WO2021232766A1 - Aqueous ammonium ion battery electrode based on pyrazine-fused ring semiconductor - Google Patents

Aqueous ammonium ion battery electrode based on pyrazine-fused ring semiconductor Download PDF

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WO2021232766A1
WO2021232766A1 PCT/CN2020/136695 CN2020136695W WO2021232766A1 WO 2021232766 A1 WO2021232766 A1 WO 2021232766A1 CN 2020136695 W CN2020136695 W CN 2020136695W WO 2021232766 A1 WO2021232766 A1 WO 2021232766A1
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fused ring
pyrazine
ammonium ion
electrode
ammonium
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PCT/CN2020/136695
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French (fr)
Chinese (zh)
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林宗琼
翁洁娜
霍峰蔚
刘玉琴
黄维
史兆鑫
席乔
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西北工业大学
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M2300/0005—Acid 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

Definitions

  • the invention belongs to the technical field of electrochemistry, and particularly relates to an electrode for an aqueous battery using a pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage active material.
  • the water-based rechargeable ion battery uses an aqueous ion salt solution as the electrolyte, which inherently solves the safety hazards of traditional ion batteries that use organic electrolyte as a working medium.
  • the water-based rechargeable ion battery also has the advantages of low price of water-based electrolyte and environmentally friendly, and the battery assembly process does not require anhydrous and oxygen-free harsh environment. It has extremely high potential and bright application prospects in large-scale grid energy storage applications. .
  • the negative electrode materials that can be used for ammonium ion storage are limited to a few Prussian blue analogs and intercalable metal oxides (V 2 O 5 , h-MoO 3 ) and other inorganic electrode materials, as well as imides (such as 3,4,9,10-perylene tetracarbodiimide, poly(1,4,5,8-naphthalenetetracarbodiimide)) organic electrode materials (J.Electrochem.Soc.2012,159, A98-A103; Chem.Commun.,2018,54,9805-9808; ACSAppl.Energy Mater.2018,1,3077-3083; Nanoscale Horiz.,2019,4,991-998; J.Mater.Chem.A,2019, 7,11314-11320; Chem 2019, 5, 1537-1551; Adv.
  • the present invention proposes a water-based ammonium ion battery electrode with high energy storage density, long cycle life, low cost, and environment-friendly.
  • the electrode uses a pyrazine fused ring semiconductor with multiple ion storage sites as an ammonium ion storage material, and can realize electrochemical insertion and extraction of ammonium ions in a non-flammable aqueous solution of ammonium ions and an atmospheric environment.
  • a water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor, using pyrazine fused ring aromatic hydrocarbon as ammonium ion storage material, and electrochemical insertion and extraction of ammonium ions can be realized in an ammonium ion aqueous electrolyte solution and atmospheric environment;
  • the aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure;
  • the ammonium ion aqueous electrolyte solution is made of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate.
  • a water-based ammonium ion battery electrode which uses pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage material.
  • the aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure;
  • the electrode includes a collector Fluid and dried electrode slurry coated on the current collector, the electrode slurry is a pyrazine fused ring aromatic compound and a conductive agent, a binder and a solvent, the pyrazine fused ring aromatic compound, a conductive agent
  • the mass ratio with binder is 6:3:1-9:0:1.
  • the pyrazine fused ring aromatic hydrocarbon includes but is not limited to one of the following general structural formulas:
  • Ar 1 , Ar 2 and Ar 3 groups independently include aromatic hydrocarbons or heterocyclic aromatic hydrocarbons; R 1 and R 2 groups independently include H, halogen, alkyl, haloalkyl, amino, hydroxyl, and alkoxy , Mercapto, ester, acyl, cyano, sulfonic, aromatic or heterocyclic aromatic.
  • the aromatic hydrocarbons are monocyclic or condensed ring aromatic hydrocarbons, including but not limited to benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene and derivatives containing substituents.
  • heterocyclic aromatic hydrocarbons are monocyclic or condensed ring heterocyclic aromatic hydrocarbons, including but not limited to pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline , Quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphofluorene, silicon fluorene, phenothiazine and derivatives containing substituents.
  • the substituents in the substituent-containing derivatives include, but are not limited to, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, aromatic or hetero Ring aromatic group.
  • a method for preparing water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors the steps are as follows:
  • Step 1 Mix the pyrazine fused ring aromatic compound with the conductive agent, the binder, and the solvent uniformly to form an electrode slurry; the mass ratio of the pyrazine fused ring aromatic compound, the conductive agent and the binder is 6:3:1 9:0:1;
  • Step 2 Coating the electrode slurry on the current collector to form pole pieces
  • Step 3 Put the above pole piece in a vacuum oven for baking and drying, the drying temperature is 25-200°C, and the drying time is 1-36h.
  • the solvent is water or an organic solvent
  • the organic solvent includes but is not limited to N-pyrrolidone, dimethyl sulfoxide or dimethyl formamide.
  • a test method for water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors is carried out in a three-electrode system.
  • the preparation and assembly process of the three-electrode system is as follows:
  • Step 1 Prepare activated carbon counter electrode pole piece by mixing activated carbon, conductive agent and binder;
  • Step 2 Separate the prepared water-based ammonium ion battery electrode based on the pyrazine fused ring semiconductor and the activated carbon counter electrode pole piece with a diaphragm material, put it into the battery case, and inject one of the ammonium ion water-based electrolyte solutions as an electrolyte;
  • Step 3 Insert the reference electrode
  • Step 4 Perform battery performance test.
  • the reference electrode includes, but is not limited to, Ag/AgCl electrode or calomel electrode.
  • the present invention proposes a water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor. Compared with the existing water-based rechargeable ammonium ion battery technology, the present invention has the following beneficial effects: using ammonium ions and aromatic The coordination of nitrogen atoms uses pyrazine fused ring semiconductors with multiple ion storage sites as ammonium ion storage materials to increase the specific capacity of water-based rechargeable ammonium ion batteries.
  • the present invention is first prepared at a current density than 50mAg -1 355mAhg -1 capacity of aqueous ammonium ion based battery electrode pyrazine ring fused semiconductor, a rapid discharge of the electrode at a current density of 600mAg -1 capacity ratio can reach 190mAhg -1 .
  • Figure 1 is the structural formula of the pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention
  • Example 2 is a charge-discharge curve diagram of an electrode for an aqueous ammonium ion battery based on a pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention
  • FIG. 3 is a graph showing the rate performance curve of an electrode for an aqueous ammonium ion battery based on a pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention
  • Example 4 is the structural formula of the pyrazine fused ring semiconductor DPQDPP prepared in Example 2 of the present invention
  • Example 5 is a graph showing the charge and discharge curves of the electrode of the water-based ammonium ion battery based on the pyrazine fused ring semiconductor DPQDPP prepared in Example 2 of the present invention.
