Rechargeable water-based zinc ion battery with wide temperature range and long cycle life

文档序号:1189861 发布日期:2020-08-28 浏览:7次 中文

阅读说明:本技术 一种宽温度范围和长循环寿命的可充水系锌离子电池 (Rechargeable water-based zinc ion battery with wide temperature range and long cycle life ) 是由 陈军 马一琳 张秋 张凯 卢勇 李林 严振华 李海霞 于 2020-06-02 设计创作,主要内容包括:一种宽温度范围和长循环寿命的可充水系锌离子电池,属于化学电源领域。所述电池中正极材料为聚苯胺等有机材料或可逆脱嵌锌离子的过渡金属化合物;负极材料包括金属锌片、锌箔、锌粉、粉末多孔锌电极、或锌合金;宽液相温度范围电解液以水为溶剂,高溶解度无机盐为溶质,溶质包括氯化锌、溴化锌、碘化锌等。本发明使用宽液相温度窗口的电解液和高循环稳定性的聚苯胺等有机正极材料、过渡金属化合物构建低成本、高安全性、长循环寿命、宽温度范围的可充水系锌离子电池,可在-90℃至60℃的极宽温度范围下表现出较高的能量密度和长循环寿命,在极地考察、太空探索、深海探测等特殊场合及规模储能领域具有广阔应用前景。(A rechargeable water system zinc ion battery with wide temperature range and long cycle life belongs to the field of chemical power sources. The positive electrode material in the battery is organic materials such as polyaniline or transition metal compounds capable of reversibly deintercalating zinc ions; the negative electrode material comprises a metal zinc sheet, a zinc foil, zinc powder, a powder porous zinc electrode or a zinc alloy; the electrolyte with wide liquid phase temperature range takes water as a solvent, and inorganic salt with high solubility as a solute, wherein the solute comprises zinc chloride, zinc bromide, zinc iodide and the like. The rechargeable water-based zinc ion battery with low cost, high safety, long cycle life and wide temperature range is constructed by using the electrolyte with wide liquid phase temperature window, organic positive electrode materials such as polyaniline and the like with high cycle stability and transition metal compounds, can show higher energy density and long cycle life in the extremely wide temperature range of-90 ℃ to 60 ℃, and has wide application prospect in special occasions such as polar investigation, space exploration, deep sea exploration and the like and the field of large-scale energy storage.)

1. A rechargeable aqueous zinc ion battery having a wide temperature range and a long cycle life, characterized in that: the battery is formed by taking an organic compound containing an electrochemical active functional group or a transition metal compound capable of reversibly intercalating zinc ions as a positive electrode active substance, a zinc-based material as a negative electrode active substance, an aqueous solution taking inorganic high-solubility zinc salt as a solute as an electrolyte in a wide liquid phase temperature range, a Celgard 3501 water-based membrane as a diaphragm, a conductive agent and a binder added to prepare a positive electrode, and a current collector as a positive electrode carrier.

2. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of claim 1, wherein: besides the high-solubility zinc salt, the electrolyte can also be formed by mixing one or more of low-solubility zinc salt, high-solubility zinc/lithium/sodium/potassium/magnesium/calcium/aluminum salt.

3. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of claim 2, wherein: the high-solubility zinc salt is one or more of zinc chloride, zinc bromide, zinc iodide or zinc tetrafluoroborate; the low-solubility zinc salt is one or more of zinc sulfate, zinc trifluoromethanesulfonate, zinc bis (trifluoromethanesulfonyl imide) or zinc perchlorate.

4. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of claim 1, wherein: the organic compound containing the electrochemical active functional group comprises one or more of polyaniline or benzoquinone and organic matter of which the polybenzoquinone contains a carbonyl functional group; the transition metal compound capable of reversibly deintercalating zinc ions comprises a doped metal element M1Transition metal M of2An oxide; wherein M is1Is one or more of Li, Na, K, Mg, Ca, Zn, Al or Mn, M2Is one or more of Mn, V, Ni or Co.

5. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of claim 1, wherein: the zinc-based material is a metal zinc sheet, a zinc foil, zinc powder or a porous zinc/zinc alloy electrode.

6. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of any one of claims 1 to 5, wherein: the electrolyte with wide temperature range contains cations with the concentration range of 1-30mol kg-1Wherein the cation comprises one or more of zinc ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion and aluminum ion; the anion comprises one or more of trifluoromethyl sulfonyl ion, bis (trifluoromethyl sulfimide) ion, perchlorate, sulfate radical, nitrate radical, tetrafluoroborate radical, chloride ion, bromide ion and iodide ion.

7. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of any one of claims 1 to 5, wherein: the electrolyte with the wide temperature range also comprises an additive which is one or more of simple alcohols, sulfones and ethers organic solvents.

8. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of any one of claims 1 to 5, wherein: the conductive agent in the anode material is one or more of Ketjen black, conductive carbon black, acetylene black and microcrystalline graphite, and the binder is one or two of polytetrafluoroethylene or polyvinylidene fluoride.

9. The wide temperature range and long cycle life rechargeable aqueous zinc-ion battery of any one of claims 1 to 5, wherein: the current collector in the anode material is one of a titanium mesh, a titanium foil, a stainless steel mesh, a stainless steel foil and a carbon rod.

Technical Field

The invention relates to a rechargeable water-based zinc ion battery with a wide temperature range and a long cycle life, and belongs to the field of novel chemical power sources.

Background

The development of large-scale energy storage technology is important for the effective utilization of renewable energy and the construction of a novel energy society. At present, lithium ion batteries with high energy density and commercialized lead-acid batteries are widely applied to the commercial fields of mobile phone mobile communication, electric automobiles and the like. The lead-acid battery has low cost, but has limited energy density and cycle life, and lead has toxicity and is easy to cause environmental hidden trouble. The lithium ion battery shows high energy density, but has the problems of lithium resource shortage, high manufacturing cost, unsafe organic electrolyte and the like, so that the further development of the lithium ion battery is limited, and particularly the application of the lithium ion battery in a large-scale energy storage system is limited. The rechargeable water system zinc ion battery has the advantages of rich zinc cathode resources, low cost, high capacity and the like, and compared with an organic electrolyte, the water system electrolyte does not contain flammable components, is high in operation safety, environment-friendly, does not need a strict assembly environment, and has extremely high application value and huge development prospect in a large-scale energy storage system.

However, the aqueous zinc ion battery is limited by the thermal stability temperature and freezing point of the aqueous solution, and the application temperature range is narrow, so that the normal use in special environments, especially low-temperature environments, is difficult to meet. Therefore, solving the problem of overlarge environmental effect of the battery and expanding the working temperature range of the battery becomes an important problem to be solved urgently. The poor low-temperature performance of the water-based battery is mainly related to factors such as liquid-solid conversion of aqueous solution at low temperature, reduction of ionic conductivity, increase of interface impedance between an electrode and electrolyte, and deterioration of contact. The reason that the freezing point of water is high is that the hydrogen bond structure widely exists in the water, so that the freezing point of the water deviates from the freezing point law of the oxygen group element hydride, and the freezing point of the electrolyte can be reduced by breaking the hydrogen bond structure in the water. The metal ions with high charges and small ionic radius have coordination with oxygen atoms in water, and the oxygen atoms occupied by the metal ions and adjacent water molecules are difficult to form hydrogen bonds, so that the strength of the hydrogen bonds in the water is greatly weakened. The extent to which the hydrogen bonding structure is destroyed is closely related to the concentration of the metal ion.

Currently, the main positive electrode materials of aqueous zinc ion batteries are conventional inorganic materials such as vanadium-based oxides, manganese-based oxides, and prussian blue analogues. The battery completes the charge and discharge process through reversible embedding/releasing of zinc ions in crystal lattices of active substances, and the active substances are easy to generate structural changes in the repeated charge and discharge process so as to influence the cycle life of the battery. This makes it still unable to meet the requirements of long cycle life or high specific capacity/energy density. The search for a positive electrode material with high stability and high reversibility is also one of the important research points for improving the performance of the zinc ion battery.

Therefore, an aqueous zinc ion battery with low cost, high safety, long cycle life and wide temperature range is urgently to be developed, and the aqueous zinc ion battery serving as a novel energy storage system with excellent electrochemical performance has very important significance in the application of special occasions such as polar investigation, space exploration, deep sea exploration and the like and the field of large-scale energy storage.

Disclosure of Invention

The invention aims to solve the problems of short cycle life, poor rate performance and poor environmental adaptability of the water-based zinc ion battery researched in the prior art, and provides a novel water-based zinc ion battery which is excellent in performance, stable in cycle, capable of meeting the requirement of being used in a wide temperature range and long in cycle life.

