CN115043429A - Preparation method of layered hydroxyl copper pyrovanadate anode material - Google Patents
Preparation method of layered hydroxyl copper pyrovanadate anode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims abstract description 15
- ZMHWUUMELDFBCZ-UHFFFAOYSA-M copper(1+);hydroxide Chemical compound [OH-].[Cu+] ZMHWUUMELDFBCZ-UHFFFAOYSA-M 0.000 title claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 18
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 18
- 239000010406 cathode material Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims 1
- -1 hydroxyl pyroglutamic acid copper Chemical compound 0.000 abstract description 13
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 14
- 239000002073 nanorod Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000530268 Lycaena heteronea Species 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
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- 229910002473 Cu3V2O7(OH)2·2H2O Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
The invention discloses a preparation method of a layered hydroxyl copper pyrovanadate anode material, which comprises the following steps: step 1: adding a vanadium source into deionized water, heating and stirring at 90 +/-5 ℃ to dissolve, and obtaining a vanadium source solution; step 2: adding a copper source into deionized water, and uniformly stirring at room temperature to obtain a copper source solution; and step 3: adding the copper source solution into the vanadium source solution, and uniformly mixing to obtain a mixed solution; wherein the molar ratio of vanadium/copper atoms in the vanadium source and the copper source is 1 (1-4); and 4, step 4: and (3) magnetically stirring the mixed solution obtained in the step (3) to react to obtain a precipitate, and sequentially filtering, washing and drying to obtain the layered hydroxyl copper pyrovanadate anode material. The invention adopts a coprecipitation method, can realize the macro preparation of the hydroxyl pyroglutamic acid copper under the conditions of normal temperature and normal pressure, has simple and convenient preparation process and less condition limitation, is easy to realize large-scale popularization and application, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of magnesium ions, in particular to a preparation method of a layered hydroxyl pyroglutamic acid copper cathode material.
Background
In recent years, due to safety problems of lithium dendrites, complicated methods for preventing the formation of lithium dendrites, and supply shortage problems of lithium resources, multivalent ions (Mg) have been based 2+ 、Ca 2+ 、Zn 2+ Or Al 3+ ) Alternative technologies for batteries have attracted increasing attention. Among other advantages, rechargeable magnesium batteries have many advantages over lithium ion batteries, such as abundant magnesium resources, smaller ionic radii (0.72 a), and higher theoretical capacity (3833 mAh cm) -3 ). However, strong electrostatic interaction between magnesium ions and host materials and slow solid state diffusion kinetics of magnesium ions remain major factors that limit the development of magnesium ion batteries. Therefore, the development of a high-performance positive electrode material is urgently required.
Copper hydroxypyrovanadate (Cu) 3 V 2 O 7 (OH) 2 ·2H 2 O, CVOH) is a compound of V 2 O 7 Column, Cu 3 O 6 (OH) 2 Layered compound composed of layers and interlayer water molecules. Interlayer spacing is large, and interlayer intercalated water molecules can partially shield the electrostatic attraction between magnesium ions and a main material; in the direction perpendicular to the layers, there is a tunnel structure and vanadium atoms are exposed which can undergo redox reactions, so that Mg 2+ In which intercalation/deintercalation has good kinetic conditions. Copper atoms and vanadium atoms can participate in redox reaction, so that the theoretical specific capacity of the cathode material is high, and the cathode material is a potential candidate cathode material for a magnesium ion battery. Currently, copper hydroxyvanadates have been successfully applied as electrode materials. For example, patent CN 109103432A discloses a pyrovanadic acid copper/nitrogen-doped graphene composite nanosheet synthesized in one step by a hydrothermal method at 120-180 ℃ for 10-18 h, and using PVP and organic amine as additives, wherein the composite material has good electrochemical performance as a lithium ion battery cathode material. Patent CN2021113490348 disclosesA hydroxyl pyroglutamic acid copper micro-sphere prepared by a hydrothermal method by taking benzoic acid as an additive is successfully applied to a water-based magnesium ion battery and has 262 mAh g -1 High specific capacity and excellent cycling stability (capacity retention after 20000 cycles is 92%). However, both the flake shape and the spherical shape have the defect of easy agglomeration, and the one-dimensional nano structure (such as a nano