  • a water-based ammonium ion battery electrode based on pyrazine fused ring semiconductors uses pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage material, and electrochemical insertion and extraction of ammonium ions can be realized in an ammonium ion aqueous electrolyte solution and an atmospheric environment.
  • the above-mentioned ammonium ion storage material is a pyrazine condensed ring aromatic hydrocarbon, which is that the aromatic hydrocarbon molecule contains at least one pyrazine unit and has a condensed ring structure.
  • the above-mentioned pyrazine fused ring aromatic hydrocarbon includes but is not limited to one of the following general structural formulas:
  • the Ar 1 , Ar 2 and Ar 3 groups in the above general structural formula independently include aromatic hydrocarbons or heterocyclic aromatic hydrocarbons.
  • the R 1 and R 2 groups in the above general structural formula independently include H, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, Aromatics or heterocyclic aromatics.
  • the above-mentioned aromatic hydrocarbons are monocyclic or condensed ring aromatic hydrocarbons, including but not limited to aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene, and derivatives containing substituents.
  • aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene, and derivatives containing substituents.
  • the above-mentioned heterocyclic aromatic hydrocarbons are monocyclic or fused-ring heterocyclic aromatic hydrocarbons, including but not limited to pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquine Heterocyclic aromatic hydrocarbons such as morpholine, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphofluorene, silicon fluorene, phenothiazine, and derivatives containing substituents.
  • the substituents in the above-mentioned substituent-containing derivatives include, but are not limited to, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, and aromatic groups. Or heterocyclic aromatic groups and so on.
  • the ammonium ion aqueous electrolyte solution is selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium fluoride, ammonium iodide, ammonium bromide and ammonium triflate.
  • ammonium sulfate ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium fluoride, ammonium iodide, ammonium bromide and ammonium triflate.
  • ammonium ion aqueous electrolyte solution is selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium fluoride, ammonium iodide, ammonium bromide and ammonium triflate.
  • concentration of the ammonium salt is 0.1M-21M.
  • the preparation steps of the water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor include the following:
  • the pyrazine fused ring aromatic compound is uniformly mixed with a conductive agent, a binder, and a solvent to form an electrode slurry.
  • the solvent includes, but is not limited to, deionized water or an organic solvent.
  • the organic solvent is N-pyrrolidone, two The mass ratio of methyl sulfoxide or dimethylformamide, pyrazine fused ring aromatic compound, conductive agent and binder is 6:3:1-9:0:1.
  • the drying temperature is 25-200°C, and the drying time is 1-36h.
  • battery performance tests such as charge-discharge specific capacity, Coulomb efficiency, rate performance test, etc. are carried out in a three-electrode system.
  • the preparation and assembly process of the three-electrode system is as follows:
  • Activated carbon is mixed with conductive agent and binder to prepare activated carbon counter electrode pole piece;
  • Insert a reference electrode which includes but is not limited to Ag/AgCl electrode or calomel electrode.
  • a water-based ammonium ion battery electrode based on the pyrazine fused ring semiconductor diquinoxalino[2,3-a:2',3'-c]phenazine (DQP, the structural formula is shown in Figure 1), and the specific preparation method As follows: Grind and mix 80 mg of pyrazine fused ring aromatic compound DQAPZ, 20 mg of carbon nanotubes, and 10 mg of polyvinylidene fluoride binder, add an appropriate amount of N-pyrrolidone and stir to obtain a uniform slurry, and evenly coat it on clean titanium On the foil, dry in a vacuum oven at 60°C for 12 hours.
  • DQP diquinoxalino[2,3-a:2',3'-c]phenazine
  • the specific preparation method of the activated carbon electrode sheet is as follows: add activated carbon and polyvinylidene fluoride to N-pyrrolidone at 9:1, stir to obtain a uniform slurry; then use suction filtration to make the slurry into a carbon electrode ,Dry in a vacuum oven at 60°C for 12h.
  • the three-electrode system of the DQP-based water-based ammonium ion battery electrode is assembled as follows: the DQP-based water-based ammonium ion battery electrode prepared above is used as the working electrode, glass fiber is used as the diaphragm, the activated carbon electrode is used as the counter electrode, and Ag/AgCl The electrode is used as a reference electrode, the above-mentioned electrodes are sequentially placed in the battery cell body, 0.5M ammonium sulfate aqueous solution is added as the electrolyte, and the battery is tightened.
  • the charging and discharging curve of DQP-based water-based ammonium ion battery electrodes is shown in Figure 2.
  • the working range of -1.0 ⁇ 0.6V (vs.Ag/AgCl) charging and discharging are performed at a current density of 50mAg -1 Tests showed that the discharge specific capacity reached 360mAhg -1 , the discharge specific capacity reached 355mAhg -1 , and the coulombic efficiency was 98.6%.
  • the rate performance test of the electrode of the water-based ammonium ion battery based on DQP is shown in FIG. discharging at a current density of 50,100,200,400,600mAg -1, respectively, the specific capacity 355,300,260,220,190mAhg -1.
  • a pyrazine-based condensed ring semiconductor bipyrido[3',2':5,6; 2”,3”:7,8]quinoxalino[2,3-i]dipyrido[3,2 -a: 2',3'-c] phenazine (DPQDPP, the structural formula is shown in Figure 4) water-based ammonium ion battery electrode, the specific preparation method is as follows: 80mg pyrazine fused ring aromatic compound DPQDPP, 20mg carbon nanotubes , 10mg of polyvinylidene fluoride binder is ground and mixed evenly, add an appropriate amount of N-pyrrolidone and stir to obtain a uniform slurry, evenly coat it on a clean titanium foil, and dry it in a vacuum oven at 60°C for 12 hours.
  • the three-electrode system of the DPQDPP-based water-based ammonium ion battery electrode is assembled as follows: the DPQDPP-based water-based ammonium ion battery electrode prepared above is used as the working electrode, glass fiber is used as the separator, and the activated carbon electrode in Example 1 is used as the counter Electrode, Ag/AgCl electrode as the reference electrode, put the above-mentioned electrodes in the battery cell in turn, add 0.5M ammonium sulfate aqueous solution as electrolyte, and tighten the battery.
  • the charge-discharge curve of the electrode of the water-based ammonium ion battery based on DPQDPP is shown in Figure 5.
