CN112626556B - Method for preparing difunctional ternary metal hydroxyl nitride electrocatalyst by using waste lithium cobaltate - Google Patents
Method for preparing difunctional ternary metal hydroxyl nitride electrocatalyst by using waste lithium cobaltate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- -1 hydroxyl nitride Chemical class 0.000 title claims abstract description 40
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 26
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 9
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 39
- 230000003197 catalytic effect Effects 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000011065 in-situ storage Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000005805 hydroxylation reaction Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910020639 Co-Al Inorganic materials 0.000 description 3
- 229910020675 Co—Al Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The application discloses a method for preparing a bifunctional ternary metal hydroxyl nitride electrocatalyst by using waste lithium cobaltate, which comprises the following steps of (1) crushing a waste lithium cobaltate anode material, sieving, grinding a screen lower material into powder, soaking in dilute hydrochloric acid, and taking a supernatant as A; (2) Adding sodium hydroxide solution into the solution A until the pH value of the solution is 7 to obtain B; (3) respectively adding ferric nitrate solution and ethanol into the B to obtain C; (4) Putting foamed aluminum with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously discharging foamed aluminum plasma in a nitrogen atmosphere to enable the foamed aluminum plasma to perform chemical reaction on the surface; (5) And washing the self-supporting electrode, and then vacuum drying to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst. The method is simple, the whole production process is simple, the conditions are mild, the process is easy to control, the cost is low, and the method is suitable for large-scale production.
Description
Technical Field
The application belongs to the fields of waste resource utilization and catalytic chemistry, relates to a preparation method of a difunctional electrocatalyst, and in particular relates to a method for preparing a difunctional ternary metal hydroxyl nitride electrocatalyst by using waste lithium cobaltate.
Background
Renewable electric energy driven electrocatalytic decomposition of water has been considered the most promising way to produce clean hydrogen fuel from rich water resources, support energy safety and emissions reduction. The key of the large-scale application of the electrolyzed water is how to reduce the overpotential of the anodic Oxygen Evolution Reaction (OER) and the cathodic Hydrogen Evolution Reaction (HER), realize the high-current hydrogen production under low potential, and further reduce the electric energy consumption and the hydrogen production cost. Researches show that noble metals such as Ru, ir, pt and the like and oxides thereof have the most excellent hydrogen evolution catalytic performance, but the wide application of the materials is limited by the high price and the lack of resources. Therefore, the development of the cheap and efficient non-noble metal water electrolysis catalyst has very important scientific significance and practical value.
The existing catalyst generally has high catalytic activity only for one reaction (OER or HER), and has high catalytic activity for both reactions at the same time. However, in the process of the electrolytic water reaction, two different types of catalysts are required to jointly catalyze the oxygen evolution reaction and the hydrogen evolution reaction so as to improve the overall reaction rate. This in turn makes the water electrolysis apparatus more complex and increases the running cost. Current research on electrocatalysts has focused mainly on developing single-function electrocatalysts with a single Hydrogen Evolution Reaction (HER) or Oxygen Evolution Reaction (OER), but achieving dual functionalities (hydrogen evolution and oxygen evolution catalysis) simultaneously on a single catalyst basis presents a significant challenge.
Lithium ion batteries using lithium cobaltate materials as the positive electrode have been widely used in commerce due to their unique series of advantages such as low cost and long cycle life. However, due to the limitation of the service life of the battery material, the retirement period of the battery material is gradually reached, and a large number of abandoned lithium ion batteries face the disposal problem after retirement. Because the waste electrode material contains recyclable metals (such as cobalt and the like), if the waste electrode material is directly discarded as dangerous waste, the disposal cost is increased on one hand, and the waste of useful resources is directly caused on the other hand, so that the effects of recycling and increasing the value of the waste material cannot be realized. Therefore, the research and development of recycling of lithium ion battery materials has very important significance. If the cobalt element in the lithium cobalt oxide anode material is recycled, and is prepared and assembled into a heterogeneous nano material with a hierarchical structure, the double-function full-water-splitting catalyst is synthesized, so that the problems can be effectively solved, the double-function full-water-splitting catalyst can be applied to the field of water electrolysis as a catalyst, the cost of water electrolysis can be reduced, the environmental pressure can be relieved, and the high-efficiency recycling of waste resources can be realized.
