CN116282156A - Magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, preparation method and application - Google Patents
Magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, preparation method and application Download PDFInfo
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- CN116282156A CN116282156A CN202310393945.3A CN202310393945A CN116282156A CN 116282156 A CN116282156 A CN 116282156A CN 202310393945 A CN202310393945 A CN 202310393945A CN 116282156 A CN116282156 A CN 116282156A
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 54
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002057 nanoflower Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000009830 intercalation Methods 0.000 abstract description 9
- 230000002687 intercalation Effects 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 26
- 210000004027 cell Anatomy 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
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- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- FKBGOUXGDAMMHP-UHFFFAOYSA-N [V+5].[O-2].[Mn+2] Chemical compound [V+5].[O-2].[Mn+2] FKBGOUXGDAMMHP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
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- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention discloses a magnesium ion pre-intercalation hydrated vanadium oxide positive electrode material, a preparation method and application thereof, wherein the positive electrode material is Mg x V 10 O 24 ·nH 2 O, wherein x is the mole number of magnesium ions embedded in the positive electrode material, x and n are rational numbers, and x and n are both larger than 0. The invention adopts a simple high-temperature precipitation method, and can synthesize Mg with uniform size and shape in one step 2+ Pre-intercalated hydrated vanadium oxide nanoflower magnesium ionsThe battery anode material solves the difficult problem of slow diffusion dynamics in the existing magnesium storage technology, and also solves the technical bottleneck of poor cycle stability of the inserted diffusion type magnesium ion battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a magnesium ion pre-intercalation hydrated vanadium oxide positive electrode material, a preparation method and application.
Background
In order to alleviate the increasingly serious energy and environmental crisis, the development of sustainable energy storage technologies is urgent. Commercial Lithium Ion Batteries (LIBs) have been developed to the bottleneck stage due to lithium starvation, limited energy density, and safety issues during cycling. Therefore, the development of the next-generation battery system is critical to meet the increasing demand. Magnesium ion batteries (RMBs) are considered to be one of the promising candidates for energy storage devices due to their advantages of rich magnesium resource reserves, high volumetric energy density, and no dendrite threat. The main challenge of magnesium ion batteries comes from the divalent Mg 2+ The slow ion diffusion kinetics, low discharge capacity and poor cycling stability resulting from strong electrostatic interactions with the host material severely hamper the development of RMBs. Currently, the reported positive electrode materials applied to RMBs mainly include transition metal oxides, sulfides, selenides, and the like. However, the rate performance and cycle stability of these cathode materials are still to be further improved.
Vanadium oxide is an important vanadium-based material, and has been widely used in the field of energy storage due to the polyvalent state and structural variability of vanadium. However, the vanadium oxide cathode materials generally have problems of low conductivity and slow solid state diffusion kinetics, which severely limit the development of magnesium ion batteries. As disclosed in patent CN110078121A, a method for preparing a vanadium pentoxide nanoflower magnesium ion battery anode material by a high-temperature calcination method is disclosed, and the initial discharge specific capacity of the electrode material prepared by the method is 120 mAh.g -1 The capacity retention rate was only 70% after 60 cycles, showing poor electrochemical performance. To solve the problems of the above-mentioned vanadium oxide electrode materials, patent CN109638257a discloses a composite vanadium pentoxide positive electrodeThe invention improves the conductivity and the structural stability of vanadium pentoxide by doping a carbon source and other elements into a vanadium source, and when the vanadium pentoxide is applied to a lithium-magnesium hybrid battery, the initial charge-discharge of about 200mAh g can be obtained -1 Is a reversible specific capacity of (a). Nevertheless, the direct application of the electrode material prepared by the invention to magnesium ion batteries is still the direction of future efforts.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a magnesium ion pre-intercalation hydrated vanadium oxide positive electrode material, a preparation method and application thereof, so as to solve the problems of low conductivity and slow solid diffusion kinetics of the vanadium oxide positive electrode material in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, wherein the positive electrode material is Mg x V 10 O 24 ·nH 2 O, wherein x is the mole number of magnesium ions embedded in the positive electrode material, x and n are rational numbers, and x and n are both larger than 0, and products with different values of x and n can be obtained by adjusting the proportion of magnesium nitrate hexahydrate and vanadium pentoxide.
Preferably, the shape of the positive electrode material is a nanometer flower shape, and the petal thickness is 50-100 nm.
