CN109734065B - Nano porous metal compound material, preparation method and application - Google Patents
Nano porous metal compound material, preparation method and application Download PDFInfo
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- CN109734065B CN109734065B CN201910193325.9A CN201910193325A CN109734065B CN 109734065 B CN109734065 B CN 109734065B CN 201910193325 A CN201910193325 A CN 201910193325A CN 109734065 B CN109734065 B CN 109734065B
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Abstract
The invention relates to a nano porous metal compound material with adjustable porosity and pore diameter, a preparation method and application thereof. According to an alloy phase diagram, pure metal and metal compound or pure metal and non-metal simple substance in a certain proportion are designed to be subjected to arc melting in a protective atmosphere to prepare an alloy ingot, then the alloy ingot is subjected to remelting and rapid solidification melt-spinning by controlling the rotating speed of a copper roller, and finally the alloy strip is subjected to microcosmic galvanic couple selective corrosion to obtain the nano porous metal compound material. The preparation method has simple and controllable process and is environment-friendly. The porosity of the prepared self-supporting nano porous metal compound is controlled by the proportion of pure metal and metal compound or pure metal and non-metal simple substance when the alloy ingot is smelted, and the size of the pore diameter is controlled by the rotation speed of a copper roller during strip casting.
Description
Technical Field
The invention relates to a nano porous metal compound material, a preparation method and application thereof, belonging to the preparation technology of porous materials.
Background
The preparation of nano materials is one of the most active research directions in the field of new materials. Conventionally, nanostructured metal compounds have been synthesized mainly by a solvothermal method or the like. In large-scale preparation, the problems of poor controllability and reproducibility, environmental pollution and the like are faced. The nano-porous metal compound prepared by the method exists in a powder form, and a conductive agent and an adhesive are needed to be further prepared into a functional film layer or an electrode in the practical application process. The electrochemical stability is poor due to poor contact between the conductive agent and the binder. At the same time, the internal resistance is high, which also leads to a reduction in energy efficiency. With the continuous improvement of the requirements of the leading-edge research on the material characteristics, the nano functional material needs to be comprehensively considered in the aspects of preparation method, component control, structural design and the like.
The dealloying method, also called selective corrosion, is to utilize the characteristic of large difference in electrode potential between alloy components to selectively dissolve elements with active chemical properties, so that the elements enter an electrolyte solution, and the rest components spontaneously form three-dimensional continuous porous metal in the modes of atomic diffusion, aggregation and the like. Over the past decades, this method has been usedThe prepared nano-porous metal and alloy are widely applied in many fields (Corros. Sci.2018, 134, 78.). However, this method is applied only to metals because metals have flexible metal bonds and high atomic diffusion ability, and have low formation energy when self-assembled to form a metal crystal skeleton. Metal compounds, such as phosphides, sulfides, selenides, borides, nitrides, etc., are mainly composed in the form of ionic or covalent bonds, have low diffusivity and high formation energy, and cannot be prepared by dealloying methods. How to introduce a porous structure into a metal compound to obtain a nano porous metal compound with an ultra-high specific surface area, so that the nano porous metal compound has dual attributes of a pore structure and a nano function, and is a great challenge in the field of material preparation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a universal nano porous metal compound material, a preparation method and application thereof. The preparation process is simple and controllable, environment-friendly, and the porosity and pore diameter of the prepared self-supporting nano porous metal compound are adjustable.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a nanoporous metallic compound material comprising a transition metal element and a non-metal element, the nanoporous metallic compound material having a bicontinuous nanoporous structure; wherein the metal compound has the chemical formula of (A)zE1-z）x（CkD1-k）yA, E is a transition metal element, C, D is a nonmetal element; z is more than or equal to 0 and less than or equal to 1, k is more than or equal to 0 and less than or equal to 1, x is more than 0, and y is more than 0.
Further, A, E are transition metal elements different from each other, and C, D are nonmetal elements different from each other.
Further, the transition metal element comprises at least one of Ni, Co, Fe, Cu and Cr, and the nonmetal element comprises at least one of P, S, Se, B and Te.
Further, in the nano-porous metal compound material, the molar ratio of the transition metal element to the nonmetal element is 1-10:1-10, and further 3-9: 1-8.
Further, the transition metal element is at least one of Ni, Co and Fe, and the nonmetal element is at least one of P, S, Se and B.