Disclosure of Invention
In order to overcome the defects in the prior art, the application provides a method for preparing the difunctional ternary metal hydroxyl nitride electrocatalyst by utilizing waste lithium cobaltate, wherein iron, cobalt ions and foamed aluminum can quickly react with nitrogen atoms in situ under a nitrogen atmosphere of plasma discharge, element distribution is effectively regulated under the action of plasma discharge, and finally ternary metal hydroxyl nitride with a large number of active sites is formed.
The technical scheme provided by the application is as follows:
the method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate sequentially comprises the following steps:
(1) Pulverizing waste lithium cobalt oxide anode material, sieving, taking the undersize, grinding the undersize into powder, soaking in dilute hydrochloric acid, and taking the supernatant as A;
(2) Adding sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
in this step, the pH of the solution B needs to be controlled to be 7, i.e., the solution is neutral, the pH of the solution is closely related to the concentration of cobalt ions in the solution, the concentration of cobalt ions affects the in-situ reaction in the subsequent plasma discharge process, during the plasma discharge reaction, each element has a competition reaction, the amount of cobalt atoms contained in the catalyst material and the active site thereof are related to the final catalytic performance thereof, and the cobalt element needs to cooperate with other elements to improve the catalytic performance of the catalyst, so the content thereof needs to be controlled within a certain range, and the pH of the solution is less than 7 or greater than 7, so the catalyst of the present application cannot be prepared;
(3) Respectively and sequentially adding 5-10mL of ferric nitrate solution and 5-10mL of ethanol into the B, and uniformly stirring to obtain C;
in the step, ferric nitrate is added, so that the overall reaction rate is accelerated through the oxidation-reduction reaction of ferric iron and foamed aluminum in the subsequent plasma discharge treatment process, the ferric iron can show extremely strong oxidizing property under the current solution environment, the foamed aluminum has extremely strong reducing property, the ferric iron and the foamed aluminum can undergo oxidation-reduction reaction, nano particles with regular morphology can be rapidly and efficiently prepared, and the hydroxyl metal compound can be generated in the subsequent chemical reaction process after ethanol is introduced into a reaction system;
(4) Putting foamed aluminum with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum in a nitrogen atmosphere to enable the foamed aluminum to quickly and efficiently react on the surface;
in the step, nitrogen generates a large amount of electron energy in the process of plasma discharge, can activate metal ions around aluminum foam to react with nitrogen, and generates a hydroxy metal compound in the discharge process under an ethanol solution system of a large amount of ferric iron, and the hydroxy metal compound and the metal nitride with controllable content and specific distribution have a difunctional catalytic effect;
(5) And washing the self-supporting electrode by absolute ethyl alcohol and deionized water for 3-6 times in sequence, and vacuum drying to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst.
As a limitation of the present application:
in step (1), the undersize is pulverized to a particle size of 400 mesh.
And (II) in the step (1), the concentration of the dilute hydrochloric acid is 3-6M, and the soaking time is 3-8h.
(III) in the step (3), the concentration of the ferric nitrate is 100-150mM.
(IV) in the step (4), the voltage of the plasma discharge is 50V, and the reaction is 10-120s;
in the step, the plasma discharge voltage and the discharge time have important influence on the morphology and the particle size of the final product, and when the discharge voltage is less than 50V, the metal ions do not react sufficiently on the foamed aluminum, so that the self-supporting electrode has poor cohesiveness, the electrocatalyst is easy to fall off in the electrocatalytic process, and the catalysis effect is influenced; when the discharge voltage is more than 50V, more nano particles are rapidly generated in the discharge process, and are easy to agglomerate, so that the transmission of electrolyte ions and electrons among the nano particles is weakened, and the electrocatalytic performance is reduced;
when the plasma discharge time is less than 10s, the nitriding reaction is insufficient in the discharge process, so that the synthesis of nitrided metal in the bifunctional electrocatalyst is affected, and the performance of the nanocomposite electrocatalyst is reduced; when the plasma discharge time is more than 120s, although nitriding completely reacts in the discharge process, the synthesis of the hydroxy metal compound is affected, the hydroxy metal compound is unevenly distributed, and the dual-function electrocatalytic performance is reduced.
