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CN112803083A - Zinc ion battery containing zinc complex - Google Patents

Zinc ion battery containing zinc complex Download PDF

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Publication number
CN112803083A
CN112803083A CN202110170299.5A CN202110170299A CN112803083A CN 112803083 A CN112803083 A CN 112803083A CN 202110170299 A CN202110170299 A CN 202110170299A CN 112803083 A CN112803083 A CN 112803083A
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zinc
ion battery
electrolyte
ligands
complex
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黄鹏
巫海洋
赖超
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Jiangsu Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

本发明公开了一种含有锌配合物的锌离子电池，涉及锌离子电池的技术领域。本发明的锌离子电池包括正极、负极、介于正负极之间的隔膜和电解质组成，所述电解质含有锌配合物。本发明开发的含有锌配合物的锌离子电池电解液体系成本低廉，制备简单，安全环保，在电化学测试过程中表现出优良的稳定性。能够抑制锌枝晶的生长从而保护锌离子电池电极，显著提升锌离子电池的循环寿命。在水系锌离子电池领域、储能领域、环保领域中有着较大的应用潜力。

Figure 202110170299

The invention discloses a zinc ion battery containing a zinc complex, and relates to the technical field of zinc ion batteries. The zinc ion battery of the present invention comprises a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and an electrolyte, and the electrolyte contains a zinc complex. The zinc ion battery electrolyte system containing the zinc complex developed by the invention has the advantages of low cost, simple preparation, safety and environmental protection, and excellent stability in the electrochemical test process. It can inhibit the growth of zinc dendrites to protect the electrodes of zinc ion batteries and significantly improve the cycle life of zinc ion batteries. It has great application potential in the field of aqueous zinc-ion batteries, energy storage, and environmental protection.