rod) has certain advantages for the rapid transmission of ions and electrons, can inhibit the agglomeration of crystals to a certain extent and has good diffusion kinetics. The patent CN 113772727A discloses a method for preparing iron-doped copper pyrovanadate nanorods by a hydrothermal method, wherein the hydrothermal reaction condition is that the iron-doped copper pyrovanadate nanorods are reacted for 2-4 hours at 170-190 ℃; and the lithium ion battery anode material is used as an anode material of a high-performance water-based zinc ion battery, and higher capacity (256.4 mAh g-1) and cycle stability are obtained. However, no matter what morphology of copper hydroxypyrovanadate, the preparation method is currently limited to a hydrothermal method, the reaction conditions are harsh, higher reaction temperature and pressure are required, and the reaction process is sealed in a polytetrafluoroethylene reaction kettle; the product yield is low, and the product synthesized at one time is only in milligram level. And a certain amount of organic template is required to be added to control the size and the appearance of the crystal, the organic template can inhibit the growth of the crystal to a certain extent, the preparation time is prolonged, the cost is increased, and the preparation workload is increased. Therefore, the defects of the current preparation method are not beneficial to industrialized mass production, and the popularization and application of the hydroxyl pyroglutamic acid copper anode material in the field of secondary batteries such as magnesium ion batteries and the like are limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a layered copper hydroxypyrovanadate cathode material, so as to solve the problems that reaction conditions are harsh, the yield of products is low, the size and the morphology of crystals need to be controlled by an organic template agent, but the use of the organic template agent can prolong the preparation time and is difficult to realize mass preparation of products when the copper hydroxypyrovanadate is prepared in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a layered hydroxyl copper pyrovanadate anode material comprises the following steps:
step 1: adding a vanadium source into deionized water, heating and stirring at 90 +/-5 ℃ to dissolve, and obtaining a vanadium source solution;
step 2: adding a copper source into deionized water, and uniformly stirring at room temperature to obtain a copper source solution;
and step 3: adding the copper source solution into the vanadium source solution, and uniformly mixing to obtain a mixed solution; wherein the molar ratio of vanadium/copper atoms of the vanadium source and the copper source is 1 (1-4);
and 4, step 4: and (3) magnetically stirring the mixed solution obtained in the step (3) to react to obtain a precipitate, and sequentially filtering, washing and drying to obtain the layered hydroxyl copper pyrovanadate anode material.
The invention also provides application of the layered copper hydroxypyrovanadate anode material, and the layered copper hydroxypyrovanadate anode material for the magnesium ion battery is obtained by macroscopic preparation through the preparation method, and can be used for batch preparation of magnesium ion batteries, lithium ion batteries, zinc ion batteries and sodium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts a coprecipitation method, induces the nucleation rate of crystals by regulating and controlling the atomic molar ratio between a vanadium source and a copper source, leads the crystals to nucleate in a large amount in a short time, grows the hydroxyl pyroglutamic acid copper nanorods with uniform appearance and size, solves the problems of harsh synthesis conditions, low yield and the like in the traditional synthesis method, has simple and convenient material preparation, can realize the preparation of a large amount of products under the conditions of normal temperature and normal pressure, obviously improves the production efficiency, and is suitable for industrial large-scale production and application
2. The hydroxyl pyroglutamic acid copper prepared by the method is a nanorod with the length of 1 mu m and the diameter of 40-50 nm, and the nano structure can shorten Mg 2+ Transmission path of, increasing Mg 2+ The solid diffusion kinetics is realized, the specific surface area is large, the transmission of ions and electrons is facilitated, more active sites are more beneficial to the generation of oxidation reduction, and more specific capacity is provided.
3. The material prepared by the method of the invention has excellent performanceInverse capacity, rate capability (current density of 0.2A g) -1 Specific capacity of 277.31 mAh g -1 ) And excellent cycle stability (the capacity retention rate is 96.97% after 400 cycles, and the coulombic efficiency is always stable at 100%), thereby solving the problem of slow diffusion kinetics in the existing magnesium storage technology.
