阅读说明：本技术 一种含有MnxV2O7纳米颗粒的电池正极及其高压水系电池 (Containing MnxV2O7Battery positive electrode of nano particles and high-voltage aqueous battery thereof ) 是由 尹博思 马天翼 于 2021-07-27 设计创作，主要内容包括：本发明属于材料技术领域,涉及一种含有Mn-(x)V-(2)O-(7)纳米颗粒的电池正极及其高压水系电池。一种含有Mn-(x)V-(2)O-(7)纳米颗粒的电池正极,是通过原位生长法或抽真空法将Mn-(x)V-(2)O-(7)纳米颗粒与导电柔性基底结合形成的柔性电池正极,其中2<x<2.5。该材料首次被发现具有储锌性能。Mn-(x)V-(2)O-(7)纳米颗粒具有双活性中心,V～(5+)具有缓冲作用,Mn～(2+)随着锌离子的嵌入/脱出而发生氧化还原反应。该材料首次作为储锌材料用做电池正极,拓展了锌离子正极材料种类的选择范围。测试表明,锌离子可以有效的在材料晶格内嵌入/脱出,实现锌离子的高效可逆存储。该材料具有高容量、高倍率以及超长循环性能等优势。(The invention belongs to the technical field of materials, and relates to a Mn-containing alloy x V 2 O 7 A nanoparticle positive electrode for a battery and a high-voltage aqueous battery using the same are provided. Containing Mn x V 2 O 7 The battery anode of nano particles is prepared by in-situ growing or vacuumizing Mn x V 2 O 7 A flexible battery positive electrode formed by combining nanoparticles with a conductive flexible substrate, wherein 2<x<2.5. The material is found to have zinc storage performance for the first time. Mn x V 2 O 7 Nano-particlesThe granule has double active centers, V 5+ Having a buffering action of Mn 2+ The redox reaction occurs with the intercalation/deintercalation of zinc ions. The material is used as a zinc storage material as a battery anode for the first time, and the selection range of the types of zinc ion anode materials is expanded. Tests show that zinc ions can be effectively embedded in/removed from material lattices, and efficient reversible storage of the zinc ions is realized. The material has the advantages of high capacity, high multiplying power, super-long cycle performance and the like.)

1. Containing Mn_xV₂O₇The battery anode of nano particles is characterized in that Mn is added by an in-situ growth method or a vacuum pumping method_xV₂O₇A flexible battery positive electrode formed by combining nanoparticles with a conductive flexible substrate, wherein 2<x<2.5。

2. An Mn-containing composition according to claim 1_xV₂O₇The battery anode of the nano-particles is characterized in that the conductive flexible substrate is one of carbon nano-tubes, carbon cloth and foamed nickel.

3. An Mn-containing composition according to claim 1_xV₂O₇The battery positive electrode of nano particles is characterized in that the battery positive electrode contains Mn_xV₂O₇The preparation method of the nanoparticle battery positive electrode comprises the following steps: dissolving a manganese source and a vanadium source in boiling water, stirring, adding dimethyl imidazole, continuously stirring, adding a pretreated conductive flexible substrate, reacting, standing, filtering, drying and calcining to obtain a target product.

4. A Mn-containing composition according to claim 3_xV₂O₇The battery anode of the nano-particles is characterized in that the manganese source is one or more than two of manganese chloride, manganese sulfate, manganese acetate or manganese nitrate.

5. A Mn-containing composition according to claim 4_xV₂O₇The battery anode of the nano-particles is characterized in that the vanadium source is one or more than two of ammonium metavanadate or vanadium pentoxide.

6. The method of claim 5Containing Mn_xV₂O₇A nanoparticle battery positive electrode characterized by having, in terms of mole ratio, a manganese source: the vanadium source is 1: 1-1.25.

7. A Mn-containing composition according to claim 6_xV₂O₇The battery anode of the nano particles is characterized in that the reaction conditions are that the reaction is carried out for 6 hours at 100 ℃ and the calcination is carried out for 3 hours at 450 ℃.

8. A high-voltage aqueous battery comprising Mn as set forth in claim 1_xV₂O₇The positive electrode, the negative electrode zinc sheet, the electrolyte and the diaphragm of the battery with the nano particles are assembled into a button battery through a tablet press or are assembled into a flexible battery through flexible packages such as aluminum plastic films and the like.