Figure 202110170299

Description

Zinc ion battery containing zinc complex
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a zinc ion battery containing a zinc complex.
Background
Due to the increasing environmental pollution and the continuous energy consumption, renewable energy sources and renewable energy storage technologies are becoming more and more important for social development. The electrochemical energy storage technology is a cleaner energy storage mode. Over the past decades, zinc ion batteries have been considered as the most promising alternative to the next generation of energy storage technologies due to their abundant zinc resources, low cost, and capacityHigh in quantity and friendly to the environment. The zinc ion battery has very high theoretical capacity (820 mAh g)–1) This provides a theoretical basis for replacing lithium ion batteries. The zinc metal has great natural abundance, and the smelting and storage difficulty of the zinc metal is far lower than that of the lithium, which means lower cost. In addition, the zinc ion battery mainly adopts mild aqueous electrolyte, and the aqueous electrolyte is safer and more environment-friendly compared with organic electrolyte adopted by a lithium ion battery.
Despite the great advantages of zinc ion batteries, the development of highly efficient electrolytes for zinc ion batteries is still in an early stage. To date, the electrolyte of zinc ion batteries has been predominantly inorganic zinc salts, such as: zinc sulfate, zinc chloride, zinc nitrate, etc. These zinc salts exhibit low discharge efficiency and cycle stability when used as zinc ion battery electrolytes, and are highly susceptible to dendrite generation during cycling, resulting in short circuits and battery damage. Therefore, the invention of a zinc ion battery containing the zinc complex is crucial.
Disclosure of Invention
In view of the problems noted in the background and the deficiencies of the prior art, it is an object of the present invention to provide a zinc-ion battery containing a zinc complex, which improves the performance of the zinc-ion battery significantly compared to the conventional zinc-ion battery.
The technical scheme of the invention is as follows:
the zinc ion battery comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and an electrolyte, wherein the electrolyte comprises an aqueous electrolyte, an organic electrolyte and a solid electrolyte, and the main component of the zinc ion battery is soluble zinc salt and contains a zinc complex.
Preferably, the positive electrode of the present invention is selected from one or more of manganese-based compound/composite material, vanadium-based compound/composite material, prussian blue-based compound/composite material, and organic frame-based compound/composite material.
Preferably, the negative electrode of the present invention is selected from one of zinc flakes, zinc powder, electrogalvanized zinc, foamed zinc or elemental zinc material.
Preferably, the battery diaphragm of the present invention is selected from one or more of non-woven fabric, glass fiber, polyamide, polyester terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and polycarbonate.
Preferably, the electrolyte of the present invention comprises a soluble zinc salt and a zinc complex. The soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoro-silicate, zinc trifluoromethanesulfonate and zinc gluconate. The central metal atom/ion of the zinc complex is zinc atom/ion, and the ligand is an oxygen-containing ligand, a nitrogen-containing ligand, an oxygen-containing nitrogen-containing ligand, a sulfur-selenium-containing ligand and a phosphorus-and-arsenic-containing ligand.
Compared with the prior art, the invention has the following beneficial effects:
1. the zinc ion battery electrolyte system containing the zinc complex has simple manufacturing process and low cost.
2. The zinc ion battery electrolyte system containing the zinc complex shows excellent electrochemical performance in a zinc ion battery.
Drawings
Fig. 1 time-voltage curves for assembling zinc symmetric cells using blank electrolytes.
Fig. 2 time-voltage curves for assembling zinc symmetric cells using the target electrolyte 1.
Fig. 3 time-voltage curves for assembling zinc symmetric cells using the target electrolyte 2.
Fig. 4 time-voltage curves for assembling zinc symmetrical cells using the target electrolyte 3.
Fig. 5 time-voltage curves for assembling zinc symmetric cells using the target electrolyte 4.
Fig. 6 time-voltage curves for assembling zinc symmetric cells using the target electrolyte 5.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
A zinc ion battery containing a zinc complex comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and an electrolyte, wherein the electrolyte comprises an aqueous electrolyte, an organic electrolyte and a solid electrolyte.
The anode material is selected from one or more of manganese-based compound/composite material, vanadium-based compound/composite material, Prussian blue compound/composite material and organic framework compound/composite material.
The negative electrode material is one of zinc sheets, zinc powder, electrogalvanizing, foamed zinc or a zinc simple substance material.