  • the charge and discharge are performed at a current density of 50mAg -1
  • the specific charge capacity is 208mAhg -1
  • the specific discharge capacity is 135 mAhg -1
  • the coulombic efficiency is 65%.

Abstract

Disclosed is an aqueous ammonium ion battery electrode based on a pyrazine-fused ring semiconductor, wherein a coordination effect between ammonium ions and aromatic nitrogen atoms in a pyrazine-fused ring semiconductor is used, and the pyrazine-fused ring semiconductor having multiple ion storage sites acts as an ammonium ion storage material to improve the specific capacity of an aqueous rechargeable ammonium ion battery. The aqueous ammonium ion battery electrode based on the pyrazine-fused ring semiconductor and having a specific capacity reaching 355 mAhg-1 at a current density of 50 mAg-1 is prepared for the first time, and the specific capacity of the electrode during rapid discharge at a current density of 600 mAg-1 can still reach 190 mAhg-1.

Description

一种基于吡嗪稠环半导体的水系铵离子电池电极Aqueous ammonium ion battery electrode based on pyrazine fused ring semiconductor
本申请要求于2020年05月18日提交中国专利局、申请号为CN202010418812.3、发明名称为“一种基于吡嗪稠环半导体的水系铵离子电池电极”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on May 18, 2020, the application number is CN202010418812.3, and the invention title is "A water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor". The entire content is incorporated into this application by reference.
技术领域Technical field
本发明属于电化学技术领域，特别涉及一种以吡嗪稠环芳烃作为铵离子存储活性材料的水系电池电极。The invention belongs to the technical field of electrochemistry, and particularly relates to an electrode for an aqueous battery using a pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage active material.
背景技术Background technique
水系可充电离子电池以离子盐水溶液作为电解液，在本征上解决了以有机电解液为工作媒介的传统离子电池的安全隐患问题。另外，水系可充电离子电池还具有水系电解液价格低廉且环境友好、电池组装过程无需无水无氧的苛刻环境等优点，在大规模电网储能应用中具有极高的潜力和明朗的应用前景。The water-based rechargeable ion battery uses an aqueous ion salt solution as the electrolyte, which inherently solves the safety hazards of traditional ion batteries that use organic electrolyte as a working medium. In addition, the water-based rechargeable ion battery also has the advantages of low price of water-based electrolyte and environmentally friendly, and the battery assembly process does not require anhydrous and oxygen-free harsh environment. It has extremely high potential and bright application prospects in large-scale grid energy storage applications. .
现有水相电池的研究大多以金属阳离子作为电荷载体，然而地球上金属元素的含量有限且分布不均，过量、开采金属矿物会对环境造成不可逆的破坏。开发以非金属阳离子作为电荷载体的水系电池在保护环境、维持资源的可持续性方面具有绝对的优势。与一价金属阳离子极为类似的铵离子具有水合离子半径小、摩尔质量小、独特的拓扑化学结构、廉价易得等优势，在电池研究的基础领域逐渐受到重视(Energy Environ.Sci.,2019,12,3203-3224)。Most of the existing researches on water-phase batteries use metal cations as charge carriers. However, the content of metal elements on the earth is limited and unevenly distributed. Excessive and mining of metal minerals will cause irreversible damage to the environment. The development of water-based batteries using non-metal cations as charge carriers has absolute advantages in protecting the environment and maintaining the sustainability of resources. Ammonium ions, which are very similar to monovalent metal cations, have the advantages of small hydrated ion radius, small molar mass, unique topological chemical structure, and low cost and easy availability. They have gradually attracted attention in the basic field of battery research (Energy Environment.Sci., 2019, 12,3203-3224).
然而，相比于以金属阳离子作为电荷载体的水系金属离子可充电电池，水系可充电铵离子电池的发展极为缓慢。自2017年美国俄勒冈州立大学秀磊课题组报道了第一例“摇椅式”的水系铵离子全电池(Angew.Chem.Int.Ed.2017,56,13026-13030)以来，迄今为止水系铵离子电池的报道仍不满10例，且在电池性能(如比容量、能量密度等)尚落后于发展最为成熟的水系锂离子电池。这种缓慢且落后的发展背后最为主要的原因为铵离子存储电极材料的严重缺乏。例如，迄今为止，可用于铵离子存储的负极材料仅限于少数的普鲁士蓝类似物和可插层金属氧化物(V 2O 5、 h-MoO 3)等无机电极材料，以及酰亚胺类(如3,4,9,10－苝四甲酰二亚胺、聚(1,4,5,8-萘四碳二酰亚胺))有机电极材料(J.Electrochem.Soc.2012,159,A98-A103；Chem.Commun.,2018,54,9805-9808；ACSAppl.Energy Mater.2018,1,3077-3083；Nanoscale Horiz.,2019,4,991-998；J.Mater.Chem.A,2019,7,11314-11320；Chem 2019,5,1537-1551；Adv.Mater.2020,1907802)。上述这些已报道的负极材料在水系电解液的稳定工作电压范围内存储铵离子的比容量有限(低于160mAhg -1)，组成的全电池能量密度均低于60Whkg -1，无法满足实际的储能应用。因此，需要研制新的高比容量的水系铵离子电池电极。 However, compared with water-based metal ion rechargeable batteries that use metal cations as charge carriers, the development of water-based rechargeable ammonium ion batteries is extremely slow. Since 2017, the research group of Xiulei of Oregon State University in the United States reported the first case of "rocking chair" water-based ammonium ion battery (Angew.Chem.Int.Ed.2017,56,13026-13030), so far the water-based ammonium ion There are still less than 10 battery reports, and the battery performance (such as specific capacity, energy density, etc.) is still behind the most mature water-based lithium-ion battery. The main reason behind this slow and backward development is the serious lack of ammonium ion storage electrode materials. For example, so far, the negative electrode materials that can be used for ammonium ion storage are limited to a few Prussian blue analogs and intercalable metal oxides (V 2 O 5 , h-MoO 3 ) and other inorganic electrode materials, as well as imides ( Such as 3,4,9,10-perylene tetracarbodiimide, poly(1,4,5,8-naphthalenetetracarbodiimide)) organic electrode materials (J.Electrochem.Soc.2012,159, A98-A103; Chem.Commun.,2018,54,9805-9808; ACSAppl.Energy Mater.2018,1,3077-3083; Nanoscale Horiz.,2019,4,991-998; J.Mater.Chem.A,2019, 7,11314-11320; Chem 2019, 5, 1537-1551; Adv. Mater. 2020, 1907802). The above-mentioned negative electrode materials that have been reported have a limited specific capacity for storing ammonium ions within the stable working voltage range of the aqueous electrolyte (less than 160mAhg -1 ), and the energy density of the composed full battery is less than 60Whkg -1 , which cannot meet the actual storage requirements. Can be applied. Therefore, it is necessary to develop a new high specific capacity water-based ammonium ion battery electrode.
