CN114094091B - Molybdenum-zinc vanadate positive electrode material and preparation method thereof - Google Patents
Molybdenum-zinc vanadate positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum zinc vanadate anode material and a preparation method thereof. The chemical formula of the molybdenum zinc vanadate is Zn 3 MoV 2 O 8 The preparation method comprises the following steps: 1) Mixing a vanadium-containing compound, a molybdenum-containing compound and a zinc-containing compound according to a molar ratio of vanadium element, molybdenum element and zinc element of 2; 2) Heating the precursor mixture to 200-450 ℃ for heat treatment, and then grinding to obtain an intermediate product; 3) And sintering the intermediate product in a reducing atmosphere at 600-800 ℃ to obtain the molybdenum-zinc vanadate anode material. The molybdenum zinc vanadate anode material has high purity and small primary particle size, and an anode prepared from the molybdenum zinc vanadate anode material can provide zinc ions required by the operation of a water system zinc ion battery, so that the prepared water system zinc ion battery has high charge-discharge specific capacity.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a molybdenum zinc vanadate anode material and a preparation method thereof.
Background
With the continuous development of technology, people have an increasing demand for electrochemical energy storage devices with high energy/power density and high safety in daily production and life, and rechargeable secondary batteries are considered as the key to solve the global energy crisis. The lithium ion battery has the advantages of high energy conversion efficiency, long service life, small self-discharge and the like, and currently occupies a leading position in the consumer electronics market. However, the lithium ion battery has the problems of flammability and toxicity of organic electrolyte, high manufacturing cost and the like, and the lithium ion battery has low content of lithium element in the earth crust, so that the application of the lithium ion battery in the field of large-scale energy storage is greatly limited.
The water-based zinc ion battery has the advantages of high safety, environmental friendliness, low manufacturing cost and the like, and the earth has abundant zinc resources, so the water-based zinc ion battery is considered to be one of the most promising secondary batteries for solving the problem of large-scale energy storage. The water system zinc ion battery mainly comprises an active positive electrode, a diaphragm, a zinc salt aqueous solution electrolyte, a metal zinc negative electrode and the like. Zn 2+ The zinc ion battery has two positive charges, and can generate multi-electron oxidation reduction reaction in the electrochemical energy storage process, so that the water system zinc ion battery has higher charge-discharge specific capacity. It has been found that, in an aqueous zinc ion battery, the use of an alkaline electrolyte tends to generate zinc dendrites and irreversible discharge by-products, which ultimately affect the cycle life and charge/discharge capacity of the aqueous zinc ion battery, and therefore, a neutral or weakly acidic aqueous electrolyte is suitably selected. The utilization rate of zinc in the cathode of the water-based zinc ion battery is often low, zinc dendrites are easy to appear even in neutral or weakly acidic water-based electrolyte, and potential safety hazards exist. Researchers generally believe that: the development of a novel zinc-rich cathode material completely provides zinc ions required by the operation of the water-based zinc ion battery by using a cathode active substance, and is a necessary way for the industrialization of the water-based zinc ion battery from a laboratory.
Disclosure of Invention
The invention aims to provide a molybdenum zinc vanadate positive electrode material.
The second objective of the present invention is to provide a preparation method of the above molybdenum zinc vanadate positive electrode material.
The invention also provides a zinc ion battery anode containing the molybdenum zinc vanadate anode material.
The fourth object of the present invention is to provide an aqueous zinc ion battery comprising the above-mentioned molybdenum zinc vanadate positive electrode material.
The technical scheme adopted by the invention is as follows:
a positive electrode material of molybdenum zinc vanadate has a chemical formula of Zn 3 MoV 2 O 8 。
Preferably, the molybdenum zinc vanadate isThe electrode material is cubic system and the unit cell parameter is
α＝β＝γ＝90°。
The preparation method of the molybdenum zinc vanadate anode material comprises the following steps:
1) Mixing a vanadium-containing compound, a molybdenum-containing compound and a zinc-containing compound according to a molar ratio of vanadium element to molybdenum element to zinc element of 2;
2) Heating the precursor mixture to 200-450 ℃ for heat treatment, and then grinding to obtain an intermediate product;
3) And sintering the intermediate product in a reducing atmosphere at 600-800 ℃ to obtain the molybdenum-zinc vanadate anode material.