The diaphragm is selected from one or more of non-woven fabrics, glass fibers, polyamide, polyester terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene ethylene, polytetrafluoroethylene, polyvinylidene fluoride and polycarbonate.
The electrolyte comprises soluble zinc salt, and is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoro-sulfonate, zinc trifluoromethanesulfonate and zinc gluconate.
The electrolyte of the present invention contains a zinc complex.
The central metal atom/ion of the zinc complex is zinc atom/ion, and the ligand is at least one of oxygen-containing ligand, nitrogen-containing ligand, oxygen-containing nitrogen-containing ligand, sulfur-selenium-containing ligand and phosphorus-and arsenic-containing ligand.
The oxygen-containing ligand comprises at least one of carboxylic acid ligand, nitrogen-containing carboxylic acid ligand, crown ether ligand, pillar arene, calixarene, cyclodextrin, cucurbituril, beta-diketone chelating ligand, dialkyl ligand, diaryl phosphorous acid, glucose, terephthalic acid, trimesic acid and clusters.
The nitrogen-containing ligand comprises at least one of pyridine ligand, triazole ligand, carbazole ligand, imidazole ligand, ethylenediamine, dimethylformamide, hydrazine ligand, propylenediamine, diketone cyclobutene diol, butanediamine, dialkylamine, pyrazine, bipyridine, terpyridine, phthalocyanine ligand, zinc halide-ammonia complex, 1, 10-phenanthroline and 2, 9-dimethyl substituent thereof.
The oxygen-nitrogen-containing ligand comprises at least one of amino acid, 8-hydroxyquinoline, salicylamide schiff base complex and ethylenediamine tetraacetic acid.
The sulfur-selenium-containing ligand comprises at least one of thiol, thiourea, thiosemicarbazide, dialkylthiocarbamate and dithiolene ligand.
The phosphorus and arsenic-containing ligand of the present invention comprises at least one of binaphthyl diphenyl phosphine, triphenyl phosphorus, bis (diphenyl phosphine) methane, 1, 2-bis (diphenyl phosphine) ethane, alpha-phenylene-bis (dimethylarsine) and derivatives thereof.
Example 1
This example provides a zinc ion battery electrolyte containing an oxygen-zinc complex based on zinc gluconate, which is composed of a soluble zinc salt, the oxygen-zinc complex and deionized water, wherein the zinc salt is zinc sulfate (ZnSO)4) The oxygen-containing zinc complex is zinc gluconate (C)12H22O14Zn), wherein zinc sulfate (ZnSO)4) At a concentration of 1mol/L, zinc gluconate (C)12H22O14Zn) is 0.01mol/L, and the balance is water.
45.5mg of zinc gluconate and 2.87g of zinc sulfate were dissolved in 10mL of water, and stirred for 24 hours to obtain a target electrolyte 1.
2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain a blank electrolyte.
The prepared target electrolyte 1 and blank electrolyte are used for preparing a zinc symmetrical battery. The zinc symmetrical battery of the embodiment comprises a pair of metal zinc sheets, electrolyte and a diaphragm, wherein the diaphragm is made of glass fiber, and button type battery assembly is completed in air.
The electrochemical test of the zinc symmetrical cell of the present example was carried out on a LAND test system, the test temperature being kept constant at 25 ℃.
Fig. 1 is a time-voltage curve of a zinc symmetric cell assembled using a blank electrolyte.
Fig. 2 is a time-voltage curve of a symmetrical zinc cell assembled using the target electrolyte 1.
In the case of the blank electrolyte, short circuits occurred after 35 hours of cycling of the zinc symmetrical cell. In the case of the target electrolyte 1, the zinc symmetrical cell can be stably cycled for more than 85 hours. The result shows that the cycle life of the zinc ion battery electrolyte symmetrical battery based on the zinc gluconate oxygen-containing zinc complex is obviously prolonged.
Example 2
The embodiment provides zinc ion battery electrolyte of a nitrogen-zinc-containing complex based on zinc ethylenediamine, which comprises soluble zinc salt, the nitrogen-zinc-containing complex and deionized water, wherein the zinc salt is zinc sulfate (ZnSO)4) The nitrogen-containing zinc complex is ethylenediamine zinc, wherein zinc sulfate (ZnSO)4) The concentration of (2) is 1mol/L, and the balance is water.
10mg of ethylenediamine and 2.87g of zinc sulfate were dissolved in 10mL of water, and the mixture was stirred for 24 hours to obtain a target electrolyte 2.
2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain a blank electrolyte.
The prepared target electrolyte 2 and blank electrolyte are used for preparing a zinc symmetrical battery. The zinc symmetrical battery of the embodiment comprises a pair of metal zinc sheets, electrolyte and a diaphragm, wherein the diaphragm is made of glass fiber, and button type battery assembly is completed in air.
The electrochemical test of the zinc symmetrical cell of the present example was carried out on a LAND test system, the test temperature being kept constant at 25 ℃.
Fig. 3 is a time-voltage curve of a zinc symmetrical cell assembled using the target electrolyte 2.
In the case of the blank electrolyte, short circuits occurred after 35 hours of cycling of the zinc symmetrical cell. In the case of using the target electrolyte 2, the zinc symmetrical cell can be stably cycled for more than 100 hours. The cycle life of the zinc ion battery electrolyte symmetrical battery based on the nitrogen-containing zinc complex of the zinc ethylenediamine is obviously prolonged.