Drawings
FIG. 1 is an XRD analysis of copper hydroxypyrolovanadate prepared in large quantities in example 1;
FIG. 2 is an SEM image of 20000 times magnification of copper hydroxypyrovanadate macro-prepared in example 1;
FIG. 3 is an SEM image of copper hydroxypyrovanadate prepared by the hydrothermal method of comparative example 1, at magnification of 35000 times;
FIG. 4 shows the scan rate of 0.8-5 mV s in example 1 -1 Cyclic voltammetry of (a);
FIG. 5 shows the scan rate of 0.4-2 mV s in comparative example 1 -1 Cyclic voltammetry of (a);
FIG. 6 shows that the current density of example 1 is 0.2 to 2A g -1 The constant current charge-discharge curve of (1);
FIG. 7 shows comparative example 1 having a current density of 0.25 to 5A g -1 The constant current charge-discharge curve of (1);
FIG. 8 is a graph of the rate test of example 1 at different current densities.
FIG. 9 shows the results of example 1 at a constant current density of 3A g -1 Cycle stability test chart.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood by those skilled in the art that the specific embodiments described herein are for purposes of illustration and explanation only and are not intended to be limiting. Accordingly, substitutions and alterations may be made to the above examples without departing from the spirit and scope of the claims.
First, examples and comparative examples
Example 1
(1) NaVO (sodium VO) 3 (0.2 kg, 1.65 mol) is added into 0.5L deionized water, heated and stirred at 90 plus or minus 5 ℃ to be dissolved, and light yellow sodium metavanadate solution is obtained; adding CuCl 2 ·2H 2 O（0.3 kg, 2.131 mol) into 0.5L of deionized water, wherein the molar ratio of the sodium metavanadate to the copper chloride dihydrate is equal to about 1: 1.3; stirring and mixing uniformly at room temperature to obtain a blue copper chloride solution; adding a copper chloride solution into a sodium metavanadate solution to obtain a yellow mixed solution immediately;
(2) stirring the obtained yellow mixed solution at normal temperature and normal pressure for 24 hours, filtering, and washing with deionized water for 2-3 times; and finally drying in a constant-temperature drying oven at 80 ℃ for 12 hours to obtain the final copper hydroxypyrovanadate with the yield of 89.23%.
Example 2
(1) NaVO (sodium VO) 3 (0.3 kg, 2.46 mol) is added into 1L deionized water, heated and stirred at 90 plus or minus 5 ℃ to be dissolved, and light yellow sodium metavanadate solution is obtained; adding CuCl 2 ·2H 2 O (0.4 kg, 2.346 mol) was added to 1L of deionized water in a molar ratio of sodium metavanadate to copper chloride dihydrate equal to about 1: 1; stirring and mixing uniformly at room temperature to obtain a blue copper chloride solution; adding a copper chloride solution into a sodium metavanadate solution to obtain a yellow mixed solution immediately;
(2) stirring the obtained yellow mixed solution at normal temperature and normal pressure for 2 hours, filtering, and washing with deionized water for 2-3 times; and finally drying in a constant-temperature drying oven at 80 ℃ for 12 hours to obtain the final copper hydroxypyrovanadate with the yield of 86.54 percent.
Example 3
(1) NaVO (sodium VO) 3 (3 kg, 24.6 mol) is added into 10L deionized water, heated and stirred at the temperature of 90 +/-5 ℃ and dissolved to obtain a light yellow sodium metavanadate solution; adding CuCl 2 ·2H 2 O (6.91 kg, 36.9 mol) was added to 10L of deionized water, the molar ratio of sodium metavanadate to copper chloride dihydrate was about equal to 1: 1.6; stirring and mixing uniformly at room temperature to obtain a blue copper chloride solution; adding a copper chloride solution into a sodium metavanadate solution to obtain a yellow mixed solution immediately;
(2) stirring the obtained yellow mixed solution at normal temperature and normal pressure for 4 hours, filtering, and washing with deionized water for 2-3 times; finally drying for 12 h in a constant-temperature drying oven at 80 ℃ to obtain the final hydroxyl pyroglutamic acid copper salt with the yield of 90.87%.