The invention also provides a preparation method of the magnesium ion pre-intercalation hydrated vanadium oxide positive electrode material, which comprises the following steps:
step 1: to V 2 O 5 Adding hydrogen peroxide solution, carrying out exothermic reaction to obtain yellow-orange transparent solution, and adding deionized water to obtain solution A; wherein the mass percentage of hydrogen peroxide in the hydrogen peroxide solution is more than or equal to 30 percent, and V in the solution A 2 O 5 The concentration of (2) is 0.01-0.2 mol/L;
step 2: dissolving a magnesium source in deionized water to obtain a solution B; wherein the concentration of magnesium in the magnesium source in the solution B is 0.01-0.5 mol/L;
step 3: mixing the solution A and the solution B, heating to 200-400 ℃, and reacting for 2-10 hours to obtain orange-red flocculent precipitate;
step 4: and (3) collecting the precipitate obtained in the step (3), centrifugally washing, and drying to obtain the positive electrode material.
Preferably, in step 1, V in solution A 2 O 5 The concentration of (C) is 0.05-0.1 mol/L.
Preferably, in step 2, the concentration of magnesium element in the magnesium source in solution B is 0.05-0.3 mol/L.
Preferably, in step 3, V in solution A and solution B 2 O 5 The molar concentration ratio of the vanadium element to the magnesium element in the magnesium source is 1:10, and the concentration ratio is further optimized for the raw material consumption, so that the growth of MVOH is facilitated.
Preferably, in step 4, the precipitate is washed 3 times with deionized water and absolute ethanol, respectively; and then drying for 8-12 h at 60-80 ℃.
The invention provides application of a magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, which is used for preparing a water-based magnesium ion battery and can realize excellent electrochemical performance of high capacity, high multiplying power and high cycle stability.
The invention provides application of a magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, which is used for preparing lithium ion batteries, sodium ion batteries, calcium ion batteries and zinc ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. the positive electrode material is prepared by Mg 2+ The pre-intercalated hydrated vanadium oxide ensures that the anode material has nano flower shape, which not only can increase the specific surface area of the material and expose more redox active sites, but also can shorten Mg 2+ Accelerating the diffusion path of Mg 2+ Diffusion kinetics of (c). In addition, the electrode sample has
Can provide rapid intercalation/deintercalation channels for magnesium ions; pre-embedded Mg 2+ And structureThe water can increase the conductivity of the electrode material and improve the specific capacity and the cycling stability of the positive electrode material.
2. The preparation method prepares the pre-intercalated hydrated vanadium oxide by a high-temperature chemical precipitation method, thereby realizing one-step synthesis of Mg with uniform size and shape 2+ The pre-intercalated hydrated vanadium oxide nano flower magnesium ion battery anode material has excellent multiplying power performance and cycle stability, and the preparation process is simple and easy to operate, and has good industrial application prospect.
3. The magnesium battery system constructed by the positive electrode material adopts Mg 2+ The pre-intercalated hydrated vanadium oxide is used as a magnesium ion battery anode material, the active carbon is used as a cathode material, and 4.5M Mg (NO 3 ) 2 The aqueous solution is electrolyte and assembled into a button cell battery, and the button cell battery can show 172 mAh.g at 0.5C -1 When the multiplying power is increased by 100 times to 50C, 92 mAh.g can be output -1 When the recovery rate is set to 0.5C, the specific capacity is quickly recovered to 174 mAh.g -1 Excellent rate capability; in addition, the battery also has an ultra-long cycle life (capacity retention rate is 78% after 10000 cycles), the coulombic efficiency is stabilized at 100%, and excellent electrochemical performance is shown.
Drawings
FIG. 1 is an XRD analysis pattern of the MVOH sample prepared in example 1;
FIG. 2 is a TGA analysis of the MVOH sample prepared in example 1;
FIG. 3 is a TEM image and a TEM image of the MVOH sample prepared in example 1;
FIG. 4 shows a coin cell system scan rate of 1 mV.s -1 Cyclic voltammograms of 3 turns before the MVOH electrode;
FIG. 5 is a graph of the rate capability of MVOH electrode of a coin cell system;
FIG. 6 is a charge-discharge curve of MVOH electrode of the coin cell system;
FIG. 7 shows a current density of 4 A.g for a button cell system -1 And (3) a cyclic stability test chart of the MVOH electrode.