And (fifth), in the step (5), the drying temperature is 60-100 ℃ and the drying time is 6-12h.
And (six) in the step (4), the thickness of the foamed aluminum is 0.01cm.
The application also has the limit that the difunctional ternary metal hydroxyl nitride electrocatalyst is in a nano morphology formed by crosslinking nano particles, and the particle size is 50-100nm; the morphology and structure of the application are well known to influence the catalytic performance, and the morphology and structure of the application are favorable for the transmission of ions and electrons, thus laying a foundation for the good catalytic performance.
In the plasma discharge treatment process, cobalt ions, iron ions and foamed aluminum can react with activated nitrogen in situ rapidly under the action of ethanol, the introduction of the ethanol and parameters of plasma discharge are critical to the preparation of the bifunctional metal oxynitride electrocatalyst, and the ethanol and the plasma discharge can control the formation and the content distribution of the metal oxynitride and further influence the morphology and the catalytic activity of a product. It is the technological parameters disclosed by the application to prepare, thus finally forming the nano catalyst with excellent bifunctional catalytic activity, and the existence of ethanol and the in-situ introduction of nitrogen in the process are closely related to the catalytic activity of the catalyst.
The preparation method is used as a whole to prepare the catalyst, and the steps are closely related and can not be split.
Compared with the prior art, the application has the following advantages:
1. in the preparation process, the waste lithium cobaltate material is subjected to high-efficiency resource utilization by utilizing a redox and plasma discharge method so as to prepare the difunctional ternary metal hydroxyl nitride electrocatalyst, the reaction condition is mild, the production process is simple and controllable, and the method is suitable for large-scale industrial production.
2. Nitrogen atoms are introduced in situ in the plasma discharge process, and the element distribution of the electrocatalyst can be controlled by a plasma discharge method, so that the ternary metal hydroxyl nitride with dual-function electrocatalytic activity is prepared, and the hydrogen evolution and oxygen evolution catalytic performances of the ternary metal hydroxyl nitride are greatly improved.
3. In the catalytic process, ternary metal and hydroxyl nitride are used for synergistic catalysis, so that the catalyst has excellent difunctional electrocatalytic activity, excellent hydrogen and oxygen evolution electrocatalytic activity and high catalytic stability.
4. Realizes the recycling of waste, can realize large-scale production and industrialization.
The method is suitable for recycling and reutilizing the lithium cobalt oxide anode material recovered from the waste lithium ion battery, and is further used for preparing the ternary metal hydroxyl nitride with the difunctional electrocatalytic activity.
The following description of the application will provide further details of embodiments of the application with reference to the accompanying drawings.
Drawings
FIG. 1 is a graph of the performance of an oxygen evolving LSV of a sample made in example 1 of the present application;
FIG. 2 is a graph of hydrogen evolution LSV performance of the sample prepared in example 2 of the present application;
FIG. 3 is a scanning electron microscope image of a sample prepared in example 3 of the present application;
FIG. 4 is an elemental analysis chart of a sample obtained in example 4 of the present application;
FIG. 5 is a graph showing comparison of hydrogen evolution LSV curves of samples prepared in examples 4, 5 and 6, respectively, according to the present application;
FIG. 6 is a graph showing comparison of the LSV curves of oxygen evolution of samples prepared in examples 4, 5 and 6 of the present application, respectively;
FIG. 7 is a graph comparing the dual function full hydrolysis LSV curves of the samples prepared in example 4, example 5 and example 6 of the present application, respectively.
Detailed Description
The reagents used in the examples described below were all commercially available reagents, and the preparation methods and detection methods used were all conventional techniques unless otherwise specified.