Example 4
The procedure of this example was followed in the same manner as in example 1 except that the resulting yellow mixed solution was stirred at 50 ℃ for 6 hours to give a yield of 88.56%.
Example 5
The procedure of this example was followed in the same manner as in example 1 except that the resulting yellow mixed solution was stirred at 70 ℃ for 13 hours to give a yield of 88.21%.
Examples 6 to 9
The method of preparation of layered copper hydroxypyrolignate of this example was the same as in example 3 except that the molar ratios of sodium metavanadate to copper chloride dihydrate were 1:2, 1:2.5, 1:3, and 1:4, respectively, and the yields were 89.63%, 89.32%, 90.31%, and 90.45%, respectively.
Comparative example 1
(1) NaVO (sodium VO) 3 (13 g) Dissolving in 120 mL of deionized water and adjusting the pH to 6 with 1M HCl, and recording as a solution A; adding CuCl 2 ·2H 2 O (0.104 g) was dissolved in 24 mL deionized water and 1 mL solution A, denoted solution B, was added; benzoic acid (0.146 g) was dissolved in 24 mL of ethanol and identified as solution C; mixing the solution B and the solution C in a beaker, adding 24 mL of DMF solution, and uniformly mixing for 30 min under magnetic stirring to obtain a precursor solution;
(2) transferring the obtained precursor into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a forced air drying oven, heating to 100 ℃, preserving heat for 20 hours, taking out the precursor and cooling to room temperature to obtain a reaction product; and filtering the reaction product to obtain a solid product, washing the solid product with DMF (dimethyl formamide) and absolute ethyl alcohol respectively, centrifuging for multiple times, and drying to obtain the copper hydroxypyrovanadate with the yield of 57.74%.
Comparative example 2
(1) NaVO (sodium VO) 3 (13 g) Dissolving in 120 mL of deionized water and adjusting the pH to 6 with 1M HCl, and recording as a solution A; adding CuCl 2 ·2H 2 O (0.104 g) was dissolved in 24 mL deionized water and 1 mL solution A, denoted solution B, was added; benzoic acid (0.146 g) dissolved in 24 mL ethanol was designated solution C; mixing half of solution B and solution C in a furnaceAdding 24 mL of DMF solution into a cup, uniformly mixing for 20 min under magnetic stirring, adding the other half of solution B into the mixed solution, and continuing magnetic stirring for 30 min to finally obtain a precursor solution;
(2) transferring the obtained precursor into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a forced air drying box, heating to 120 ℃, preserving heat for 20 hours, taking out the stainless steel reaction kettle and cooling to room temperature to obtain a reaction product; and filtering the reaction product to obtain a solid product, washing the solid product with DMF (dimethyl formamide) and absolute ethyl alcohol respectively, centrifuging for multiple times, and drying to obtain the copper hydroxypyrovanadate with the yield of 58.64%.
Second, result and analysis
Structural characterization of prepared layered copper hydroxyvanadates
(1) Characterization of XRD
FIG. 1 is an X-ray diffraction (XRD) analysis of the layered copper hydroxyvanadates prepared in example 1, comparing all diffraction peaks with monoclinic Cu, with standard card JCPDS #80-1170 3 V 2 O 7 (OH) 2 ·2H 2 The height of the standard peak of O is coincident, which shows that the prepared product is phase-pure Cu 3 V 2 O 7 (OH) 2 ·2H 2 O。
The layered copper hydroxypyrolignates prepared in examples 2 to 9 and comparative examples 1 to 2 were tested by the same method, and the results were substantially the same as those of example 1.
(2) SEM characterization
FIG. 2 is a scanning electron microscope image of 20000 times of magnification of the macroscopically prepared layered copper hydroxypyrovanadate obtained in example 1, and it can be seen from the image that the macroscopically prepared layered copper hydroxyvanadate of the present invention is a nanorod with uniform size, the length of the nanorod is about 1 μm, the diameter of the nanorod is 40-50 nm, and the nanostructure can shorten the Mg content 2+ Transmission path of, increasing Mg 2+ Solid state diffusion kinetics of (a); the specific surface area of the material is greatly increased, the diffusion transfer of ions and electrons is facilitated in the charging and discharging process, more active sites can be provided, and the specific capacity of the electrode material is improved. FIG. 3 shows the scanning of layered copper pyrovanadate prepared by the hydrothermal method of comparative example 1 at a magnification of timesAs can be seen from the drawing of an electron microscope, the copper hydroxypyrovanadate prepared under the hydrothermal condition has an irregular microsphere structure with the diameter of about 1.5 microns, has uniform size and is a microsphere formed by the agglomeration growth of nano particles.