Detailed Description
The invention will be further described with reference to the drawings and examples.
1. Magnesium ion pre-intercalation hydrated vanadium oxide positive electrode material
In the invention, the problems of low conductivity and slow solid diffusion kinetics of the vanadium oxide positive electrode material in the prior art are considered, so the invention considers the improvement of the vanadium oxide positive electrode material, and in the improvement process, the unexpected discovery is that the conductivity of the electrode material can be obviously improved by pre-embedding metal ions and structural water between vanadium oxide layers, and the material has large interlayer spacing after further analysis
This creates good conditions for magnesium ion migration, and at the same time, the presence of structural water also effectively shields Mg 2+ High electrostatic interaction force with host material to improve Mg 2+ Diffusion kinetics of (c); in addition, pre-embedded Mg 2+ And structural water is used as a 'pillar' between layers, so that the structural stability of the electrode material is enhanced, and the cycle life of the battery can be further prolonged. After further research on the anode material, the invention discovers that the button cell assembled with the active carbon anode has excellent electrochemical magnesium storage performance and mainly comprises high reversible capacity (the specific capacity is 172mAh g when the multiplying power is 0.5C) -1 ) And rate capability (rate expansion 100 times to 50C, 92mAh g can be output still) -1 Is a specific capacity of (2); when the specific capacity is recovered to 0.5C, the recovery rate reaches 100%, and is 174mAh g -1 ). In addition, the product has an extremely long cycle life (capacity retention rate is 78% after 10000 cycles), and the coulombic efficiency is always stabilized at 100%. The invention solves the difficult problem of slow diffusion dynamics in the existing magnesium storage technology, and also solves the technical bottleneck of poor circulation stability of the inserted diffusion type magnesium ion battery; therefore, the improvement of the series of structures ensures that MVOH as the magnesium ion battery anode material shows excellent rate performance and cycle stability. More difficult to obtain, the MVOH electrode has the advantages of simple preparation process, easy operation, low cost and high magnesium storage performance, and is an ideal magnesium ion battery anode material.
2. Examples and comparative examples
Example 1
The preparation method comprises the following steps:
(1) In vanadium pentoxide (V) 2 O 5 To 0.25 g) was added 3mL of 30% hydrogen peroxide (H) 2 O 2 ) After the exothermic reaction was completed, a yellowish orange clear solution was displayed and 50mL of deionized water was added and noted as solution a;
(2) Magnesium nitrate hexahydrate (Mg (NO) 3 ) 2 ·6H 2 O,1.8 g) was dissolved in 50mL deionized water, designated solution B;
(3) Adding the solution B into the solution A, placing the solution A on a heating plate at 300 ℃ for reaction for 6 hours, collecting a precipitate, respectively cleaning the precipitate with absolute ethyl alcohol and deionized water for 3 times, and drying the precipitate in a vacuum drying oven at 70 ℃ for 12 hours to obtain the MVOH brown powder sample.
Example 2
The preparation method comprises the following steps:
(1) In vanadium pentoxide (V) 2 O 5 To 0.5 g) was added 3mL of 30% by volume hydrogen peroxide (H) 2 O 2 ) After the exothermic reaction was completed, a yellowish orange clear solution was displayed and 50mL of deionized water was added and noted as solution a;
(2) Magnesium nitrate hexahydrate (Mg (NO) 3 ) 2 ·6H 2 O,1.8 g) was dissolved in 50mL deionized water, designated solution B;
(3) Adding the solution B into the solution A, placing the solution A on a heating plate at 250 ℃ for reaction for 8 hours, collecting a precipitate, respectively cleaning the precipitate with absolute ethyl alcohol and deionized water for 3 times, and drying the precipitate in a vacuum drying oven at 70 ℃ for 12 hours to obtain the MVOH brown powder sample.
Example 3
The preparation method comprises the following steps:
(1) In vanadium pentoxide (V) 2 O 5 To 0.25 g) was added 3mL of 30% hydrogen peroxide (H) 2 O 2 ) After the exothermic reaction was completed, a yellowish orange clear solution was displayed and 50mL of deionized water was added and noted as solution a;
(2) Will be hexahydratedMagnesium nitrate (Mg (NO) 3 ) 2 ·6H 2 O,3.6 g) was dissolved in 50mL deionized water, designated solution B;
(3) Adding the solution B into the solution A, placing the solution A on a heating plate at 300 ℃ for reaction for 8 hours, collecting a precipitate, respectively cleaning the precipitate with absolute ethyl alcohol and deionized water for 3 times, and drying the precipitate in a vacuum drying oven at 70 ℃ for 12 hours to obtain the MVOH brown powder sample.