Example 3
The embodiment provides a zinc ion battery electrolyte containing an oxygen-containing and nitrogen-containing zinc complex based on 8-hydroxyquinolinolato zinc, which consists of soluble zinc salt, a zinc complex and deionized water, wherein the zinc salt is zinc sulfate (ZnSO)4) The zinc complex is 8-hydroxyquinoline zinc, wherein zinc sulfate (ZnSO)4) The concentration of (2) is 1mol/L, and the balance is water.
35mg of 8-hydroxyquinoline and 2.87g of zinc sulfate were dissolved in 10mL of water, and the mixture was stirred for 24 hours to obtain a target electrolyte solution 3.
2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain a blank electrolyte.
The prepared target electrolyte 3 and blank electrolyte are used for preparing a zinc symmetrical battery. The zinc symmetrical battery of the embodiment comprises a pair of metal zinc sheets, electrolyte and a diaphragm, wherein the diaphragm is made of glass fiber, and button type battery assembly is completed in air.
The electrochemical test of the zinc symmetrical cell of the present example was carried out on a LAND test system, the test temperature being kept constant at 25 ℃.
Fig. 4 is a time-voltage curve of a zinc symmetrical battery assembled using the target electrolyte 3.
In the case of the blank electrolyte, short circuits occurred after 35 hours of cycling of the zinc symmetrical cell. In the case of using the target electrolyte 3, the zinc symmetrical cell can be stably cycled for more than 110 hours. The cycle life of the zinc ion battery electrolyte symmetrical battery based on the oxygen-containing and nitrogen-containing zinc complex of 8-hydroxyquinoline zinc is obviously prolonged.
Example 4
The embodiment provides a thiourea zinc sulfate-based sulfur-selenium complex-containing zinc ion battery electrolyte, which consists of soluble zinc salt, a zinc complex and deionized water, wherein the zinc salt is zinc sulfate (ZnSO)4) The zinc complex is thiourea zinc sulfate, wherein the zinc sulfate (ZnSO)4) The concentration of (2) is 1mol/L, and the balance is water.
Thiourea (20 mg) and zinc sulfate (2.87 g) were dissolved in 10mL of water and stirred for 24 hours to obtain a target electrolyte solution (4).
2.87 (parts by weight) g ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain a blank electrolyte.
The prepared target electrolyte 4 and blank electrolyte are used for preparing a zinc symmetrical battery. The zinc symmetrical battery of the embodiment comprises a pair of metal zinc sheets, electrolyte and a diaphragm, wherein the diaphragm is made of glass fiber, and button type battery assembly is completed in air.
The electrochemical test of the zinc symmetrical cell of the present example was carried out on a LAND test system, the test temperature being kept constant at 25 ℃.
Fig. 5 is a time-voltage curve of a zinc symmetrical battery assembled using the target electrolyte 4.
In the case of the blank electrolyte, short circuits occurred after 35 hours of cycling of the zinc symmetrical cell. In the case of the target electrolyte 4, the zinc symmetrical cell can be stably cycled for more than 110 hours. The method shows that the cycle life of the zinc ion battery electrolyte symmetrical battery based on the thiourea zinc sulfate-containing selenium-zinc complex is obviously prolonged.
Example 5
The embodiment provides a zinc ion battery electrolyte containing an arsenic-zinc complex based on alpha-phenylene-bis (dimethylarsine) zinc, which consists of soluble zinc salt, a zinc complex and deionized water, wherein the zinc salt is zinc sulfate (ZnSO)4) The zinc complex is alpha-phenylene-bis (dimethylarsine) zinc, wherein zinc sulfate (ZnSO)4) The concentration of (2) is 1mol/L, and the balance is water.
50mg of alpha-phenylene-bis (dimethylarsine) and 2.87g of zinc sulfate were dissolved in 10mL of water, and the mixture was stirred for 24 hours to obtain a target electrolyte 5.
2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain a blank electrolyte.
The prepared target electrolyte 5 and blank electrolyte are used for preparing a zinc symmetrical battery. The zinc symmetrical battery of the embodiment comprises a pair of metal zinc sheets, electrolyte and a diaphragm, wherein the diaphragm is made of glass fiber, and button type battery assembly is completed in air.
The electrochemical test of the zinc symmetrical cell of the present example was carried out on a LAND test system, the test temperature being kept constant at 25 ℃.
Fig. 6 is a time-voltage curve of a zinc symmetrical battery assembled using the target electrolyte 5.
In the case of the blank electrolyte, short circuits occurred after 35 hours of cycling of the zinc symmetrical cell. In the case of using the target electrolyte 5, the zinc symmetrical cell can be stably cycled for more than 70 hours. The result shows that the cycle life of the zinc ion battery electrolyte symmetric battery containing the arsenic zinc complex based on the alpha-phenylene-bis (dimethylarsine) zinc is obviously prolonged.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (12)