Preferably, the vanadium-containing compound in the step 1) is vanadium pentoxide (V) 2 O 5 ) Ammonium metavanadate (NH) 4 VO 3 ) Vanadium dioxide (VO) 2 ) Vanadium (V) oxide 2 O 3 ) Vanadyl acetylacetonate (C) 10 H 14 O 5 V).
Preferably, the molybdenum-containing compound in step 1) is molybdenum dioxide (MoO) 2 ) Molybdenum trioxide (MoO) 3 ) Ammonium molybdate tetrahydrate (H) 24 Mo 7 N 6 O 24 ·4H 2 O), molybdenum acetylacetonate (C) 10 H 14 MoO 6 ) Molybdic acid (H) 2 Mo 2 O 7 ) Ammonium molybdate (H) 8 MoN 2 O 4 ) At least one of (1).
Preferably, the zinc-containing compound in step 1) is zinc acetate (C) 4 H 6 O 4 Zn) and zinc oxide (ZnO).
Preferably, the time of the heat treatment in the step 2) is 2 to 10 hours.
Preferably, the heat treatment of step 2) is performed in an air atmosphere.
Preferably, the sintering time in the step 3) is 7-15 h.
Preferably, step 3) isThe reducing atmosphere is Ar-H 2 Mixed gas, N 2 -H 2 One of mixed gas, hydrogen and ammonia.
A zinc ion battery anode comprises the molybdenum zinc vanadate anode material.
An aqueous zinc ion battery comprising the above-described molybdenum zinc vanadate positive electrode material.
The beneficial effects of the invention are: the molybdenum-zinc vanadate anode material has high purity and small primary particle size, and an anode prepared from the molybdenum-zinc vanadate anode material can provide zinc ions required by the operation of a water system zinc ion battery, so that the prepared water system zinc ion battery has high charge-discharge specific capacity.
Specifically, the method comprises the following steps:
1) The chemical formula of the molybdenum zinc vanadate anode material is Zn 3 MoV 2 O 8 The zinc ion battery positive electrode material is a brand new compound and also a novel zinc ion battery positive electrode material;
2) Each molecule of the molybdenum zinc vanadate anode material contains 3 zinc ions, has the zinc-rich characteristic, and can provide working ions required for participating in electrochemical reaction for a zinc ion battery, so that the selection of the anode material is not limited to zinc metal any more, and the selection range of the anode material is greatly expanded;
3) Vanadium and molybdenum elements in the molybdenum zinc vanadate anode material are in respective lowest valence states (+ 3 and + 4), and the theoretical capacity is up to 308mAh/g by utilizing multi-electron reaction along with the extraction and the embedding of zinc ions, so that the molybdenum zinc vanadate anode material is the highest record in the anode material capable of providing the zinc ions at present;
4) The molybdenum zinc vanadate anode material has good electrochemical performance and is suitable for serving as an anode material of a water-system zinc ion battery;
5) The preparation method of the molybdenum zinc vanadate anode material is simple, convenient to operate and good in industrialization prospect.
Drawings
Fig. 1 is an SEM image of the molybdenum zinc vanadate positive electrode material in example 1.
Fig. 2 is an XRD pattern of the molybdenum zinc vanadate anode material of example 2.
Fig. 3 is a charge/discharge curve of the aqueous zinc-ion battery in the application example.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a molybdenum zinc vanadate anode material comprises the following steps:
1) Reacting NH 4 VO 3 、C 10 H 14 MoO 6 And ZnO are mixed according to the molar ratio of the vanadium element to the molybdenum element to the zinc element of 2;
2) Placing the precursor mixture in an air atmosphere, heating to 200 ℃, carrying out heat treatment for 8h, naturally cooling to room temperature, and then grinding to obtain an intermediate product;
3) Placing the intermediate product in N 2 -H 2 Atmosphere (N) 2 And H 2 The volume ratio of (1) to (5) is 95), sintering at 600 ℃ for 12h to obtain the molybdenum zinc vanadate anode material.
And (3) performance testing:
the Scanning Electron Microscope (SEM) image of the molybdenum zinc vanadate cathode material of the present example is shown in fig. 1.
As can be seen from fig. 1: the particle size of the primary particles of the molybdenum zinc vanadate cathode material is smaller than 50nm, so that the solid phase diffusion distance of Zn ions is greatly shortened, and the molybdenum zinc vanadate cathode material serving as the cathode material of the water-based zinc ion battery is beneficial to full play of electrochemical performance.