Example 4
The preparation method comprises the following steps:
(1) In vanadium pentoxide (V) 2 O 5 To 0.5 g) was added 3mL of 30% by volume hydrogen peroxide (H) 2 O 2 ) After the exothermic reaction was completed, a yellowish orange clear solution was displayed and 50mL of deionized water was added and noted as solution a;
(2) Magnesium nitrate hexahydrate (Mg (NO) 3 ) 2 ·6H 2 O,3.6 g) was dissolved in 50mL deionized water, designated solution B;
(3) Adding the solution B into the solution A, placing the solution A on a heating plate at 300 ℃ for reaction for 4 hours, collecting a precipitate, respectively cleaning the precipitate with absolute ethyl alcohol and deionized water for 3 times, and drying the precipitate in a vacuum drying oven at 70 ℃ for 12 hours to obtain the MVOH brown powder sample.
Examples 5 to 6
The preparation method of MVOH in examples 5 to 6 was the same as in example 1, except that the heating reaction temperature was 200℃and 300℃respectively.
The following comparative examples are manganese vanadium oxide and vanadium pentoxide cathode materials prepared by the prior art:
comparative example 1
(1) 2mmol of ammonium metavanadate was dissolved in 70mL of deionized water and stirred at room temperature for 30min, designated as solution A;
(2) 1mL of 12.27mol/L hydrochloric acid was added to the solution A, and stirred for 10min to give an orange-yellow solution, which was designated as solution B;
(3) Dissolving 3mmol of manganese acetate in 10mL of deionized water, and performing ultrasonic treatment until the manganese acetate is dissolved, and marking the solution as a solution C;
(4) Dropwise adding the solution C into the solution B, and stirring and mixing at normal temperature to obtain yellow transparent liquid;
(5) Transferring the yellow transparent solution obtained in the step (4) into an 80mL reaction kettle, reacting for 72 hours at 200 ℃, removing the reaction kettle, naturally cooling to room temperature, and finally obtaining manganese-vanadium oxide (Mn) through the steps of filtering, washing and drying 0.04 V 2 O 5 ·1.17H 2 O) nanoribbons.
Comparative example 2
(1) 6mmol of ammonium metavanadate, 15mmol of oxalic acid and 0.5g of cetyltrimethylammonium bromide are dissolved in 15mL of deionized water and 45mL of ethylene glycol mixed solution, and after being uniformly mixed by magnetic stirring, the mixed solution is transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
(2) Transferring the sealed reaction kettle into a baking oven, preserving heat for 24 hours at 180 ℃ to obtain a reaction product, filtering the product, repeatedly washing the product by absolute ethyl alcohol and deionized water, and then placing the product into a vacuum drying oven, and drying the product at 60 ℃ for 10 hours to obtain a vanadium oxide precursor;
(3) And (3) placing the vanadium oxide precursor obtained in the step (2) in a muffle furnace, heating to 450 ℃ at a heating rate of 4 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the vanadium pentoxide anode material.
3. Structural characterization
(1) XRD characterization
FIG. 1 is an XRD analysis pattern of MVOH prepared in example 1, in comparison with a standard card, and all diffraction peaks of the resulting sample are compared with monoclinic V 10 O 24 ·nH 2 The standard peaks of O match, which indicates that the product produced has V 10 O 24 ·nH 2 And O.
(2) ICP-OES characterization
Table 1 shows the results of the test of ICP-OES of hydrated MVOH prepared in example 1, wherein the molar ratio of magnesium to vanadium elements in the prepared sample is 0.8:10, so the chemical formula of the prepared sample can be expressed as Mg 0.8 V 10 O 24 ·nH 2 O。
Table 1 ICP-OES analysis: mg/V element ratio of MVOH
| Sample of | Magnesium element (W/%) | Vanadium element (W/%) | Mg/V |
| MVOH | 1.74 | 46.58 | 0.8/10 |
(3) TGA characterization
FIG. 2 is a TGA analysis of MVOH prepared in example 1. As can be seen from the graph, the loss of weight below 100deg.C corresponds to the physical adsorption of water in the sample, while the loss of structural water in the sample in the range of 100-400deg.C corresponds to 7.2% in total, and corresponds to Mg 0.8 V 10 O 24 ·nH 2 4 structural waters in O. The final determinable sample has the chemical formula of Mg 0.8 V 10 O 24 ·4H 2 O。
The MVOH prepared in examples 2 to 6 was examined in the same manner as above, and the results were substantially identical to those in example 1.