1.一种含有锌配合物的锌离子电池，其特征在于锌离子电池由正极、负极、介于正负极之间的隔膜和电解质组成，所述电解质包括水系电解质、有机系电解质、固态电解质。1. a zinc ion battery containing zinc complex is characterized in that the zinc ion battery is made up of positive electrode, negative electrode, diaphragm and electrolyte between positive and negative electrode, and described electrolyte comprises aqueous electrolyte, organic electrolyte, solid electrolyte . 2.根据权利要求1所述的含有锌配合物的锌离子电池，其特征在于上述正极材料选自锰基化合物/复合材料、钒基化合物/复合材料、普鲁士蓝类化合物/复合材料、有机框架类化合物/复合材料中的一种或多种。2. The zinc ion battery containing zinc complex according to claim 1 is characterized in that above-mentioned positive electrode material is selected from manganese-based compound/composite material, vanadium-based compound/composite material, Prussian blue compound/composite material, organic framework One or more of compound/composite materials. 3.根据权利要求1所述的含有锌配合物的锌离子电池，其特征在于上述负极材料为锌片、锌粉、电镀锌、泡沫锌或锌单质材料中的一种。3 . The zinc ion battery containing zinc complex according to claim 1 , wherein the negative electrode material is one of zinc flakes, zinc powder, electro-galvanized zinc, foamed zinc or zinc elemental material. 4 . 4.根据权利要求1所述的含有锌配合物的锌离子电池，其特征在于上述膈膜选自无纺布、玻璃纤维、聚酰胺、聚对苯二甲酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丙乙烯、聚四氟乙烯、聚偏氟乙烯、聚碳酸酯中的一种或多种。4. The zinc ion battery containing zinc complex according to claim 1, wherein the diaphragm is selected from non-woven fabric, glass fiber, polyamide, polyethylene terephthalate, polyimide, polyamide One or more of ethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and polycarbonate. 5.根据权利要求1所述的含有锌配合物的锌离子电池，其特征在于上述电解质中包含可溶性锌盐，为硫酸锌、氯化锌、硝酸锌、乙酸锌、氟化锌、六氟酸锌、三氟甲磺酸锌、葡萄糖酸锌中的至少一种。5. The zinc ion battery containing zinc complex according to claim 1, characterized in that the electrolyte contains soluble zinc salt, which is zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, hexafluoric acid At least one of zinc, zinc trifluoromethanesulfonate, and zinc gluconate. 6.根据权利要求5所述的含有锌配合物的锌离子电池，其特征在于上述电解质中包含锌配合物。6 . The zinc ion battery containing a zinc complex according to claim 5 , wherein the electrolyte contains a zinc complex. 7 . 7.根据权利要求6所述的含有锌配合物的锌离子电池，其特征在于锌配合物的中心金属原子/离子为锌原子/离子，配体为含氧配体、含氮配体、含氧含氮配体、含硫硒配体、含磷和砷的配体中的至少一种。7. The zinc-ion battery containing zinc complex according to claim 6, wherein the central metal atom/ion of the zinc complex is a zinc atom/ion, and the ligand is an oxygen-containing ligand, a nitrogen-containing ligand, a At least one of oxygen-nitrogen-containing ligands, sulfur-containing selenium ligands, phosphorus- and arsenic-containing ligands. 8.根据权利要求7所述的含有锌配合物的锌离子电池，其特征在于所述含氧配体，包含羧酸类配体、含氮羧酸类配体、冠醚类配体、柱芳烃、杯芳烃、环糊精、瓜环、β-二酮类螯合配体、二烷基配体、二芳基亚磷酸、葡萄糖、对苯二甲酸、均苯三酸、团簇中的至少一种。8 . The zinc-ion battery containing zinc complexes according to claim 7 , wherein the oxygen-containing ligands comprise carboxylic acid-based ligands, nitrogen-containing carboxylic acid-based ligands, crown ether-based ligands, columnar Aromatics, calixarenes, cyclodextrins, cucurbits, β-diketones, chelating ligands, dialkyl ligands, diarylphosphites, glucose, terephthalic acid, trimesic acid, and in clusters at least one. 9.根据权利要求7所述的含有锌配合物的锌离子电池，其特征在于所述含氮配体，包含吡啶类配体、三氮唑类配体、咔唑类配体、咪唑类配体、乙二胺、二甲基甲酰胺、肼类配体、丙二胺、二酮环丁烯二醇、丁二胺、二烷基胺、吡嗪、联吡啶、三联吡啶、酞菁配体、卤化锌-氨配合、1,10-菲咯啉及其2,9-二甲基取代物中的至少一种。9 . The zinc-ion battery containing zinc complexes according to claim 7 , wherein the nitrogen-containing ligands comprise pyridine-based ligands, triazole-based ligands, carbazole-based ligands, and imidazole-based ligands. 10 . Ethylenediamine, dimethylformamide, hydrazine ligands, propylenediamine, diketocyclobutenediol, butanediamine, dialkylamine, pyrazine, bipyridine, terpyridine, phthalocyanine ligand At least one of the compound, zinc halide-ammonia complex, 1,10-phenanthroline and its 2,9-dimethyl substitution. 10.根据权利要求7所述的含有锌配合物的锌离子电池，其特征在于所述含氧氮配体，包含氨基酸、8-羟基喹啉、水杨酰胺西佛碱配合物、乙二胺四乙酸中的至少一种。10. The zinc-ion battery containing zinc complex according to claim 7, wherein the oxygen-nitrogen-containing ligand comprises amino acid, 8-hydroxyquinoline, salicylamide Schiff base complex, ethylenediamine at least one of tetraacetic acid. 11.根据权利要求7所述的含有锌配合物的锌离子电池，其特征在于所述含硫硒配体，包含硫醇、硫脲、氨基硫脲、二烷基硫代氨基甲酸盐、二硫纶配体中的至少一种。11. The zinc ion battery containing zinc complex according to claim 7, wherein the sulfur-containing selenium ligand comprises thiol, thiourea, thiosemicarbamate, dialkylthiocarbamate, at least one of the disulfide ligands. 12.根据权利要求7所述的含有锌配合物的锌离子电池，其特征在于所述含磷和砷的配体，包含联萘二苯膦、三苯基磷、双(二苯基膦)甲烷、1,2-双(二苯基膦)乙烷、α-苯撑-双二甲胂及其衍生物中的至少一种。12 . The zinc-ion battery containing zinc complexes according to claim 7 , wherein the ligands containing phosphorus and arsenic comprise binaphthyldiphenylphosphine, triphenylphosphine, bis(diphenylphosphine) 12 . At least one of methane, 1,2-bis(diphenylphosphine)ethane, α-phenylene-bisdimethylarsine and derivatives thereof.
CN202110170299.5A 2021-02-08 2021-02-08 Zinc ion battery containing zinc complex Pending CN112803083A (en)