发明内容Summary of the invention
为了避免现有技术的不足之处，本发明提出一种储能密度高、循环寿命长、成本低、环境友好的水系铵离子电池电极。该电极以具有多离子存储位点的吡嗪稠环半导体为铵离子存储材料，在不易燃的铵离子水溶液和大气环境中即可实现铵离子的电化学插入和脱出。In order to avoid the shortcomings of the prior art, the present invention proposes a water-based ammonium ion battery electrode with high energy storage density, long cycle life, low cost, and environment-friendly. The electrode uses a pyrazine fused ring semiconductor with multiple ion storage sites as an ammonium ion storage material, and can realize electrochemical insertion and extraction of ammonium ions in a non-flammable aqueous solution of ammonium ions and an atmospheric environment.
为了解决上述技术问题，本发明采用的技术方案是：In order to solve the above technical problems, the technical solutions adopted by the present invention are:
一种基于吡嗪稠环半导体的水系铵离子电池电极，以吡嗪稠环芳烃为铵离子存储材料，在铵离子水系电解质溶液和大气环境中即可实现铵离子的电化学插入和脱出；所述的吡嗪稠环芳烃的芳烃分子中至少含有一个吡嗪单元，且为稠环结构；所述的铵离子水系电解质溶液为以硫酸铵、氯化铵、硝酸铵、碳酸铵、碳酸氢铵、氟化铵、碘化铵、溴化铵和三氟甲磺酸铵中的一种或多种配制而成的水溶液，且其中铵盐的浓度为0.1M-21M。A water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor, using pyrazine fused ring aromatic hydrocarbon as ammonium ion storage material, and electrochemical insertion and extraction of ammonium ions can be realized in an ammonium ion aqueous electrolyte solution and atmospheric environment; The aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure; the ammonium ion aqueous electrolyte solution is made of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate. , Ammonium fluoride, ammonium iodide, ammonium bromide and ammonium trifluoromethanesulfonate in one or more of the aqueous solutions, and the concentration of the ammonium salt is 0.1M-21M.
一种水系铵离子电池电极，以吡嗪稠环芳烃作为铵离子存储材料，所述的吡嗪稠环芳烃的芳烃分子中至少含有一个吡嗪单元，且为稠环结构；所述电极包括集流体和涂覆在所述集流体上的电极浆料干燥物，所述电极浆料为吡嗪稠环芳烃化合物与导电剂、粘结剂和溶剂，所述吡嗪稠环芳烃化合物、导电剂和粘结剂的质量比例为6：3：1-9：0：1。A water-based ammonium ion battery electrode, which uses pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage material. The aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure; the electrode includes a collector Fluid and dried electrode slurry coated on the current collector, the electrode slurry is a pyrazine fused ring aromatic compound and a conductive agent, a binder and a solvent, the pyrazine fused ring aromatic compound, a conductive agent The mass ratio with binder is 6:3:1-9:0:1.
所述的吡嗪稠环芳烃包括但不限于以下结构通式的一种：The pyrazine fused ring aromatic hydrocarbon includes but is not limited to one of the following general structural formulas:
Figure PCTCN2020136695-appb-000001
Figure PCTCN2020136695-appb-000001
结构通式中Ar 1、Ar 2和Ar 3基团独立的包括芳烃或杂环芳烃；R 1和R 2基团独立的包括H、卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳烃或杂环芳烃。 In the general structural formula, Ar 1 , Ar 2 and Ar 3 groups independently include aromatic hydrocarbons or heterocyclic aromatic hydrocarbons; R 1 and R 2 groups independently include H, halogen, alkyl, haloalkyl, amino, hydroxyl, and alkoxy , Mercapto, ester, acyl, cyano, sulfonic, aromatic or heterocyclic aromatic.
所述的芳烃为单环或稠环芳烃，包括但不限于苯、萘、蒽、菲、芘、苝、芴及其含取代基的衍生物。The aromatic hydrocarbons are monocyclic or condensed ring aromatic hydrocarbons, including but not limited to benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene and derivatives containing substituents.
所述的杂环芳烃为单环或稠环杂环芳烃，包括但不限于吡咯、呋喃、噻吩、噻唑、二唑、三唑、吡啶、嘧啶、哒嗪、吡嗪、喹啉、异喹啉、喹喔啉、酞嗪、苯并噻唑、苯并二唑、菲罗啉、咔唑、磷芴、硅芴、吩噻嗪及其含取代基的衍生物。The heterocyclic aromatic hydrocarbons are monocyclic or condensed ring heterocyclic aromatic hydrocarbons, including but not limited to pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline , Quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphofluorene, silicon fluorene, phenothiazine and derivatives containing substituents.
所述含取代基的衍生物中的取代基包括但不限于卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳香基或杂环芳香基。The substituents in the substituent-containing derivatives include, but are not limited to, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, aromatic or hetero Ring aromatic group.
一种基于吡嗪稠环半导体的水系铵离子电池电极的制备方法，步骤如下：A method for preparing water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors, the steps are as follows:
步骤1：将吡嗪稠环芳烃化合物与导电剂、粘结剂、溶剂混合均匀，形成电极浆料；吡嗪稠环芳烃化合物、导电剂和粘结剂的质量比例为6：3：1-9：0：1；Step 1: Mix the pyrazine fused ring aromatic compound with the conductive agent, the binder, and the solvent uniformly to form an electrode slurry; the mass ratio of the pyrazine fused ring aromatic compound, the conductive agent and the binder is 6:3:1 9:0:1;
步骤2：将所述电极浆料涂覆在集流体上，形成极片；Step 2: Coating the electrode slurry on the current collector to form pole pieces;
步骤3：将上述极片置于真空烘箱中烘烤干燥，干燥温度为25～200℃，干燥时间为1～36h。Step 3: Put the above pole piece in a vacuum oven for baking and drying, the drying temperature is 25-200°C, and the drying time is 1-36h.
所述的溶剂为水或有机溶剂，所述有机溶剂包括但不限于N-吡咯烷 酮、二甲基亚砜或二甲基甲酰胺。The solvent is water or an organic solvent, and the organic solvent includes but is not limited to N-pyrrolidone, dimethyl sulfoxide or dimethyl formamide.