(II) electrochemical performance test of layered hydroxyl copper pyrovanadate prepared in macroscopic quantity
The electrochemical performance test of the invention adopts a three-electrode system, takes the hydroxyl pyroglutamic acid copper prepared in the example 1 and the comparative example 1 loaded on the carbon cloth as a working electrode, a graphite electrode as a counter electrode, a saturated calomel electrode as a reference electrode, and 0.5 mol/L MgCl 2 Is used as electrolyte and is assembled in a traditional H-shaped three-electrode electrolytic tank. Cyclic Voltammetry (CV) and constant current charge and discharge (GCD) tests were performed on the copper hydroxypyrolignate positive electrode material using an electrochemical workstation (CHI 660E), respectively.
(1) Cyclic voltammogram
FIGS. 4 and 5 show the macro-and hydrothermal preparation of copper hydroxypyrovanadate at 0.5M MgCl 2 Cyclic voltammograms in solution (CV curves). In FIG. 4, the insertion and extraction behavior of magnesium ions was studied at a scan rate of 0.8-5 mV/s and a voltage window of-0.8V. It can be seen that unlike the carbon material with rectangular CV curves, these curves exhibit pseudocapacitance characteristics with a significantly broad redox peak, indicating that copper hydroxypyrolignate nanorods are pseudocapacitance electrode materials, and fig. 5 also exhibits similar pseudocapacitance characteristics. These broad peaks correspond to the intercalation and deintercalation of magnesium ions, and the specific electrochemical reaction chemical formula is as follows:
xMg 2+ + 2xe - + CVOH ⇌ Mg x CVOH （1）
CVOH has a typical layered structure, and is very advantageous for the insertion and extraction of ions and electrons, and x in formula (1) represents Mg inserted between layers of CVOH 2+ The number of moles. As can be seen from the CV curve of FIG. 1, the CVOH electrode has a faster response speed with the change of the scanning voltage, because the CVOH is a nanorod with a length of 1 μm and a diameter of 40-50 nm, and the nanostructure can shorten the Mg content 2+ Transmission path of, increasing Mg 2+ Solid state diffusion kinetics and the large specific surface area also facilitates dissociationAnd more active sites are more favorable for redox generation and provide more specific capacity for the transmission of electrons and electrons.
(2) Constant current charging and discharging
FIG. 6 and FIG. 7 show 0.5M MgCl with macro-scale preparation and hydrothermal preparation of copper hydroxypyrolvanadate as working electrode 2 Constant current charge and discharge curves (GCD) tested at different current densities for the electrolyte. It can be seen that, consistent with the analysis results of the CV curves, the voltage and time are in a nonlinear relationship, indicating that redox reactions occur during charging and discharging due to the faraday pseudocapacitance mechanism occurring on or near the surface of the material. As shown in FIG. 6, when the current density was 0.2A g -1 Specific capacity of 277.31 mAh g -1 And the hydrothermal method for preparing the copper hydroxypyrolvanadate is 0.25A g -1 Shows 262 mAh g at a small magnification -1 The reversible discharge capacity of the lithium secondary battery is equivalent to the electrochemical performance of the hydroxyl pyroglutamic acid copper prepared in macro scale with that prepared by a hydrothermal method, and the fact that the hydroxyl pyroglutamic acid copper prepared in macro scale is an excellent electrode material is shown, and the simple and convenient macro preparation method can replace the traditional hydrothermal method. The specific capacity gradually decreases with the increase of the current density, because the increase of the current density accelerates the charging and discharging process, sufficient time is not obtained for ion and electron transfer, oxidation-reduction reaction and the like, and the increase of the current density also causes the over-saturation or over-consumption of protons in the electrolyte, so that the internal resistance and the ionic resistance coefficient increase, and the specific capacity tends to decrease.