9. The high-voltage aqueous battery according to claim 8, wherein the electrolyte is a mixed electrolyte of lithium bistrifluoromethanesulfonimide and zinc trifluoromethanesulfonate, and is configured as a water-in-salt electrolyte, a semi-solid gel electrolyte or an all-solid electrolyte.

10. The high-pressure aqueous battery according to claim 9, wherein the separator is one of a cellulose separator, a polypropylene film, a separator paper, and a polymer semipermeable membrane; the zinc cathode is one of a zinc metal sheet, a zinc foil, zinc powder and an in-situ growth zinc nano material.

Technical Field

The present invention belongs to the field of material technologyThe technical field relates to a Mn-containing alloy_xV₂O₇A nanoparticle positive electrode for a battery and a high-voltage aqueous battery using the same are provided.

Background

With rapid development of global economy, rapid expansion of population numbers, and rapid progress of mobile electronic devices and the like, global energy consumption is rapidly increasing. At the present rate of consumption, global energy will face exhaustion in the near future. Thus, governments have been heavily advocating the development of clean, sustainable energy sources (wind, solar, hydro, tidal, etc.). Meanwhile, the research and development of a new-generation energy storage system which is efficient and safe and is matched with the energy storage system are urgent. The energy storage technology is one of core technologies for promoting the energy cleanness and electrification of the world, breaking energy resources and environmental constraints and realizing transformation and upgrading of global energy. To firmly and orderly promote the sustainable development of clean energy, the innovation of low-cost energy storage technology is necessary.

Compared with the current commercialized battery, the water-based zinc ion battery has many advantages, such as no memory effect, ultra-long service life, low product reject ratio, high energy storage efficiency, environmental friendliness and the like, so that the water-based zinc ion battery is expected to become an energy storage module more reliable than other batteries. At present, anode materials of water-based zinc ion batteries are mostly concentrated on manganese oxides and vanadium oxides, the capacities of the manganese oxides and the vanadium oxides are high, but the former has the problem of unavoidable electrode dissolution, and the latter has a low voltage platform and cannot meet daily use requirements. The search for new materials with high performance is imminent.

Mn produced in the present invention_xV₂O₇(2<x<2.5) the material belongs to the monoclinic system, in which Mn is responsible for²⁺The material has an ultra-long cycle life. Meanwhile, the double active centers enable the material to have higher capacity and a discharge platform higher than that of single vanadium oxide.

Disclosure of Invention

The invention aims to provide a positive electrode material Mn of a zinc ion battery_xV₂O₇(2<x<2.5) nanoparticles. The material is found to have zinc storage performance for the first time. Mn_xV₂O₇The nanoparticles have a double active center, V⁵⁺Having a buffering action of Mn²⁺The redox reaction occurs with the intercalation/deintercalation of zinc ions.

In order to achieve the purpose, the technical scheme of the invention is as follows: containing Mn_xV₂O₇The battery anode of nano particles is prepared by in-situ growing or vacuumizing Mn_xV₂O₇A flexible battery positive electrode formed by combining nanoparticles with a conductive flexible substrate, wherein 2<x<2.5。

Preferably, one of the above contains Mn_xV₂O₇The battery anode of the nano-particles, the conductive flexible substrate is one of carbon nano-tubes, carbon cloth and foamed nickel.

Preferably, one of the above contains Mn_xV₂O₇A battery positive electrode of nanoparticles, said battery positive electrode containing Mn_xV₂O₇The preparation method of the nanoparticle battery positive electrode comprises the following steps: dissolving a manganese source and a vanadium source in boiling water, stirring, adding dimethyl imidazole, continuously stirring, adding a pretreated conductive flexible substrate, reacting, standing, filtering, drying and calcining to obtain a target product.

Preferably, one of the above contains Mn_xV₂O₇The manganese source is one or more than two of manganese chloride, manganese sulfate, manganese acetate or manganese nitrate.

Preferably, one of the above contains Mn_xV₂O₇The battery anode of the nano-particle is characterized in that the vanadium source is one or more than two of ammonium metavanadate or vanadium pentoxide.

Preferably, one of the above contains Mn_xV₂O₇Nanoparticle battery positive electrode, in molar ratio, manganese source: the vanadium source is 1: 1-1.25.