Further, the porosity of the nano-porous metal compound material is 20-80%, preferably 30-70%; the pore diameter is 5-400 nm, preferably 10-200 nm. The applicant researches and discovers that the nano-porous metal compound material with the porosity and the pore diameter characteristics has excellent strength, toughness and active surface area.
Further, the nanoporous metallic compound material comprises Ni3P、Co9S8、Co0.85Se、Co3B、(CozNi1-z)3P, wherein 0 < z < 1.
The preparation method of the nano-porous metal compound material is characterized by comprising the following steps:
s1, determining the molar ratio of the transition metal element and the nonmetal element required by the raw material according to the composition of the target nano-porous metal compound material, the alloy phase diagram of the contained metal compound and actual requirements;
s2, determining the raw material ratio according to the molar ratio data obtained in S1; preparing an alloy ingot by a smelting method;
wherein the raw material comprises a simple substance of the nonmetal element, at least one of a compound of a transition metal element and a nonmetal element, and a simple substance of the transition metal element;
s3, carrying out strip throwing treatment on the alloy ingot obtained in the step S2 to obtain an alloy strip;
and S4, carrying out microscopic galvanic corrosion on the alloy strip obtained in the S3 to obtain the nano porous metal compound material.
Further, in S2, the molar ratio of the content of the transition metal element to the content of the nonmetal element in the raw material is 75-95:5-20, generally 80-90:10-20, preferably 85-90: 10-15. The applicant researches and discovers that the porosity of the material can be regulated and controlled by controlling the molar ratio of the transition metal element to the nonmetal element in the raw material, and generally, the higher the ratio of the nonmetal element in the raw material is, the higher the porosity of the material is.
Further, in S2, the raw material is placed in an arc melting apparatus under a protective atmosphere to prepare an alloy ingot.
Further, in S3, the rotation speed of the roller during the tape-spinning treatment is 800-. The applicant has found that by controlling the rotational speed of the roller, the pore size of the pores can be controlled, generally speaking, the faster the rotational speed, the smaller the pore size of the pores, and the greater the porosity. Optionally, the roller is a copper roller.
Further, in S4, a three-electrode system is used for microscopic galvanic corrosion, an Ag/AgCl electrode is used as a reference electrode, a carbon sheet is used as a counter electrode, an alloy strip is used as a working electrode, the etching voltage is controlled to be-0.1-0.5 Vvs Ag/AgCl, the etching time is controlled to be 1500-. Generally, increasing the voltage appropriately can shorten the etching time.
In the application, in the smelting process, pure metal and metal compound or pure metal and nonmetal simple substance can be selected as raw materials, and the porosity of the finally obtained nano porous metal compound material can be controlled by designing a reasonable molar ratio of the transition metal element to the nonmetal element. In the process of rapid solidification and melt spinning, alloy liquid drops dropped due to remelting are rapidly quenched on the cold surface of the roller, and a strip-shaped uniform nanocrystal two-phase structure (alloy strip: containing a metal phase and a metal compound phase) can be obtained. The pore size of the ribbon can be adjusted by controlling the rate of rotation of the rollers.
The homogeneous nanocrystal two-phase structure is due to the phenomenon of phase separation. According to an alloy phase diagram, metal and metal compound or metal and nonmetal simple substance with proper proportion are melted at high temperature and then rapidly solidified, and metal phases and metal compound phases which are uniformly distributed and mutually interpenetrated can be formed.
Microscopic galvanic corrosion refers to: by utilizing the electrochemical stability difference between the metal phase and the metal compound phase, a certain voltage is applied to the strip through the electrochemical workstation three-electrode system, so that the metal phase with poor electrochemical stability in the strip is dissolved, and the stable metal compound phase is reserved to form a nano-porous structure. In this way, the metal phase can be etched and the metal compound phase can be retained by utilizing the characteristic that the electrochemical stability of the metal phase and the metal compound phase in the alloy strip is different, so that the nano porous structure is formed.
Further, the electrochemical workstation three-electrode system is as follows: the alloy strip is used as a working electrode, Ag/AgCl and the like can be used as reference electrodes, and graphite flakes and the like can be used as counter electrodes. It is further important to use a suitable, more selective medium as the electrolyte solution.