一种基于吡嗪稠环半导体的水系铵离子电池电极的测试方法，在三电极体系中进行的，所述的三电极体系制备和组装过程如下：A test method for water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors is carried out in a three-electrode system. The preparation and assembly process of the three-electrode system is as follows:
步骤1：以活性炭与导电剂、粘结剂混合制备活性炭对电极极片；Step 1: Prepare activated carbon counter electrode pole piece by mixing activated carbon, conductive agent and binder;
步骤2：用隔膜材料将制备的基于吡嗪稠环半导体的水系铵离子电池电极和活性炭对电极极片隔开，放入电池壳中，注入铵离子水系电解质溶液中的一种作为电解液；Step 2: Separate the prepared water-based ammonium ion battery electrode based on the pyrazine fused ring semiconductor and the activated carbon counter electrode pole piece with a diaphragm material, put it into the battery case, and inject one of the ammonium ion water-based electrolyte solutions as an electrolyte;
步骤3：插入参比电极；Step 3: Insert the reference electrode;
步骤4：进行电池性能测试。Step 4: Perform battery performance test.
所述的参比电极包括但不限于Ag/AgCl电极或甘汞电极。The reference electrode includes, but is not limited to, Ag/AgCl electrode or calomel electrode.
有益效果Beneficial effect
本发明提出的一种基于吡嗪稠环半导体的水系铵离子电池电极，与现有水系可充电铵离子电池技术相比较，本发明具有如下有益效果：利用铵离子与吡嗪稠环半导体中芳香氮原子的配位作用，以具有多离子存储位点的吡嗪稠环半导体作为铵离子存储材料，提高水系可充电铵离子电池的比容量。本发明首次制备了在50mAg -1电流密度下比容量达到355mAhg -1的基于吡嗪稠环半导体的水系铵离子电池电极，该电极在600mAg -1电流密度的快速放电下比容量仍可达到190mAhg -1。 The present invention proposes a water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor. Compared with the existing water-based rechargeable ammonium ion battery technology, the present invention has the following beneficial effects: using ammonium ions and aromatic The coordination of nitrogen atoms uses pyrazine fused ring semiconductors with multiple ion storage sites as ammonium ion storage materials to increase the specific capacity of water-based rechargeable ammonium ion batteries. The present invention is first prepared at a current density than 50mAg -1 355mAhg -1 capacity of aqueous ammonium ion based battery electrode pyrazine ring fused semiconductor, a rapid discharge of the electrode at a current density of 600mAg -1 capacity ratio can reach 190mAhg -1 .
说明书附图Attached drawings
图1是本发明实施例1制备的吡嗪稠环半导体DQP的结构式；Figure 1 is the structural formula of the pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention;
图2是本发明实施例1制备的基于吡嗪稠环半导体DQP的水系铵离子电池电极的充放电曲线图；2 is a charge-discharge curve diagram of an electrode for an aqueous ammonium ion battery based on a pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention;
图3是本发明实施例1制备的基于吡嗪稠环半导体DQP的水系铵离子电池电极的倍率性能曲线图；3 is a graph showing the rate performance curve of an electrode for an aqueous ammonium ion battery based on a pyrazine fused ring semiconductor DQP prepared in Example 1 of the present invention;
图4是本发明实施例2制备的吡嗪稠环半导体DPQDPP的结构式；4 is the structural formula of the pyrazine fused ring semiconductor DPQDPP prepared in Example 2 of the present invention;
图5是本发明实施例2制备的基于吡嗪稠环半导体DPQDPP的水系铵离子电池电极的充放电曲线图。5 is a graph showing the charge and discharge curves of the electrode of the water-based ammonium ion battery based on the pyrazine fused ring semiconductor DPQDPP prepared in Example 2 of the present invention.
具体实施方式Detailed ways
下面结合实施例和附图对本发明进一步说明。The present invention will be further described below in conjunction with embodiments and drawings.
现结合实施例、附图对本发明作进一步描述：The present invention will now be further described in conjunction with the embodiments and drawings:
基于吡嗪稠环半导体的水系铵离子电池电极，以吡嗪稠环芳烃为铵离子存储材料，在铵离子水系电解质溶液和大气环境中即可实现铵离子的电化学插入和脱出。A water-based ammonium ion battery electrode based on pyrazine fused ring semiconductors uses pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage material, and electrochemical insertion and extraction of ammonium ions can be realized in an ammonium ion aqueous electrolyte solution and an atmospheric environment.
上述铵离子存储材料为吡嗪稠环芳烃，其在于芳烃分子中至少含有一个吡嗪单元，且为稠环结构。The above-mentioned ammonium ion storage material is a pyrazine condensed ring aromatic hydrocarbon, which is that the aromatic hydrocarbon molecule contains at least one pyrazine unit and has a condensed ring structure.
优选地，上述吡嗪稠环芳烃包括但不限于以下结构通式的一种：Preferably, the above-mentioned pyrazine fused ring aromatic hydrocarbon includes but is not limited to one of the following general structural formulas:
Figure PCTCN2020136695-appb-000002
Figure PCTCN2020136695-appb-000002
优选地，上述结构通式中Ar 1、Ar 2和Ar 3基团独立的包括芳烃或杂环芳烃。 Preferably, the Ar 1 , Ar 2 and Ar 3 groups in the above general structural formula independently include aromatic hydrocarbons or heterocyclic aromatic hydrocarbons.
优选地，上述结构通式中R 1和R 2基团独立的包括H、卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳烃或杂环芳烃。 Preferably, the R 1 and R 2 groups in the above general structural formula independently include H, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, Aromatics or heterocyclic aromatics.
优选地，上述芳烃为单环或稠环芳烃，包括但不限于苯、萘、蒽、菲、芘、苝、芴等芳烃及其含取代基的衍生物。Preferably, the above-mentioned aromatic hydrocarbons are monocyclic or condensed ring aromatic hydrocarbons, including but not limited to aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene, and derivatives containing substituents.
优选地，上述杂环芳烃为单环或稠环杂环芳烃，包括但不限于吡咯、呋喃、噻吩、噻唑、二唑、三唑、吡啶、嘧啶、哒嗪、吡嗪、喹啉、异喹啉、喹喔啉、酞嗪、苯并噻唑、苯并二唑、菲罗啉、咔唑、磷芴、硅芴、吩噻嗪等杂环芳烃及其含取代基的衍生物。Preferably, the above-mentioned heterocyclic aromatic hydrocarbons are monocyclic or fused-ring heterocyclic aromatic hydrocarbons, including but not limited to pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquine Heterocyclic aromatic hydrocarbons such as morpholine, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphofluorene, silicon fluorene, phenothiazine, and derivatives containing substituents.