(3) Multiplying power test
FIG. 8 is a macro scale preparation of copper hydroxypyrolignate in 0.5M MgCl as an electrode material for aqueous magnesium ion batteries in example 1 2 And (4) a multiplying power test chart in the electrolyte. The results show that the CVOH nanorods have excellent reversible capacity stability at different current densities, when the current density is 0.3A g -1 The reversible capacity of the first turn is 284.95 mAh g -1 Although the specific capacity gradually decreases as the current density increases, the current density increases to 1A g -1 The specific capacity is still maintained at 148.35 mAh g -1 When the current density is renewedBack to 0.3A g -1 The reversible capacity is instantaneously restored to 260.49 mAh g -1 The CVOH prepared by the preparation method is proved to have excellent rate capability.
(4) Test for cycling stability
A macro quantity of CVOH prepared in example 1 was added at 3A g -1 The current density and voltage window of the battery are-0.8V, constant current charging and discharging circulation is carried out for 400 times, and the circulation stability is tested. Fig. 9 is a graph of specific capacity and coulombic efficiency at different cycle numbers. The retention rate of the capacity after 400 cycles is 96.97%, the coulombic efficiency is stabilized at 100%, and the result shows that the layered copper hydroxypyrovanadate prepared in a macroscopic quantity has excellent cycle stability as an electrode material of a water system magnesium ion battery, and the insertion and the extraction of magnesium ions are highly reversible, so that the layered copper hydroxyvanadate has large interlayer spacing and large specific surface area, reduces the transmission resistance of the ions, and is beneficial to the insertion and the extraction of the magnesium ions.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a layered copper hydroxypyrovanadate anode material is characterized by comprising the following steps:
step 1: adding a vanadium source into deionized water, heating and stirring at 90 +/-5 ℃ to dissolve, and obtaining a vanadium source solution;
step 2: adding a copper source into deionized water, and uniformly stirring at room temperature to obtain a copper source solution;
and step 3: adding the copper source solution into the vanadium source solution, and uniformly mixing to obtain a mixed solution; wherein the molar ratio of vanadium/copper atoms of the vanadium source and the copper source is 1 (1-4);
and 4, step 4: and (3) magnetically stirring the mixed solution obtained in the step (3) to react to obtain a precipitate, and sequentially filtering, washing and drying to obtain the layered hydroxyl copper pyrovanadate anode material.
2. The method for preparing the layered copper hydroxypyrovanadate cathode material according to claim 1, wherein the vanadium source comprises one of orthovanadate, pyrovanadate and metavanadate.
3. The method for preparing the layered copper hydroxypyrolignate cathode material according to claim 1, wherein the copper source comprises one of copper chloride and a hydrate thereof, copper sulfate and a hydrate thereof, copper nitrate and a hydrate thereof, and copper acetate.
4. The preparation method of the layered copper hydroxypyrovanadate cathode material according to claim 1, wherein in the step 1, the vanadium concentration of the vanadium source solution is 0.05-5 mol/L.
5. The method for preparing the layered copper hydroxyvanadates cathode material according to claim 1, wherein in the step 2, the copper concentration of the copper source solution is 0.1-8 mol/L.
6. The method for preparing the layered copper hydroxypyrovanadate cathode material according to claim 1, wherein in the step 4, the reaction time of the mixed solution at 25-90 ℃ is 0.5-24 h.
7. The method for preparing the layered copper hydroxyvanadates cathode material according to claim 1, wherein in the step 4, the obtained precipitate is washed with deionized water for 2-5 times.
8. The preparation method of the layered copper hydroxypyrovanadate cathode material according to claim 1, wherein in the step 4, the cleaned precipitate is dried for 6-24 hours in a constant-temperature drying oven at 60-100 ℃.
9. The application of the layered copper hydroxypyrovanadate anode material is characterized in that the layered copper hydroxypyrophosphate anode material for the magnesium ion battery is obtained through macroscopic preparation according to any one of claims 1 to 8, and can be used for batch preparation of magnesium ion batteries, lithium ion batteries, zinc ion batteries and sodium ion batteries.
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