The higher selectivity means that the difference between the critical solution voltages of the metal phase and the metal compound phase is large in the electrolyte. This ensures complete removal of the metal phase and not the metal phase intact to form the nanoporous structure. Optionally, the electrolyte solution is a sulfuric acid solution.
The nano-porous metal compound material or the nano-porous metal compound material prepared by the preparation method is applied as a self-supporting electrode.
The nano porous metal compound material has enough strength and toughness, can be directly used as a self-supporting electrode, and is expected to be applied to the fields of energy storage, catalysis, sensing and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the preparation methods such as a solvothermal method and the like, the preparation method of the nano porous metal compound material disclosed by the invention does not need to use an organic reagent or other toxic reagents, and is environment-friendly, green and safe.
(2) The preparation process of the nano porous metal compound material is simple and efficient, has low cost and good reproducibility, and can realize large-scale and industrial production.
(3) The pore structure of the nano-porous metal compound material comprises porosity and pore diameter, and can be controlled by controlling parameter conditions in the preparation process of the alloy strip so as to adapt to actual industrial application.
(4) The invention is a universal preparation method, which can simply combine different metal elements and nonmetal elements to prepare the nano-porous metal compound so as to adapt to the application in different fields.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
Fig. 1 is a schematic view of a process for preparing a nanoporous metallic compound material according to the present application.
FIG. 2a shows Ni in example 185P15 Scanning transmission electron microscope high angle annular dark field (HAADF-STEM) images of the strips. FIGS. 2b-c are the energy spectrum element maps of (b) Ni, (c) P and (d) Ni + P in FIG. 2a, respectively. FIG. 2e shows Ni85P15Strips and their nanoporous nickel phosphide (np-Ni) formed after microscopic galvanic corrosion3P) X-ray diffraction (XRD) pattern.
FIG. 3 shows the components (a) Ni80P20Strip, (b) Ni85P15Strips and (c) Ni90P10 The strips are rapidly solidified by a copper roller (four thousand revolutions per minute) with the same rotating speed and then are subjected to microscopic galvanic corrosion to obtain np-Ni3P scanning electron microscope image.
FIG. 4 shows Ni85P15The strips are rapidly solidified by copper rollers with the rotating speeds of (a) one thousand revolutions per minute, (b) two thousand revolutions per minute, (c) three thousand revolutions per minute, (d) four thousand revolutions per minute and (e) five thousand revolutions per minute to form np-Ni3Scanning Electron Microscope (SEM) image of P. FIG. 4f np-Ni prepared at a speed of five thousand revolutions per minute3Cross-sectional SEM image of P.
FIG. 5a shows Co in example 290S10HAADF-STEM image of the strip. FIGS. 5b-c are plots of (b) Co and (c) S spectral element maps within the dashed line of FIG. 5a, respectively. FIG. 5d is Co90S10Strips and their nanoporous cobalt sulfide (np-Co) formed after microscopic galvanic corrosion9S8) XRD pattern of. FIG. 5d is np-Co9S8 SEM image of the front surface. FIG. 5e is np-Co9S8 SEM image of cross section.
FIG. 6a shows Co85Se15 Ribbons and nanoporous cobalt selenide (np-Co) formed by microscopic galvanic corrosion thereof0.85Se) XRD pattern. FIG. 6b is np-Co0.85SEM image of Se.
FIG. 7a shows Co85B15 Strips and their nanoporous cobalt boride (np-Co) formed after microscopic galvanic corrosion3B) XRD pattern of (a). FIG. 7b is np-Co3SEM image of B.
FIG. 8 shows Co10Ni80P10 Nano-porous bimetallic phosphide np- (Co) formed by microscopic galvanic corrosion of strip0.11Ni0.89)3SEM image of P. The inset is np- (Co)0.11Ni0.89)3SEM-EDS image of P.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Arc melting of pure nickel particles and nickel phosphide (Ni) in an argon atmosphere2P) preparing an alloy ingot. In combination with the Ni-P alloy phase diagram, reasonable atomic ratios of Ni and P are designed, and three groups of Ni and P are set in the embodiment, wherein the three groups are respectively 80:20, 85:15 and 90: 10. After the composition of the alloy ingot is determined, remelting and strip casting are carried out under an argon atmosphere. The remelted alloy ingot was rapidly cooled by a copper roller cooled surface rotating at high speed to obtain an alloy strip of uniform nanocrystal two-phase structure (see fig. 1). As can be seen from the HAADF-STEM image (see FIG. 2 a) and the element mapping image (see FIGS. 2 b-d) in FIG. 2, the Ni phase (see the lighter area in FIG. 2 a) and Ni in the banding3P phases (see darker areas in fig. 2 a) coexist.