优选地，上述含取代基的衍生物中的取代基包括但不限于卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳香基或杂环芳香基等。Preferably, the substituents in the above-mentioned substituent-containing derivatives include, but are not limited to, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, and aromatic groups. Or heterocyclic aromatic groups and so on.
优选地，所述的铵离子水系电解质溶液为以硫酸铵、氯化铵、硝酸铵、 碳酸铵、碳酸氢铵、氟化铵、碘化铵、溴化铵和三氟甲磺酸铵中的一种或多种配制而成的水溶液，且其中铵盐的浓度为0.1M-21M。Preferably, the ammonium ion aqueous electrolyte solution is selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium fluoride, ammonium iodide, ammonium bromide and ammonium triflate. One or more aqueous solutions prepared, and the concentration of the ammonium salt is 0.1M-21M.
所述基于吡嗪稠环半导体的水系铵离子电池电极，其制备步骤包括如下：The preparation steps of the water-based ammonium ion battery electrode based on pyrazine fused ring semiconductor include the following:
(1)将吡嗪稠环芳烃化合物与导电剂、粘结剂、溶剂混合均匀，形成电极浆料，其中溶剂包括但不限于去离子水或有机溶剂，所述有机溶剂为N-吡咯烷酮、二甲基亚砜或二甲基甲酰胺，吡嗪稠环芳烃化合物、导电剂和粘结剂的质量比例为6：3：1-9：0：1。(1) The pyrazine fused ring aromatic compound is uniformly mixed with a conductive agent, a binder, and a solvent to form an electrode slurry. The solvent includes, but is not limited to, deionized water or an organic solvent. The organic solvent is N-pyrrolidone, two The mass ratio of methyl sulfoxide or dimethylformamide, pyrazine fused ring aromatic compound, conductive agent and binder is 6:3:1-9:0:1.
(2)将所述电极浆料涂覆在集流体上，形成极片；(2) Coating the electrode slurry on the current collector to form pole pieces;
(3)将上述极片置于真空烘箱中烘烤干燥，干燥温度为25～200℃，干燥时间为1～36h。(3) Put the pole piece in a vacuum oven for baking and drying, the drying temperature is 25-200°C, and the drying time is 1-36h.
所述基于吡嗪稠环半导体的水系铵离子电池电极，其充放电比容量、库伦效率、倍率性能测试等电池性能测试是在三电极体系中进行的。For the pyrazine fused ring semiconductor-based aqueous ammonium ion battery electrode, battery performance tests such as charge-discharge specific capacity, Coulomb efficiency, rate performance test, etc. are carried out in a three-electrode system.
优选地，所述三电极体系的制备和组装过程如下：Preferably, the preparation and assembly process of the three-electrode system is as follows:
(1)以活性炭与导电剂、粘结剂混合制备活性炭对电极极片；(1) Activated carbon is mixed with conductive agent and binder to prepare activated carbon counter electrode pole piece;
(2)用隔膜材料将上述制备的基于吡嗪稠环半导体的水系铵离子电池电极和活性炭对电极极片隔开，放入电池壳中，注入上述铵离子水系电解质溶液中的一种作为电解液；(2) Separate the pyrazine fused ring semiconductor-based water-based ammonium ion battery electrode and the activated carbon counter electrode pole piece with a separator material, put it into the battery case, and inject one of the above-mentioned ammonium ion water-based electrolyte solutions as electrolysis liquid;
(3)插入参比电极，参比电极包括但不限于Ag/AgCl电极或甘汞电极。(3) Insert a reference electrode, which includes but is not limited to Ag/AgCl electrode or calomel electrode.
上述三电极体系的制备和组装过程均在室温条件下于大气氛围下完成，无需额外的无水无氧环境。The preparation and assembly processes of the above-mentioned three-electrode system are all completed in the atmosphere at room temperature, without the need for an additional anhydrous and oxygen-free environment.
实施例1Example 1
一种基于吡嗪稠环半导体二喹喔啉并[2,3-a:2',3'-c]吩嗪(DQP，结构式如图1所示)的水系铵离子电池电极，具体制备方法如下：将80mg吡嗪稠环芳烃化合物DQAPZ，20mg的碳纳米管，10mg的聚偏氟乙烯粘结剂研磨混合均匀，加入适量N-吡咯烷酮搅拌获得均匀的浆料，均匀的涂在干净的钛箔上，于真空烘箱中60℃干燥12h。A water-based ammonium ion battery electrode based on the pyrazine fused ring semiconductor diquinoxalino[2,3-a:2',3'-c]phenazine (DQP, the structural formula is shown in Figure 1), and the specific preparation method As follows: Grind and mix 80 mg of pyrazine fused ring aromatic compound DQAPZ, 20 mg of carbon nanotubes, and 10 mg of polyvinylidene fluoride binder, add an appropriate amount of N-pyrrolidone and stir to obtain a uniform slurry, and evenly coat it on clean titanium On the foil, dry in a vacuum oven at 60°C for 12 hours.
活性炭电极极片的具体制备方法如下：将活性炭与聚偏氟乙烯按9：1加入到N-吡咯烷基酮中，搅拌获得均匀浆料；然后用抽滤的方法将浆 料制成碳电极，于真空烘箱中60℃干燥12h。The specific preparation method of the activated carbon electrode sheet is as follows: add activated carbon and polyvinylidene fluoride to N-pyrrolidone at 9:1, stir to obtain a uniform slurry; then use suction filtration to make the slurry into a carbon electrode ，Dry in a vacuum oven at 60℃ for 12h.
作为具体实施例，基于DQP的水系铵离子电池电极的三电极体系组装如下：以上述制备的基于DQP的水系铵离子电池电极作为工作电极，玻璃纤维作为隔膜，活性炭电极作为对电极，Ag/AgCl电极作为参比电极，将上述电极依次放入电池池体中，加入0.5M的硫酸铵水溶液作为电解液，拧紧电池。As a specific example, the three-electrode system of the DQP-based water-based ammonium ion battery electrode is assembled as follows: the DQP-based water-based ammonium ion battery electrode prepared above is used as the working electrode, glass fiber is used as the diaphragm, the activated carbon electrode is used as the counter electrode, and Ag/AgCl The electrode is used as a reference electrode, the above-mentioned electrodes are sequentially placed in the battery cell body, 0.5M ammonium sulfate aqueous solution is added as the electrolyte, and the battery is tightened.