Example 1
The method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate sequentially comprises the following steps:
(11) Pulverizing and sieving lithium cobaltate cathode materials recovered from waste lithium ion batteries, taking undersize materials, grinding the undersize materials into powder, sieving with a 400-mesh sieve, putting into 3M dilute hydrochloric acid for soaking for 5 hours, and taking supernatant as A;
(12) Adding a certain amount of sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
(13) Respectively and sequentially adding 5mL of 100mM ferric nitrate solution and 5mL of ethanol into the B to obtain C;
(14) Putting foamed aluminum (thickness is 0.01 cm) with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum for 10s under the voltage of 50V in the nitrogen atmosphere, so that the foamed aluminum can quickly and efficiently carry out electrochemical reaction on the surface;
(15) Washing the self-supporting electrode with absolute ethyl alcohol and deionized water for 3 times in sequence, and vacuum drying at 60 ℃ for 8 hours to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst.
FIG. 1 is a schematic view of an LSV for oxygen evolution of a sample obtained in example 1 of the present application, at a current density of 10mA -2 The oxygen evolution overpotential of the material prepared in example 1 was 196mV, indicating that the ternary metal hydroxynitrides have excellent oxygen evolution catalytic activity.
Example 2
The method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate sequentially comprises the following steps:
(21) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, sieving with 400 mesh sieve, soaking in 6M dilute hydrochloric acid for 3h, and taking supernatant as A;
(22) Adding a certain amount of sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
(23) Sequentially adding 150mM ferric nitrate solution and 8mL of ethanol into the B respectively to obtain C;
(24) Putting foamed aluminum (thickness is 0.01 cm) with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum for 120s under the voltage of 50V in the nitrogen atmosphere, so that the foamed aluminum can quickly and efficiently carry out electrochemical reaction on the surface;
(25) Washing the self-supporting electrode by absolute ethyl alcohol and deionized water for 6 times in sequence, and vacuum drying at 100 ℃ for 12 hours to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst.
FIG. 2 is a hydrogen-evolving LSV graph of the sample obtained in example 2 of the present application at a current density of 10mA -2 When the hydrogen evolution overpotential of the material prepared in example 2 is 177mV, the ternary metal hydroxyl nitride has excellent hydrogen evolution catalytic activity.
Example 3
The method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate sequentially comprises the following steps:
(31) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, sieving with 400 mesh sieve, soaking in 5M dilute hydrochloric acid for 8h, and taking supernatant as A;
(32) Adding a certain amount of sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
(33) Sequentially adding 10mL of 110mM ferric nitrate solution and 10mL of ethanol into the B respectively to obtain C;
(34) Putting foamed aluminum (thickness is 0.01 cm) with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum for 60s under the voltage of 50V in the nitrogen atmosphere, so that the foamed aluminum can quickly and efficiently carry out electrochemical reaction on the surface;
(35) Washing the self-supporting electrode sequentially by absolute ethyl alcohol and deionized water for 5 times, and vacuum drying at 80 ℃ for 6 hours to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst.
FIG. 3 is a scanning electron microscope image of the sample prepared in example 3 of the present application at a high magnification, from which it can be seen that the sample is composed of nanoparticles having a particle size of 50-100nm.
Example 4
The method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate sequentially comprises the following steps:
(41) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, sieving with 400 mesh sieve, soaking in 5M dilute hydrochloric acid for 5h, and taking supernatant as A;
(42) Adding a certain amount of sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
(43) Sequentially adding 8mL of 120mM ferric nitrate solution and 8mL of ethanol into the B respectively to obtain C;
(44) Putting foamed aluminum (thickness is 0.01 cm) with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum for 60s under the voltage of 50V in the nitrogen atmosphere, so that the foamed aluminum can quickly and efficiently carry out electrochemical reaction on the surface;
(45) Washing the self-supporting electrode sequentially by absolute ethyl alcohol and deionized water for 3 times, and vacuum drying at 60 ℃ for 6 hours to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst;
fig. 4 is an elemental analysis chart of a sample obtained in example 4 of the present application, and the material is a ternary metal oxynitride of fe—co—al, which demonstrates that cobalt ions, iron ions, and aluminum ions in the waste lithium-oxide positive electrode material undergo hydroxylation and nitridation reactions simultaneously under the action of plasma discharge in an ethanol and nitrogen atmosphere, and the cobalt content is 9.12 percent.