The phase transition temperature of the water system electrolyte is regulated and controlled by adjusting and optimizing the components of the water system electrolyte. The high conductivity of the electrolyte is ensured, and meanwhile, the electrolyte has a wide liquid phase window and high environmental adaptability, so that the low-temperature performance and the environmental adaptability of the battery are improved. Meanwhile, the organic anode material is adopted to replace the traditional inorganic anode material. The organic positive electrode material, such as polyaniline, is different from a charge-discharge mechanism of lattice insertion/desorption, can realize reversible storage of charges through conversion of a benzene-type structure and a quinoid structure and ion adsorption, provides a foundation for the cycle stability of the battery, and brings more excellent rate performance through faster reaction kinetics. Therefore, the use of an organic material containing an electrochemically active functional group as a positive electrode active material is an important strategy for the development of an aqueous zinc ion battery having high energy density, long cycle, and high rate performance.

Technical scheme of the invention

A rechargeable water-based zinc ion battery with a wide temperature range and a long cycle life is formed by taking an organic compound containing an electrochemical active functional group such as polyaniline or a transition metal compound capable of reversibly intercalating and deintercalating zinc ions as a positive electrode active substance, a zinc-based material as a negative electrode active substance, an aqueous solution taking inorganic high-solubility zinc salt as a solute as a wide liquid phase temperature range electrolyte, a Celgard 3501 water-based film as a diaphragm, a current collector as a positive electrode carrier and a positive electrode prepared by adding a conductive agent and a bonding agent.

The electrolyte can be composed of high-solubility zinc salt (one or more of zinc chloride, zinc bromide, zinc iodide or zinc tetrafluoroborate) and also can be composed of low-solubility zinc salt (zinc sulfate, zinc trifluoromethanesulfonate, zinc bis (trifluoromethanesulfonylimide) or zinc perchlorate) mixed with one or more of high-solubility zinc/lithium/sodium/potassium/magnesium/calcium/aluminum salts.

The organic compound containing the electrochemical active functional group comprises one or more of organic matters containing carbonyl functional groups such as polyaniline or benzoquinone, and benzoquinone; the transition metal compound capable of reversibly deintercalating zinc ions comprises a doped metal element M1Transition metal M of2An oxide; wherein M is1Is one or more of Li, Na, K, Mg, Ca, Zn, Al or Mn, M2Is one or more of Mn, V, Ni or Co.

The zinc-based material is a metal zinc sheet, a zinc foil, zinc powder or a porous zinc/zinc alloy electrode.

The electrolyte with wide temperature range contains cations with the concentration range of 1-30mol kg-1Wherein the cation comprises one of zinc ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, and aluminum ionOr a plurality of the components; the anion comprises one or more of trifluoromethyl sulfonyl ion, bis (trifluoromethyl sulfimide) ion, perchlorate, sulfate radical, nitrate radical, tetrafluoroborate radical, chloride ion, bromide ion and iodide ion.

The electrolyte with the wide temperature range also comprises an additive which is one or more of simple alcohols, sulfones and ethers organic solvents.

The conductive agent in the anode material is one or more of Ketjen black, conductive carbon black, acetylene black and microcrystalline graphite, and the binder is one or two of polytetrafluoroethylene or polyvinylidene fluoride. The current collector in the anode material is one of a titanium mesh, a titanium foil, a stainless steel mesh, a stainless steel foil and a carbon rod.

The invention has the advantages and beneficial effects that:

compared with the prior art, the invention has the following beneficial effects: when the battery works, the positive electrode is subjected to benzene type/quinoid structure conversion and absorbs and desorbs ions, or zinc ions are embedded/separated, and the negative electrode zinc is dissolved/deposited, so that energy storage and conversion are realized. Compared with the traditional water system zinc ion battery, the water system zinc ion battery provided by the invention is based on the high-concentration salt solution with a wide liquid phase range, can still show higher specific capacity and energy density, long cycle life, excellent power performance and strong environmental adaptability under an extremely wide temperature range of-90 ℃ to 60 ℃, and can better meet the application requirement of large-scale energy storage.

Drawings

FIG. 1 is a charge and discharge curve at-70 ℃ to 60 ℃ of the aqueous zinc-ion battery in example 1;

FIG. 2 is a charge/discharge curve at-90 ℃ to-70 ℃ of the aqueous zinc-ion battery in example 1;

FIG. 3 is a graph showing the cycle performance at-70 ℃ of the aqueous zinc-ion battery of example 1;

fig. 4 is a charge-discharge curve of the aqueous zinc-ion battery in example 2 at different temperatures;

fig. 5 is a charge-discharge curve of the aqueous zinc-ion battery in example 3 at different temperatures.

Detailed Description

In order that the invention may be more readily understood, specific embodiments thereof will be further described with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

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