作为具体实施例，基于DQP的水系铵离子电池电极的充放电曲线如图2所示，在-1.0～0.6V(vs.Ag/AgCl)工作区间内，以50mAg -1的电流密度进行充放电测试，放电比容量达到了360mAhg -1，放电比容量达到了355mAhg -1，库伦效率为98.6％。 As a specific example, the charging and discharging curve of DQP-based water-based ammonium ion battery electrodes is shown in Figure 2. In the working range of -1.0～0.6V (vs.Ag/AgCl), charging and discharging are performed at a current density of 50mAg -1 Tests showed that the discharge specific capacity reached 360mAhg -1 , the discharge specific capacity reached 355mAhg -1 , and the coulombic efficiency was 98.6%.
作为具体实施例，基于DQP的水系铵离子电池电极的倍率性能测试如图3所示，在-1.0～0.6V(vs.Ag/AgCl)工作区间内，以不同的电流密度进行充放电测试；在50、100、200、400、600mAg -1的电流密度下的放电比容量分别达到了355、300、260、220、190mAhg -1。 As a specific example, the rate performance test of the electrode of the water-based ammonium ion battery based on DQP is shown in FIG. discharging at a current density of 50,100,200,400,600mAg -1, respectively, the specific capacity 355,300,260,220,190mAhg -1.
实施例2Example 2
一种基于吡嗪稠环半导体二吡啶并[3',2':5,6；2”,3”:7,8]喹喔啉并[2,3-i]二吡啶并[3,2-a:2',3'-c]吩嗪(DPQDPP，结构式如图4所示)的水系铵离子电池电极，具体制备方法如下：将80mg吡嗪稠环芳烃化合物DPQDPP，20mg的碳纳米管，10mg的聚偏氟乙烯粘结剂研磨混合均匀，加入适量N-吡咯烷酮搅拌获得均匀的浆料，均匀的涂在干净的钛箔上，于真空烘箱中60℃干燥12h。A pyrazine-based condensed ring semiconductor bipyrido[3',2':5,6; 2”,3”:7,8]quinoxalino[2,3-i]dipyrido[3,2 -a: 2',3'-c] phenazine (DPQDPP, the structural formula is shown in Figure 4) water-based ammonium ion battery electrode, the specific preparation method is as follows: 80mg pyrazine fused ring aromatic compound DPQDPP, 20mg carbon nanotubes , 10mg of polyvinylidene fluoride binder is ground and mixed evenly, add an appropriate amount of N-pyrrolidone and stir to obtain a uniform slurry, evenly coat it on a clean titanium foil, and dry it in a vacuum oven at 60°C for 12 hours.
作为具体实施例，基于DPQDPP的水系铵离子电池电极的三电极体系组装如下：以上述制备的基于DPQDPP的水系铵离子电池电极作为工作电极，玻璃纤维作为隔膜，实施例1中的活性炭电极作为对电极，Ag/AgCl电极作为参比电极，将上述电极依次放入电池池体中，加入0.5M的硫酸铵水溶液作为电解液，拧紧电池。As a specific example, the three-electrode system of the DPQDPP-based water-based ammonium ion battery electrode is assembled as follows: the DPQDPP-based water-based ammonium ion battery electrode prepared above is used as the working electrode, glass fiber is used as the separator, and the activated carbon electrode in Example 1 is used as the counter Electrode, Ag/AgCl electrode as the reference electrode, put the above-mentioned electrodes in the battery cell in turn, add 0.5M ammonium sulfate aqueous solution as electrolyte, and tighten the battery.
作为具体实施例，基于DPQDPP的水系铵离子电池电极的充放电曲线如图5所示，在-1.1～0.7V(vs.Ag/AgCl)工作区间内，以50mAg -1的电流密度进行充放电测试，充电比容量为208mAhg -1，放电比容量为135mAhg -1，库伦效率为65％。 As a specific example, the charge-discharge curve of the electrode of the water-based ammonium ion battery based on DPQDPP is shown in Figure 5. In the working range of -1.1~0.7V (vs.Ag/AgCl), the charge and discharge are performed at a current density of 50mAg -1 According to the test, the specific charge capacity is 208mAhg -1 , the specific discharge capacity is 135 mAhg -1 , and the coulombic efficiency is 65%.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The description of the above embodiments is only used to help understand the method and the core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (10)

  1. 一种基于吡嗪稠环半导体的水系铵离子电池电极，其特征在于，以吡嗪稠环芳烃为铵离子存储材料，在铵离子水系电解质溶液和大气环境中即可实现铵离子的电化学插入和脱出；所述的吡嗪稠环芳烃的芳烃分子中至少含有一个吡嗪单元，且为稠环结构；所述的铵离子水系电解质溶液为以硫酸铵、氯化铵、硝酸铵、碳酸铵、碳酸氢铵、氟化铵、碘化铵、溴化铵和三氟甲磺酸铵中的一种或多种配制而成的水溶液，且其中铵盐的浓度为0.1M-21M。An aqueous ammonium ion battery electrode based on pyrazine fused ring semiconductor, which is characterized in that pyrazine fused ring aromatic hydrocarbon is used as an ammonium ion storage material, and the electrochemical insertion of ammonium ions can be realized in an ammonium ion aqueous electrolyte solution and an atmospheric environment The aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure; the ammonium ion aqueous electrolyte solution is made of ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium carbonate , Ammonium bicarbonate, ammonium fluoride, ammonium iodide, ammonium bromide, and ammonium trifluoromethanesulfonate in one or more of the aqueous solutions, and the concentration of the ammonium salt is 0.1M-21M.
  2. 一种水系铵离子电池电极，以吡嗪稠环芳烃作为铵离子存储材料，所述的吡嗪稠环芳烃的芳烃分子中至少含有一个吡嗪单元，且为稠环结构；所述电极包括集流体和涂覆在所述集流体上的电极浆料干燥物，所述电极浆料为吡嗪稠环芳烃化合物与导电剂、粘结剂和溶剂，所述吡嗪稠环芳烃化合物、导电剂和粘结剂的质量比例为6：3：1-9：0：1。A water-based ammonium ion battery electrode, which uses pyrazine fused ring aromatic hydrocarbon as an ammonium ion storage material. The aromatic hydrocarbon molecule of the pyrazine fused ring aromatic hydrocarbon contains at least one pyrazine unit and has a fused ring structure; the electrode includes a collector Fluid and dried electrode slurry coated on the current collector, the electrode slurry is a pyrazine fused ring aromatic compound and a conductive agent, a binder and a solvent, the pyrazine fused ring aromatic compound, a conductive agent The mass ratio with binder is 6:3:1-9:0:1.