Example 5 comparative example
This example is a method for preparing a ternary metal hydroxy electrocatalyst using waste lithium cobaltate, similar to the preparation procedure of example 4, except that: no plasma discharge is adopted in the preparation process.
The specific steps are sequentially carried out according to the following sequence:
(51) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, sieving with 400 mesh sieve, soaking in 5M dilute hydrochloric acid for 5h, and taking supernatant as A;
(52) Adding a certain amount of sodium hydroxide solution into the solution A until the PH value of the solution is 7 to obtain B;
(53) Sequentially adding 8mL of 120mM ferric nitrate solution and 8mL of ethanol into the B respectively to obtain C;
(54) Putting foamed aluminum (thickness is 0.01 cm) with diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, and soaking the foamed aluminum on the surface of the C solution to enable the foamed aluminum to perform chemical reaction on the surface;
(55) And washing the self-supporting electrode by absolute ethyl alcohol and deionized water for 3 times in sequence, and vacuum drying at 60 ℃ for 6 hours to obtain the ternary metal hydroxyl electrocatalyst.
FIG. 5 is a graph showing the comparison of the oxygen evolution electrocatalytic performance of the samples prepared in examples 4, 5 and 6 (examples described below) of the present application. As can be seen from the figure, under the combined action of plasma discharge in nitrogen atmosphere and ethanol, the hydrogen evolution catalytic activity of the ternary metal hydroxyl nitride of Fe-Co-Al prepared in the embodiment 4 is highest, which shows that the introduction of ethanol into a plasma discharge method and a reaction system plays an important role in preparing a high-activity bifunctional electrocatalytic material, in the preparation process, metal ions in solution and ethanol are subjected to hydroxylation reaction, and simultaneously, nitrogen atoms can participate in hydroxylation and nitridation reaction in situ in the process of plasma discharge in nitrogen atmosphere, so that the ternary metal hydroxyl nitride with bifunctional electrocatalytic activity can be formed, and the cross-linked nanoparticle morphology of the application is formed, and in the catalytic hydrogen evolution process, the fact that the plasma method is not adopted in the prepared sample has very poor hydrogen evolution catalytic activity, and the nitridation of plasma in the nitrogen atmosphere plays an important role in improving the hydrogen evolution catalytic activity. In the catalytic reaction process, the catalyst provided by the application performs synergistic catalysis between three metals of Fe, co and Al and nitrogen atoms, and forms a composite active center which is favorable for hydrogen evolution catalytic reaction, so that the synergistic catalysis effect is achieved.
Example 6 comparative example
This example is a method for preparing a ternary metal nitride electrocatalyst using waste lithium cobaltate, similar to the preparation procedure of example 4, except that: ethanol is not added in the preparation process.
The specific preparation process is carried out sequentially according to the following preparation steps:
(61) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, sieving with 400 mesh sieve, soaking in 5M dilute hydrochloric acid for 5h, and taking supernatant as A;
(62) Adding a certain amount of sodium hydroxide solution into the solution A until the PH value of the solution is 7 to obtain B;
(63) Adding 8mL of 120mM ferric nitrate solution into the B to obtain C;
(64) Putting foamed aluminum (thickness is 0.01 cm) with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, invading the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum for 60s under the voltage of 50V in the nitrogen atmosphere to enable the foamed aluminum to carry out electrochemical reaction on the surface;
(65) Washing the self-supporting electrode sequentially by absolute ethyl alcohol and deionized water for 3 times, and vacuum drying at 60 ℃ for 6 hours to obtain the electrocatalyst;
FIG. 6 is a graph comparing the oxygen evolution electrocatalytic performance of samples prepared in examples 4, 5 and 6 of the present application. As can be seen from the figure, under the combined action of plasma discharge in nitrogen atmosphere and ethanol, the oxygen evolution catalytic activity of the ternary metal hydroxyl nitride of Fe-Co-Al prepared in the embodiment 4 is highest, which shows that the addition of the plasma discharge method and ethanol plays an important role in preparing the high-activity bifunctional electrocatalytic material, and in the preparation process, metal ions in the solution can participate in hydroxylation and nitridation reactions in situ during the hydroxylation reaction with ethanol at the same time of the hydroxylation reaction with ethanol in the process of the plasma discharge in nitrogen atmosphere, so that the ternary metal hydroxyl nitride with the bifunctional electrocatalytic activity can be formed, and the cross-linked nanoparticle morphology of the application is formed. In the catalytic oxygen evolution process, it can be seen that the example 6 was free of ethanol and the catalytic activity of oxygen evolution of the sample was very poor, so that the addition of ethanol had an important effect on the improvement of the catalytic activity of oxygen evolution. In the catalytic reaction process, the catalyst provided by the application performs synergistic catalysis between three metals of Fe, co and Al and nitrogen atoms, and forms a composite active center which is favorable for oxygen evolution catalytic reaction, so that the synergistic catalysis effect is achieved.