(4) SEM and TEM characterization
FIG. 3 (a) and FIG. 3 (b) are scanning electron microscope images of MVOH prepared in example 1 under magnification of 5000 times and 20000 times respectively, and it can be seen from the images that MVOH prepared in the invention shows nanoflowers with uniform morphology, the profile is clear, the petal thickness is about 60-70 nm, the nanostructure can increase the specific surface area of the material, more active sites are exposed, and Mg can be greatly shortened 2+ Is embedded Mg 2+ Providing a fast speedKinetics of rapid diffusion. Further, high resolution transmission analysis was performed on MVOH, and fig. 3 (c) is a TEM image of a MVOH sample, showing a nanoflower morphology consistent with SEM; FIG. 3 (d-e) shows clear lattice fringes, with pitches of 0.32nm and 0.49nm, corresponding to the (111) and (204) planes of the crystal, respectively. Subsequently, the MVOH sample was subjected to STEM-EDS element distribution characterization (FIG. 3 (f)), and it can be seen that the elements Mg, V and O were uniformly distributed on the surface of the MVOH sample.
4. Electrochemical performance test
MVOH prepared in example 1, acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as an adhesive are added into N-methylpyrrolidone (NMP) solution according to a mass ratio of 7:2:1, ground and mixed to slurry, uniformly coated on carbon paper with a diameter of 12mm, and dried overnight in a vacuum drying oven at 80 ℃ to obtain a positive plate of a magnesium ion battery, wherein the active material loading amount is 1-1.2 mg cm 2
The electrochemical performance test of the invention adopts a traditional button cell two-electrode system, takes an MVOH electrode as a positive electrode, takes an Active Carbon (AC) electrode as a negative electrode, and adopts 4.5M Mg (NO) 3 ) 2 The aqueous solution was used as an electrolyte, and glass fiber filter paper (pore size 1.0 to 1.6 μm) was used as a separator to be assembled in a CR2430 button cell, and electrochemical performance was tested. Cyclic Voltammetry (CV) testing was performed using a cinnabar electrochemical workstation (CHI 660E), and constant current charge and discharge (GCD) and long cycle testing were performed on a new wili multichannel battery tester (CT 4008A).
(1) Cyclic voltammogram
FIG. 4 shows that the MVOH electrode has a current density of 1mV s -1 Cyclic voltammogram (CV curve) for the first 3 cycles at voltage window 1.6-3.7V (vs mg) 2+ Mg) the intercalation and deintercalation behavior of magnesium ions was investigated. Three pairs of broad redox peaks are shown in CV curve, wherein the cathode peaks are respectively positioned at 1.98, 2.18 and 2.87V, and the anode peaks are respectively positioned at 2.71, 2.92 and 3.40V, which indicates that the MVOH electrode has the participation of multi-step redox reaction in the charge-discharge process, and corresponds to Mg 2+ And the CV curves of the first 3 turns have good overlapping property, and show better electrochemical performanceReversibility of science. The electrochemical reaction formula is as follows:
MVOH + xMg 2+ + xe - ＝ Mg x MVOH (1)
MVOH is a crystal having a large interlayer spacing, which is very advantageous for the transport of magnesium ions, and x in formula (1) represents the mole number of magnesium ions intercalated into MVOH.