In a three-electrode system of an electrochemical workstation, an accurate-correction Ag/AgCl electrode is used asReference electrode, carbon sheet as counter electrode, alloy strip as working electrode, 0.5M H2SO4Electrochemical etching is performed as an electrolyte. Etch 3000s at 0.05 Vvs Ag/AgCl etch voltage (etch current down to 10-5mA) to np-Ni3P strips (see fig. 1). The change in phase composition in the bands before and after microscopic galvanic corrosion was observed by XRD (see figure 2 e). Before etching, the phase composition is Ni phase and Ni3P phase, Ni phase completely removed after corrosion and Ni3The P phase remains.
By controlling the atomic ratio of Ni and P, the final np-Ni can be obtained3The porosity of P is regulated. According to the alloy strips with different atomic ratios in the figure 3, the alloy strips are subjected to rapid solidification through copper rollers (four thousand revolutions per minute) with the same rotating speed and then to microscopic galvanic corrosion to obtain np-Ni3SEM image of P it can be seen that np-Ni increases with the atomic proportion of P3The porosity of P increases gradually.
The finally obtained np-Ni can be treated by controlling the rotating speed of the copper roller3The aperture size of P is regulated. According to the copper roller pair Ni in FIG. 4 using different rotation speeds85P15 np-Ni obtained by rapid solidification of the strip3SEM image of P it can be seen that np-Ni was obtained as the copper roller speed increased3The pore diameter of P is gradually reduced, and the porosity is gradually increased. The above results demonstrate the controllable preparation of pore structure by this method.
Example 2
By combining a Co-S alloy phase diagram, designing the atomic ratio of Co/S to be 90:10, preparing an alloy ingot by arc melting pure cobalt particles and cobalt sulfide (CoS) by the same method as in example 1, remelting and spinning the alloy ingot, and obtaining an alloy strip in which the Co phase and the Co phase are9S8 Co-exist (see fig. 5 a-c).
In the same etching three-electrode system as in example 1, the alloy strip was etched while setting a voltage of 0.00 Vvs Ag/AgCl. 2000 s etching resulted in complete removal of Co phase from the alloy strip9S8 Phase retention (see FIG. 5 d) results in a nanoporous bicontinuous structure (see FIGS. 5 e-f)。
Example 3
By combining a Co-Se alloy phase diagram, the atomic ratio of Co/Se is designed to be 85:15, pure cobalt particles and cobalt selenide (CoSe) are subjected to electric arc melting by the same method as that of the embodiment 1, then remelting and melt spinning are carried out, and the Co phase in the obtained alloy strip0.85Se coexists (see FIG. 6 a).
The same etching three-electrode system as in example 1 was used for etching, with an etch voltage set at-0.05V vs Ag/AgCl. After electrochemical etching for 2000 s, Co phase in the alloy strip is completely removed and Co is removed0.85The Se phase remains to form a nanoporous bicontinuous structure (see fig. 6 b).
Example 4
The Co-B alloy phase diagram is combined, the atomic ratio of Co/B is designed to be 85:15, pure cobalt particles and simple substance boron are subjected to electric arc melting by the same method as the embodiment 1 and then are subjected to remelting and strip casting, and the Co phase in the obtained alloy strip3Phase B coexists (see FIG. 7 a).
The same etching three-electrode system as in example 1 was used for etching, with an etch voltage set at-0.02V vs Ag/AgCl. After electrochemical etching for 2000 s, Co phase in the alloy strip is completely removed and Co is removed3The B phase remains to form a nanoporous bicontinuous structure (see fig. 7B).
Example 5
Pure cobalt particles, pure nickel particles and nickel phosphide (Ni) were arc-melted in the same manner as in example 1 while designing the Co/Ni/P atomic ratio to be 10:80:10 in combination with the Ni-P alloy phase diagram2P) and then remelting and strip casting are carried out, and CoNi solid solution alloy phase and (Co) in the obtained alloy strip0.11Ni0.89)3And P phases coexist.