  3. 根据权利要求1或2所述的一种基于吡嗪稠环半导体的水系铵离子电池电极，其特征在于，所述的吡嗪稠环芳烃包括但不限于以下结构通式的一种：An aqueous ammonium ion battery electrode based on a pyrazine fused ring semiconductor according to claim 1 or 2, wherein the pyrazine fused ring aromatic hydrocarbon includes but is not limited to one of the following general structural formulas:
    Figure PCTCN2020136695-appb-100001
    Figure PCTCN2020136695-appb-100001
    结构通式中Ar 1、Ar 2和Ar 3基团独立的包括芳烃或杂环芳烃 In the general structure, the Ar 1 , Ar 2 and Ar 3 groups independently include aromatic hydrocarbons or heterocyclic aromatic hydrocarbons
    R 1和R 2基团独立的包括H、卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳烃或杂环芳烃。 The R 1 and R 2 groups independently include H, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, mercapto, ester, acyl, cyano, sulfonic acid, aromatic hydrocarbon or heterocyclic aromatic hydrocarbon.
  4. 根据权利要求1所述的一种基于吡嗪稠环半导体的水系铵离子电池 电极，其特征在于，所述的芳烃为单环或稠环芳烃，包括但不限于苯、萘、蒽、菲、芘、苝、芴及其含取代基的衍生物。An aqueous ammonium ion battery electrode based on a pyrazine fused ring semiconductor according to claim 1, wherein the aromatic hydrocarbon is a monocyclic or fused ring aromatic hydrocarbon, including but not limited to benzene, naphthalene, anthracene, phenanthrene, Pyrene, perylene, fluorene and derivatives containing substituents.
  5. 根据权利要求1所述的一种基于吡嗪稠环半导体的水系铵离子电池电极，其特征在于，所述的杂环芳烃为单环或稠环杂环芳烃，包括但不限于吡咯、呋喃、噻吩、噻唑、二唑、三唑、吡啶、嘧啶、哒嗪、吡嗪、喹啉、异喹啉、喹喔啉、酞嗪、苯并噻唑、苯并二唑、菲罗啉、咔唑、磷芴、硅芴、吩噻嗪及其含取代基的衍生物。An aqueous ammonium ion battery electrode based on a pyrazine fused ring semiconductor according to claim 1, wherein the heterocyclic aromatic hydrocarbon is a monocyclic or fused ring heterocyclic aromatic hydrocarbon, including but not limited to pyrrole, furan, Thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, Phosphofluorene, silicon fluorene, phenothiazine and derivatives with substituents.
  6. 根据权利要求4或5所述的一种基于吡嗪稠环半导体的水系铵离子电池电极，其特征在于，所述含取代基的衍生物中的取代基包括但不限于卤素、烷基、卤代烷基、氨基、羟基、烷氧基、巯基、酯基、酰基、氰基、磺酸基、芳香基或杂环芳香基。An aqueous ammonium ion battery electrode based on a pyrazine fused ring semiconductor according to claim 4 or 5, wherein the substituents in the substituent-containing derivatives include but are not limited to halogen, alkyl, haloalkane Group, amino group, hydroxy group, alkoxy group, mercapto group, ester group, acyl group, cyano group, sulfonic acid group, aromatic group or heterocyclic aromatic group.
  7. 一种基于吡嗪稠环半导体的水系铵离子电池电极的制备方法，其特征在于步骤如下：A method for preparing water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors is characterized in that the steps are as follows:
    步骤1：将吡嗪稠环芳烃化合物与导电剂、粘结剂、溶剂混合均匀，形成电极浆料；吡嗪稠环芳烃化合物、导电剂和粘结剂的质量比例为6：3：1-9：0：1；Step 1: Mix the pyrazine fused ring aromatic compound with the conductive agent, the binder, and the solvent uniformly to form an electrode slurry; the mass ratio of the pyrazine fused ring aromatic compound, the conductive agent and the binder is 6:3:1 9:0:1;
    步骤2：将所述电极浆料涂覆在集流体上，形成极片；Step 2: Coating the electrode slurry on the current collector to form pole pieces;
    步骤3：将上述极片置于真空烘箱中烘烤干燥，干燥温度为25～200℃，干燥时间为1～36h。Step 3: Put the above pole piece in a vacuum oven for baking and drying, the drying temperature is 25-200°C, and the drying time is 1-36h.
  8. 根据权利要求7所述的一种基于吡嗪稠环半导体的水系铵离子电池电极的制备方法，其特征在于，所述的溶剂为水或有机溶剂，所述有机溶剂包括但不限于N-吡咯烷酮、二甲基亚砜或二甲基甲酰胺。The method for preparing an aqueous ammonium ion battery electrode based on a pyrazine fused ring semiconductor according to claim 7, wherein the solvent is water or an organic solvent, and the organic solvent includes but is not limited to N-pyrrolidone , Dimethyl sulfoxide or dimethyl formamide.
  9. 一种基于吡嗪稠环半导体的水系铵离子电池电极的测试方法，其特征在于，在三电极体系中进行的，所述的三电极体系制备和组装过程如下：A method for testing water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors, which is characterized in that it is carried out in a three-electrode system, and the preparation and assembly process of the three-electrode system is as follows:
    步骤1：以活性炭与导电剂、粘结剂混合制备活性炭对电极极片；Step 1: Prepare activated carbon counter electrode pole piece by mixing activated carbon, conductive agent and binder;
    步骤2：用隔膜材料将制备的基于吡嗪稠环半导体的水系铵离子电池电极和活性炭对电极极片隔开，放入电池壳中，注入铵离子水系电解质溶液中的一种作为电解液；Step 2: Separate the prepared water-based ammonium ion battery electrode based on the pyrazine fused ring semiconductor and the activated carbon counter electrode pole piece with a diaphragm material, put it into the battery case, and inject one of the ammonium ion water-based electrolyte solutions as an electrolyte;
    步骤3：插入参比电极；Step 3: Insert the reference electrode;
    步骤4：进行电池性能测试。Step 4: Perform battery performance test.
  10. 根据权利要求9所述的一种基于吡嗪稠环半导体的水系铵离子电池电极的测试方法，其特征在于，所述的参比电极包括但不限于Ag/AgCl电极或甘汞电极。The method for testing water-based ammonium ion battery electrodes based on pyrazine fused ring semiconductors according to claim 9, wherein the reference electrode includes, but is not limited to, an Ag/AgCl electrode or a calomel electrode.
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