Example 2:
a preparation method of a molybdenum zinc vanadate anode material comprises the following steps:
1) Will V 2 O 5 、MoO 3 And C 4 H 6 O 4 Zn·2H 2 Mixing O according to a molar ratio of the vanadium element, the molybdenum element and the zinc element of 2;
2) Placing the precursor mixture in an air atmosphere, heating to 450 ℃ for 3h of heat treatment, naturally cooling to room temperature, and grinding to obtain an intermediate product;
3) Placing the intermediate product in Ar-H 2 Atmosphere (Ar and H) 2 The volume ratio of (1) to (5) is 95), sintering is carried out for 8 hours at 800 ℃, and the molybdenum-zinc vanadate anode material is obtained.
And (3) performance testing:
the X-ray diffraction (XRD) pattern of the molybdenum zinc vanadate positive electrode material of this example is shown in fig. 2.
As can be seen from fig. 2: the positions of all diffraction peaks of the molybdenum zinc vanadate anode material of the embodiment are completely consistent with the theoretical calculation result, which indicates that the high-purity molybdenum zinc vanadate anode material is obtained.
Example 3:
a preparation method of a molybdenum zinc vanadate anode material comprises the following steps:
1) C is to be 10 H 14 O 5 V、H 24 Mo 7 N 6 O 24 ·4H 2 Mixing O and ZnO according to a molar ratio of the vanadium element, the molybdenum element and the zinc element of 2;
2) Placing the precursor mixture in an air atmosphere, heating to 350 ℃, carrying out heat treatment for 4h, naturally cooling to room temperature, and then grinding to obtain an intermediate product;
3) Intermediate product is placed in H 2 Sintering for 10h at 700 ℃ in the atmosphere to obtain the molybdenum zinc vanadate anode material.
Example 4:
a preparation method of a molybdenum zinc vanadate anode material comprises the following steps:
1) VO is introduced into a reactor 2 、MoO 2 And C 4 H 6 O 4 Zn·2H 2 Mixing O according to a molar ratio of the vanadium element, the molybdenum element and the zinc element of 2;
2) Placing the precursor mixture in an air atmosphere, heating to 250 ℃, carrying out heat treatment for 6h, naturally cooling to room temperature, and grinding to obtain an intermediate product;
3) Placing the intermediate product in NH 3 Sintering for 15 hours at 650 ℃ in the atmosphere to obtain the molybdenum-zinc vanadate anode material.
Example 5:
a preparation method of a molybdenum zinc vanadate anode material comprises the following steps:
1) Will V 2 O 3 、H 2 Mo 2 O 7 And ZnO are mixed according to the molar ratio of the vanadium element to the molybdenum element to the zinc element of 2;
2) Placing the precursor mixture in an air atmosphere, heating to 300 ℃, carrying out heat treatment for 5h, naturally cooling to room temperature, and then grinding to obtain an intermediate product;
3) Placing the intermediate product in Ar-H 2 Atmosphere (Ar and H) 2 The volume ratio of (1) to (30) is 70), sintering at 750 ℃ for 9 hours to obtain the molybdenum zinc vanadate cathode material.
The application example is as follows:
an aqueous zinc ion battery, the preparation method comprises the following steps:
1) Dispersing the molybdenum zinc vanadate positive electrode material, acetylene black and polyvinylidene fluoride in example 1 in a mass ratio of 8;
2) And (2) in an indoor clean environment, packaging to prepare the button cell by taking the battery pole piece obtained in the step 1) as a positive electrode, taking the zinc foil as a negative electrode and taking the zinc trifluoromethanesulfonate aqueous solution as an electrolyte, thus obtaining the aqueous zinc ion battery.
And (3) performance testing:
a constant current charge and discharge test with a current density of 50mA/g is carried out on the water system zinc ion battery by using a high-precision charge and discharge instrument, and the charge and discharge curves of the first three circles within the voltage range of 0.2V-1.7V are shown in figure 3.
As can be seen from fig. 3: the water system zinc ion battery has higher reversible specific capacity (210 mAh/g), the coulombic efficiency of the first circle reaches 65%, the coulombic efficiency of the second circle and the subsequent circles is close to 100%, and obvious discharging platforms appear at 0.5V and 1.0V.