(2) Rate performance and charge-discharge curve
FIG. 5 shows MVOH electrode material at different rates (0.5C-50C, 1C=100 mAh g -1 ) The following ratio performance graph. As can be seen, when the multiplying power is 0.5C, the initial specific capacity output is 172mAh g -1 When the multiplying power is increased by 100 times to 50C, the output can be as high as 92mAh g -1 And when the multiplying power is recovered to 0.5C, the capacity can be immediately recovered to 174mAh g -1 Exhibits excellent rate performance advantages. FIG. 6 shows the charge and discharge curves of MVOH electrodes at different current densities, in which the current densities are 0.05, 0.1, 0.3, 0.5, 0.8, 1, 2, 3 and 4A g in order from right to left -1 . From the figure, all curves maintain similar shapes and plateau voltages. The manganese vanadium oxide synthesized in comparative example 1 was used as the positive electrode material of the magnesium ion battery at 0.05. 0.05A g -1 When the reversible discharge specific capacity is 145mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the When the current density increases to 4A g -1 The specific discharge capacity decays to about 40mAh g -1 . When the vanadium pentoxide synthesized in the comparative example 2 is used as a magnesium ion battery positive electrode material, the reversible discharge specific capacity of the vanadium pentoxide is only 120mAh g when 0.05Ag-1 -1 . Therefore, the reversible discharge specific capacity of the comparative example 1 and the comparative example 2 is far lower than that of the example 1 under different current densities, and the magnesium ion pre-intercalation hydrous oxide cathode material prepared by the invention has more excellent specific capacity and rate performance.
(3) Cycle stability test
AC// MVOH at 4A g -1 The stability of the test is tested by 10000 times of constant current charge and discharge cycles under the current density and voltage window of 1.6-3.7V. Fig. 7 shows specific capacity and coulombic efficiency at various cycle times. The initial discharge specific capacity of the MVOH electrode is92mAh g -1 After 10000 times of circulation, the output of 72mAh g -1 The specific capacity of the composite material is 78%, the retention rate of the capacity is 78%, and the coulomb efficiency is always stabilized at 100%, which proves that the MVOH prepared by the invention has better cycle stability as the positive electrode material, and the intercalation and deintercalation of magnesium ions in the MVOH structure are highly reversible, which benefits from the pre-intercalated Mg in the MVOH crystal 2+ And structural water, not only can increase the conductivity and structural stability of the electrode material.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (9)
1. A magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material is characterized in that the positive electrode material is Mg x V 10 O 24 ·nH 2 O, wherein x is the mole number of magnesium ions embedded in the positive electrode material, x and n are rational numbers, and x and n are both larger than 0.
2. The magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material according to claim 1, wherein the shape of the positive electrode material is a nanoflower shape, and the petal thickness is 50-100 nm.
3. A method for preparing a magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, which is characterized by preparing the positive electrode material according to any one of claims 1-2, and specifically comprises the following steps:
step 1: to V 2 O 5 Adding hydrogen peroxide solution, carrying out exothermic reaction to obtain yellow-orange transparent solution, and adding deionized water to obtain solution A; wherein the mass percentage of hydrogen peroxide in the hydrogen peroxide solution is more than or equal to 30 percent, and V in the solution A 2 O 5 The concentration of (2) is 0.01-0.2 mol/L;
step 2: dissolving a magnesium source in deionized water to obtain a solution B; wherein the concentration of magnesium in the magnesium source in the solution B is 0.01-0.5 mol/L;
step 3: mixing the solution A and the solution B, heating to 200-400 ℃, and reacting for 2-10 hours to obtain a precipitate;
step 4: and (3) collecting the precipitate obtained in the step (3), centrifugally washing, and drying to obtain the positive electrode material.
4. The method for preparing a magnesium ion pre-intercalated hydrated vanadium oxide cathode material according to claim 3, wherein in step 1, V in solution a 2 O 5 The concentration of (C) is 0.05-0.1 mol/L.
5. The method for preparing a magnesium ion pre-intercalated hydrated vanadium oxide cathode material according to claim 3, wherein in the step 2, the molar concentration of magnesium element of the magnesium source in the solution B is 0.05-0.3 mol/L.
6. The method for preparing a magnesium ion pre-intercalated hydrated vanadium oxide cathode material according to claim 3, wherein in step 3, V is selected from the group consisting of solution a and solution B 2 O 5 The molar concentration ratio of the vanadium element to the magnesium element in the magnesium source is 1:10.
7. The method for preparing a magnesium ion pre-intercalated hydrated vanadium oxide cathode material according to claim 3, wherein in step 4, the precipitate is washed 3 times with deionized water and absolute ethyl alcohol, respectively; and then drying for 8-12 h at 60-80 ℃.
8. The application of the magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material is characterized in that the positive electrode material is used for preparing a water-based magnesium ion battery according to any one of claims 1-2.
9. The application of the magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material is characterized in that the positive electrode material is used for preparing lithium ion batteries, sodium ion batteries, calcium ion batteries and zinc ion batteries according to any one of claims 1-2.
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