Preferably, one of the above contains Mn_xV₂O₇The reaction conditions of the battery anode of the nano particles are that the battery anode reacts for 6 hours at 100 ℃ and is calcined for 3 hours at 450 ℃.

High voltageAn aqueous battery containing Mn as described above_xV₂O₇The positive electrode, the negative electrode zinc sheet, the electrolyte and the diaphragm of the battery with the nano particles are assembled into a button battery through a tablet press or are assembled into a flexible battery through flexible packages such as aluminum plastic films and the like.

Preferably, in the above high-voltage water system battery, the electrolyte is a mixed electrolyte of lithium bistrifluoromethanesulfonimide and zinc trifluoromethanesulfonate, and is configured as a water-in-salt electrolyte, a semi-solid gel electrolyte or an all-solid electrolyte.

Preferably, in the above high-pressure water-based battery, the separator is one of a cellulose separator, a polypropylene film, a separator paper and a polymeric semipermeable membrane; the zinc cathode is one of a zinc metal sheet, a zinc foil, zinc powder and an in-situ growth zinc nano material.

Firstly, preparing vanadium-manganese precipitate, carrying out high-temperature calcination and annealing treatment to finally obtain Mn_xV₂O₇(2<x<2.5). The preparation method is simple and feasible, low in price and environment-friendly. The prepared positive electrode material of the nano-particle zinc ion battery has excellent discharge performance and cycle performance. The invention is prepared from Mn_xV₂O₇The nanoparticles are grown directly on the conductive substrate, eliminating the use of binders that would degrade cell performance.

The invention has the beneficial effects that:

mn designed in the invention_xV₂O₇(2<x<2.5) belongs to monoclinic system, has abundant tunnel structure and is in the shape of nano-particles (shown in a and b). The high-pressure water system zinc ion battery formed by the high-pressure water system zinc ion battery has the following advantages:

1. compared with the battery composed of the common zinc sulfate electrolyte, the stable electrochemical working window can reach 2.5V, but the stable electrochemical working window is only 2.0V (shown in a figure c).

2. The battery has higher capacity and excellent rate performance, and is suitable for being used during high-power discharge (as shown in a graph d).

Drawings

FIG. 1 wherein a is Mn_xV₂O₇A TEM image of (B); b isMn_xV₂O₇XRD spectrum of (1); c is at 0.2mV s^-1CV plots in different electrolytes at sweep speed; d is the rate capability in high voltage electrolyte;

Detailed Description

The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Example 1

The method comprises the following steps:

1、Mn_xV₂O₇preparation of cathode material

1mmol of manganese sulfate and 1mmol of ammonium metavanadate are weighed out and stirred in 80ml of boiling water. After five minutes, 6mmol of dimethylimidazole was slowly added thereto, and after stirring for another ten minutes, the pretreated nickel foam was added and allowed to stand at room temperature. The resulting solution was then transferred to a reaction kettle and reacted at 100 ℃ for 6 h. Standing, filtering, and drying the precipitate in a blast drying oven at 70 deg.C. Finally calcining the precursor for 3h at 450 ℃ in air atmosphere to obtain the final product Mn_xV₂O₇And (3) a positive electrode material.

2. High-pressure aqueous battery

And manually polishing the zinc sheet negative electrodes with the same area to be bright by using abrasive paper.

The positive electrode battery shell after being cleaned is Mn_xV₂O₇The anode material and the cellulose diaphragm are assembled in sequence, and a proper amount of high-pressure zinc-containing electrolyte is dripped into the diaphragm. The electrolyte is a mixed electrolyte of lithium bis (trifluoromethanesulfonyl) imide and zinc trifluoromethanesulfonate, and is prepared into a water-in-salt electrolyte, a semi-solid gel electrolyte or a full-solid electrolyte. The negative electrode, gasket, washer, and negative casing were then assembled in order. And finally, preparing the button cell by using a tablet press.

The working voltage window of the high-voltage water system battery prepared by the method is 0-2.5V, and the maximum value of common electrolyte can be 2.0V.At 0.1A g^-1At current density, the capacity is up to 700mAh g^-1. At 1.0A g^-1Under the current density, the capacity can reach 250mAh g^-1。