FIG. 7 is a graph showing comparison of the catalytic performance of the dual-function electrolyzed water prepared according to the example 4, the example 5 and the example 6 of the present application. As can be seen from the figure, the dual-function catalytic activity of the ternary metal hydroxyl nitride of Fe-Co-Al prepared in example 4 is highest under the combined action of plasma discharge in nitrogen atmosphere and ethanol, which indicates that the addition of ethanol and the plasma technology plays an important role in preparing the dual-function electrocatalytic material with high activity. In the catalytic hydrogen evolution process, it can be seen that example 5 does not use a plasma discharge method, and the catalytic activity of the sample hydrogen evolution is very poor, resulting in poor dual-function electrocatalytic activity; in the catalytic oxygen evolution process, it can be seen that example 6 was not added with ethanol, and the catalytic activity of the sample oxygen evolution was very poor, resulting in poor dual-function electrocatalytic activity.
Finally, it should be noted that: the embodiments described above are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (5)
1. The method for preparing the bifunctional ternary metal hydroxyl nitride electrocatalyst by using the waste lithium cobaltate is characterized by sequentially performing the following steps:
(1) Pulverizing waste lithium cobalt oxide anode material, sieving, taking undersize, grinding undersize into powder, soaking in dilute hydrochloric acid with concentration of 3-6M for 3-8h, taking supernatant and recording as A;
(2) Adding sodium hydroxide solution into the A until the pH value of the solution is 7 to obtain B;
(3) Respectively and sequentially adding 5-10mL of ferric nitrate solution and 5-10mL of ethanol into the B, wherein the concentration of ferric nitrate is 100-150mM, and stirring uniformly to obtain C;
(4) Putting foamed aluminum with the diameter of 1cm multiplied by 1cm into C, taking the foamed aluminum as a working electrode, taking C as a reaction solution, soaking the foamed aluminum on the surface of the C solution, and simultaneously carrying out plasma discharge on the foamed aluminum under the nitrogen atmosphere, wherein the voltage of the plasma discharge is 50V, and the reaction is carried out for 10-120s, so that the foamed aluminum can quickly and efficiently react on the surface;
(5) And washing the self-supporting electrode by absolute ethyl alcohol and deionized water for 3-6 times in sequence, and vacuum drying to obtain the bifunctional ternary metal hydroxyl nitride electrocatalyst.
2. The method for preparing a bifunctional ternary metal oxynitride electrocatalyst using lithium cobaltate according to claim 1, wherein in step (1), the undersize is pulverized to a particle size of 400 mesh.
3. The method for preparing a bifunctional ternary metal oxynitride electrocatalyst using lithium cobaltate according to claim 1, wherein in step (5), the drying temperature is 60-100 ℃, and the drying time is 6-12h.
4. The method for preparing a bifunctional ternary metal oxynitride electrocatalyst using lithium cobaltate according to claim 1, wherein in step (4), the foamed aluminum has a thickness of 0.01cm.
5. The method for preparing the bifunctional ternary metal oxynitride electrocatalyst from the lithium cobaltate according to any one of claims 1 to 4, wherein the bifunctional ternary metal oxynitride electrocatalyst is a nanotopography consisting of nanoparticle crosslinks, and has a particle size of 50 to 100nm.
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