The same etching three-electrode system as in example 1 was used for etching, with an etching voltage of 0.05V vs Ag/AgCl being set. After electrochemical etching for 3000s, CoNi solid solution alloy phase in the alloy strip is completely removed (Co0.11Ni0.89)3The P phase remains to form a nanoporous bicontinuous structure (see fig. 8). Further, (Co) may be usedxNi1-x)3The atomic ratio of the metal elements in P is adjusted to suit different application conditions.
In summary, the present patent discloses a nanoporous metal compound and a method for preparing the same, which are different from the conventional method for preparing a compound nanomaterial and have originality and advancement in principle. The above description of the embodiments is not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention is defined by the appended claims.
Claims (14)
1. A self-supporting nanoporous metallic compound material is characterized by comprising a transition metal element and a nonmetal element, the self-supporting nanoporous metallic compound material has a bicontinuous nanoporous structure, and the self-supporting nanoporous metallic compound material is in a strip shape; wherein the metal compound has the chemical formula of (A)zE1-z）x（CkD1-k）yA, E is a transition metal element, C, D is a nonmetal element; z is more than or equal to 0 and less than or equal to 1, k is more than or equal to 0 and less than or equal to 1, x is more than 0, and y is more than 0.
2. The self-supporting nanoporous metallic compound material according to claim 1, wherein the transition metal element comprises at least one of Ni, Co, Fe, Cu, Cr and the non-metal element comprises at least one of P, S, Se, B, Te.
3. The self-supporting nanoporous metal compound material according to claim 1, wherein the porosity of the self-supporting nanoporous metal compound material is 20-80%, preferably 30-70%; the pore diameter is 5-400 nm, preferably 10-200 nm.
4. The self-supporting nanoporous metallic compound material according to any one of claims 1-3, wherein the self-supporting nanoporous metallic compound material comprises Ni3P、Co9S8、Co0.85Se、Co3B、(CozNi1-z)3P, wherein 0 < z < 1.
5. The method of preparing the self-supporting nanoporous metallic compound material of any one of claims 1-4, comprising the steps of:
s1, determining the molar ratio of transition metal elements and non-metal elements required by the raw materials according to the composition of the target self-supporting nano-porous metal compound material, the alloy phase diagram of the contained metal compound and actual requirements;
s2, determining the raw material ratio according to the molar ratio data obtained in S1; preparing an alloy ingot by a smelting method;
wherein the raw material comprises a simple substance of the nonmetal element, at least one of a compound of a transition metal element and a nonmetal element, and a simple substance of the transition metal element;
s3, carrying out strip throwing treatment on the alloy ingot obtained in the step S2 to obtain an alloy strip;
and S4, carrying out microscopic galvanic corrosion on the alloy strip obtained in the S3 to obtain the self-supporting nano porous metal compound material.
6. The production method according to claim 5, wherein the molar ratio of the content of the transition metal element to the content of the nonmetal element in the raw material in S2 is 75-95: 5-20.
7. The production method according to claim 6, wherein in S2, the molar ratio of the content of the transition metal element to the content of the nonmetal element in the raw material is 80-90: 10-20.
8. The production method according to claim 6, wherein in S2, the molar ratio of the content of the transition metal element to the content of the nonmetal element in the raw material is 85-90: 10-15.
9. The production method according to claim 5, wherein in S2, the raw material is placed in an arc melting apparatus under a protective atmosphere to produce an alloy ingot.
10. The method as claimed in claim 5, wherein in S3, the rotation speed of the roller is 800-.
11. The method as claimed in claim 10, wherein in S3, the rotation speed of the roller is 1000-.
12. The method as claimed in claim 10, wherein in S3, the rotation speed of the roller is 2000-4000r/min during the melt spinning process.
13. The method as claimed in claim 5, wherein in S4, a three-electrode system is used for microscopic galvanic corrosion, an Ag/AgCl electrode is used as a reference electrode, a carbon sheet is used as a counter electrode, an alloy strip is used as a working electrode, the etching voltage is controlled to be-0.1-0.5 Vvs Ag/AgCl, and the etching time is controlled to be 1500-.
14. Use of the self-supporting nanoporous metal compound material as defined in any one of claims 1 to 4 or as prepared by the preparation method as defined in any one of claims 5 to 13 as a self-supporting electrode.
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