graphs as shown in fig. 2 and 7 are obtained. Fig. 2 is an element distribution and TEM image of the porous copper nitride nanowire array, and fig. 7 is an SEM image of the porous copper nitride nanowire array, and it can be seen from the figure that the material contains Cu and N elements, and the structure is a copper nitride nanowire according to the interplanar spacing in the copper nitride (100) direction.
The lithium-free negative electrode full cell assembled in step 5) of this example 1 was subjected to an electrochemical performance test using a multi-channel cell tester to obtain a result graph as shown in fig. 3, and as can be seen from fig. 3, the lithium-free negative electrode full cell obtained by using the porous copper nitride nanowire array as a current collector can be cycled for 100 cycles at a current density of 0.2C.
Example 2
The embodiment provides a preparation method of a porous copper nitride nanowire array, which comprises the following steps:
1) taking a copper foil with the length of 2cm, the width of 2cm and the thickness of 5 microns, putting the copper foil into a proper amount of hydrochloric acid solution for soaking and taking out, washing the copper foil cleanly by deionized water, putting the copper foil into a proper amount of acetone solution, carrying out ultrasonic cleaning, and then putting the copper foil into a proper amount of absolute ethyl alcohol solution for ultrasonic cleaning;
2) weighing 2.0mg of flaky sodium hydroxide, pouring deionized water, fully stirring to dissolve the flaky sodium hydroxide uniformly, weighing 0.4mg of ammonium persulfate powder, pouring the ammonium persulfate powder into the completely dissolved sodium hydroxide solution, and quickly stirring to obtain a mixed solution;
3) putting the copper foil for standby cleaning into the mixed solution for reaction for 40min, taking out the copper foil, rinsing for 3 times by using deionized water and absolute ethyl alcohol respectively, drying in the air, and obtaining an intermediate Cu (OH) on the surface of the copper foil2A nanowire array;
4) mixing Cu (OH)2And (3) putting the nanowire array into a tube furnace, introducing flowing ammonia gas, raising the temperature at the rate of 5 ℃/min, calcining at the temperature of 350 ℃, keeping the temperature for 4h, and naturally cooling to obtain the porous copper nitride nanowire array growing compactly on the surface of the copper foil.
Cu (OH) prepared in step 3) of example 22And (3) carrying out structural and morphological characterization on the nanowire array through a TEM (transmission electron microscope), and obtaining a result graph shown in FIG. 4, wherein as can be seen from FIG. 4, by prolonging the standing reaction time, the nanowires grown on the copper foil are thicker, and even nanosheets appear.
Example 3
This example provides a method for preparing a porous copper nitride nanowire array, which is different from example 2 in that:
in the step 3), the copper foil for standby cleaning is put into the mixed solution to react for 6 min;
the remaining steps and parameters were the same as in example 2.
Cu (OH) prepared in example 32And (3) carrying out structural and morphological characterization on the nanowire array through SEM to obtain a result graph shown in FIG. 5, wherein as shown in FIG. 5, the nanowires grown on the copper foil are shorter when the standing reaction time is shorter.
Example 4
This example provides a method for preparing a porous copper nitride nanowire array, which is different from example 2 in that:
in the step 1), a piece of copper foil with the length of 4cm, the width of 4cm and the thickness of 5 mu m is taken;
the remaining steps and parameters were the same as in example 2.
Cu (OH) prepared in example 42And (3) carrying out structural and morphological characterization on the nanowire array through SEM (scanning electron microscope), and obtaining a result graph shown in FIG. 6. As can be seen from FIG. 6, when the standing reaction time is the same, the larger the active reaction area of the copper foil is, the shorter the nanowire grows on the copper foil.
In summary, the morphology of the copper nitride nanowire array provided by the present invention is related to the morphology of the copper hydroxide nanowire array as an intermediate product, and the specific morphology of the copper hydroxide nanowire array is related to the reaction conditions, specifically including the reaction duration and the surface area of the reactant. The longer the reaction time is, the longer and thicker the grown nanowire is, and when the reaction time is further prolonged to a certain degree, the nanowire begins to become a nanosheet; the larger the active reaction area, the shorter the nanowires grown on the copper foil. Along with the increase of the reaction time, the reaction is more and more sufficient, the nanowire continuously reacts and lengthens, when the nanowire growing to a certain degree collapses and is mutually interwoven, and the nanosheet can appear after the nanowire continuously grows; the larger the active reaction area, the more nucleation sites for the nanowires, and thus the shorter the grown nanowires.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (9)
1. A preparation method of a porous copper nitride nanowire array is characterized by comprising the following steps:
s1, dissolving sodium hydroxide and ammonium persulfate in water to prepare a mixed solution, placing the copper foil in the mixed solution, standing for reaction, washing and drying to obtain a precursor Cu (OH)2A nanowire array;
s2, mixing the precursor Cu (OH)2And calcining the nanowire array under a preset condition to obtain the porous copper nitride nanowire array.
2. The method according to claim 1, wherein in the mixed solution of step S1, the mass ratio of the sodium hydroxide to the ammonium persulfate is 3: 1 to 5: 1, in the range of.
3. The method according to claim 2, wherein the conditions of the standing reaction in step S1 include a reaction temperature in the range of 20 ℃ to 30 ℃ and a reaction time in the range of 6min to 60 min.
4. The method of claim 1, wherein the copper foil is pretreated in step S1, and the pretreatment step comprises washing the copper foil with an acidic solution and an organic solution in this order.
5. The method according to any one of claims 1 to 4, wherein the preset conditions in step S2 include: the calcination temperature is within the range of 300 ℃ to 500 ℃, the calcination time is within the range of 3h to 5h, and the temperature rise rate of the tube furnace is within the range of 5 ℃/min to 10 ℃/min.
6. A porous copper nitride nanowire array, which is prepared by the method for preparing a porous copper nitride nanowire array according to any one of claims 1 to 5.
7. The array of porous copper nitride nanowires of claim 6, wherein the array of porous copper nitride nanowires comprises copper foil and copper nitride nanowires distributed in a vertical array on the surface of the copper foil.
8. The array of porous copper nitride nanowires of claim 6 or 7, wherein the copper nitride nanowires have a length in the range of 10 μm to 30 μm and a diameter in the range of 100nm to 300 nm.
9. The application of the porous copper nitride nanowire array in the lithium-free negative electrode lithium sulfur full cell field according to any one of claims 6 to 8, wherein the lithium-free negative electrode lithium sulfur full cell is assembled by using the porous copper nitride nanowire array as a negative electrode current collector and using lithium sulfide as a lithium source.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114530606A (en) * | 2022-01-06 | 2022-05-24 | 清华大学深圳国际研究生院 | Three-dimensional lithium-philic carbon interface modified copper-based current collector and preparation method and application thereof |
| CN116062712A (en) * | 2023-04-04 | 2023-05-05 | 南京邮电大学 | Sodium battery current collector based on thorn-shaped copper nitride and preparation method and application thereof |
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| CN114530606A (en) * | 2022-01-06 | 2022-05-24 | 清华大学深圳国际研究生院 | Three-dimensional lithium-philic carbon interface modified copper-based current collector and preparation method and application thereof |
| CN114530606B (en) * | 2022-01-06 | 2023-05-23 | 清华大学深圳国际研究生院 | Three-dimensional lithium-philic carbon interface modified copper-based current collector and preparation method and application thereof |
| CN116062712A (en) * | 2023-04-04 | 2023-05-05 | 南京邮电大学 | Sodium battery current collector based on thorn-shaped copper nitride and preparation method and application thereof |
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