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CN113410452A (en) * 2021-06-17 2021-09-17 中国科学技术大学 Modified zinc cathode and preparation method and application thereof
CN113707951A (en) * 2021-07-07 2021-11-26 徐州工程学院 Zinc gluconate electrolyte for zinc ion battery and application method thereof
CN113745520A (en) * 2021-09-05 2021-12-03 浙江大学 Preparation method and application of zinc cathode material for inhibiting zinc dendrites
CN114122389A (en) * 2021-11-26 2022-03-01 合肥工业大学 A zinc-manganese selenide solid solution cathode material for aqueous zinc-ion battery and preparation method thereof
CN114927771A (en) * 2022-05-25 2022-08-19 华南师范大学 Zinc ion battery electrolyte additive and application of in-situ generated SEI layer thereof in preparation of zinc ion battery
CN115275399A (en) * 2022-08-30 2022-11-01 北京理工大学长三角研究院(嘉兴) Electrolyte solution and aqueous zinc ion battery using same
CN117855631A (en) * 2024-03-05 2024-04-09 浙江瀚为科技有限公司 Vanadium-based water-based zinc ion battery and preparation method of multi-element electrolyte thereof

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CN113410452A (en) * 2021-06-17 2021-09-17 中国科学技术大学 Modified zinc cathode and preparation method and application thereof
CN113707951A (en) * 2021-07-07 2021-11-26 徐州工程学院 Zinc gluconate electrolyte for zinc ion battery and application method thereof
CN113745520A (en) * 2021-09-05 2021-12-03 浙江大学 Preparation method and application of zinc cathode material for inhibiting zinc dendrites
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CN117855631A (en) * 2024-03-05 2024-04-09 浙江瀚为科技有限公司 Vanadium-based water-based zinc ion battery and preparation method of multi-element electrolyte thereof
CN117855631B (en) * 2024-03-05 2024-05-24 浙江瀚为科技有限公司 Vanadium-based water-based zinc ion battery and preparation method of multi-element electrolyte thereof

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