Referring to the method, the molybdenum zinc vanadate positive electrode materials in the embodiments 2 to 5 are also manufactured into a water-based zinc ion battery, reversible specific capacities obtained through tests are 215mAh/g, 212mAh/g, 208mAh/g and 218mAh/g in sequence, the coulombic efficiencies in the first circle are 66%, 65%, 64% and 67% in sequence, the coulombic efficiencies in the second circle and the subsequent circle are close to 100%, and obvious discharge platforms appear at 0.5V and 1.0V as well.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The molybdenum zinc vanadate anode material is characterized in that the chemical formula of the molybdenum zinc vanadate anode material is Zn 3 MoV 2 O 8 (ii) a The molybdenum zinc vanadate anode material is a cubic crystal system, the unit cell parameters are a = b = c =8.3 \8491-8.5 \8491, and α = β = γ =90 °; the molybdenum zinc vanadate anode material is prepared by the following method: 1) Mixing a vanadium-containing compound, a molybdenum-containing compound and a zinc-containing compound according to a molar ratio of vanadium element, molybdenum element and zinc element of 2; 2) Heating the precursor mixture to 200-450 ℃ for heat treatment, and then grinding to obtain an intermediate product; 3) And sintering the intermediate product in a reducing atmosphere at 600-800 ℃ to obtain the molybdenum-zinc vanadate anode material.
2. The molybdenum-zinc vanadate positive electrode material according to claim 1, wherein: the vanadium-containing compound in the step 1) is at least one of vanadium pentoxide, ammonium metavanadate, vanadium dioxide, vanadium trioxide and vanadyl acetylacetonate.
3. The molybdenum-zinc vanadate positive electrode material according to claim 1, wherein: the molybdenum-containing compound in the step 1) is at least one of molybdenum dioxide, molybdenum trioxide, ammonium molybdate tetrahydrate, molybdenum acetylacetonate, molybdic acid and ammonium molybdate.
4. The molybdenum-zinc vanadate positive electrode material according to claim 1, wherein: the zinc-containing compound in the step 1) is at least one of zinc acetate and zinc oxide.
5. The molybdenum-zinc vanadate positive electrode material according to any one of claims 1 to 4, wherein: the time of the heat treatment in the step 2) is 2-10 h.
6. The molybdenum-zinc vanadate positive electrode material according to any one of claims 1 to 4, wherein: the sintering time in the step 3) is 7-15 h.
7. A positive electrode for a zinc-ion battery, comprising the molybdenum-zinc vanadate positive electrode material according to any one of claims 1 to 6.
8. An aqueous zinc ion battery comprising the molybdenum zinc vanadate positive electrode material according to any one of claims 1 to 6.
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| CN104752697A (en) * | 2015-03-27 | 2015-07-01 | 华南理工大学 | Mixed ion phosphate positive electrode material and preparation method thereof |
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| JP3973300B2 (en) * | 1998-09-10 | 2007-09-12 | 三菱化学株式会社 | Non-aqueous secondary battery |
| US20180212241A1 (en) * | 2017-01-23 | 2018-07-26 | Chung Yuan Christian University | Sodium secondary battery |
| CN106941158B (en) * | 2017-03-21 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of Zinc vanadate-molybdenum trioxide nanosheet electrode material of lithium battery and preparation method |
| CN109616624B (en) * | 2018-11-02 | 2021-09-21 | 长安大学 | Indium oxide coated secondary aqueous neutral zinc ion battery positive electrode material and preparation method and application thereof |
| CN110767887A (en) * | 2019-10-24 | 2020-02-07 | 华南理工大学 | Vanadium-manganese borate material, carbon-coated vanadium-manganese borate material, and preparation methods and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102412392A (en) * | 2011-09-26 | 2012-04-11 | 河北联合大学 | Method for compounding ZnV2O6 and Zn2V2O7 micro-nano-material with high temperature solid state method and use thereof |
| CN102903919A (en) * | 2012-10-23 | 2013-01-30 | 中国科学院过程工程研究所 | Anode material lithium vanadium silicate for lithium ion battery, preparation method and application of anode material |
| CN104752697A (en) * | 2015-03-27 | 2015-07-01 | 华南理工大学 | Mixed ion phosphate positive electrode material and preparation method thereof |
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