WO2021004259A1 - Symmetrical aqueous sodium-ion battery - Google Patents

Symmetrical aqueous sodium-ion battery Download PDF

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WO2021004259A1
WO2021004259A1 PCT/CN2020/097375 CN2020097375W WO2021004259A1 WO 2021004259 A1 WO2021004259 A1 WO 2021004259A1 CN 2020097375 W CN2020097375 W CN 2020097375W WO 2021004259 A1 WO2021004259 A1 WO 2021004259A1
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symmetrical
electrode material
ion battery
sodium
material layer
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PCT/CN2020/097375
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French (fr)
Chinese (zh)
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徐丽
盛鹏
李慧
王博
薛晴
赵广耀
白会涛
陈新
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全球能源互联网研究院有限公司
国家电网有限公司
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

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  • This application relates to the field of electrochemical energy storage, for example, to a symmetrical aqueous sodium ion battery.
  • the sodium ion battery is a secondary battery with a reaction principle similar to that of the lithium ion battery. Due to its advantages in raw material reserves and price, it has the potential to be used in energy storage systems.
  • a sodium ion battery usually includes a positive electrode current collector, a negative electrode current collector, a positive electrode material layer, a negative electrode material layer, and an electrolyte.
  • the positive electrode material layer is coated on the positive electrode current collector, and the negative electrode material layer is coated on the negative electrode current collector.
  • the electrolyte is poured between the positive electrode material layer and the negative electrode material layer, and the electrolyte includes sodium salt and a solvent.
  • General sodium ion batteries are asymmetric batteries, that is, the electrode material used for the positive electrode material layer and the negative electrode material layer are different, so for asymmetric batteries, the production process involves both positive and negative electrodes.
  • the preparation of the material layer, and the energy storage mechanism of the symmetric battery and the asymmetric battery is the same, and because the positive electrode material is the same as the negative electrode material layer, only one electrode material layer needs to be produced during production. That is, and because the volume change of one electrode during charging and discharging can be offset by the opposite electrode, symmetrical sodium ions have gradually become a research and development hotspot for the sake of cost reduction.
  • the electrolyte solvents in the existing symmetrical sodium ion batteries are usually organic solvents. Although this type of battery has high energy density, organic solvents are flammable and explosive, which can cause deflagration during production and use. Accidents have safety issues, and because organic solvent electrolytes are generally toxic, they are also likely to cause environmental pollution, which is not conducive to environmental protection.
  • the energy densities of the two are 30Wh/kg and 40Wh/kg, respectively. It can be seen that the symmetrical aqueous sodium ion battery has Certain development prospects, but due to the need to have a wide voltage platform and a suitable electrochemical window for electrode materials for forming water-based sodium ion batteries, there are not many electrode materials to choose from.
  • the technical problem to be solved by this application includes overcoming the limitation of the electrochemical window of water in the water-based symmetrical sodium ion battery in the prior art, which leads to the defect of low selectivity as the electrode material of the water-based sodium ion battery. , Thereby providing a symmetrical water-based sodium ion battery.
  • both the positive electrode material layer and the negative electrode material layer of the battery are composed of materials including electrode materials, conductive agents, and binders.
  • the mixing ratio of the electrode material, conductive agent, and adhesive is 8:1:1 by mass ratio.
  • the conductive agent is at least one of conductive carbon (super P), conductive graphite, and carbon nanotubes.
  • the adhesive is at least one of polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), sodium polyacrylate (PAAS), and sodium alginate .
  • PTFE polytetrafluoroethylene
  • CMC sodium carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • PAAS sodium polyacrylate
  • sodium alginate sodium alginate
  • the battery includes:
  • a positive electrode sheet which includes a positive current collector and a positive electrode material layer coated on the positive current collector;
  • a negative electrode sheet which includes a negative electrode current collector and a negative electrode material layer coated on the negative electrode current collector; an electrolyte is poured between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte of the battery is an aqueous solution of sodium salt, and the concentration of sodium ions in the electrolyte is 0.5-6 mol ⁇ L -1 .
  • the sodium salt is at least one of sodium sulfate, sodium hydroxide, sodium chloride or sodium nitrate.
  • Na x MnO 2 has a variety of crystal forms, structures and physical properties, so Na x MnO 2 has excellent stability and electrochemical performance, and this type of sodium intercalation compound has Wide working voltage range and multiple charge-discharge voltage platforms, the Na content is highly adjustable (x is 0.22-0.66), Na x MnO 2 with different sodium abundance has different electrochemical potential, so by selecting Na x MnO 2 constructs a water-based symmetrical sodium-ion battery.
  • the electrochemical window of water is only 1.23V due to the narrow electrochemical window of water, and there are many side reactions in the water system, such as hydrogen evolution from water, and electrode materials. Decomposition, side reactions of materials with water and oxygen in water, etc., will directly affect the energy density of the battery.
  • the sodium ion concentration in the electrolyte is set to 0.5-6mol ⁇ L -1 and the sodium salt concentration in the electrolyte is determined.
  • the increase in the electrochemical activity of the water can reduce the electrochemical activity of the water, which can broaden the electrochemical stability window of the water, thereby improving the electrochemical performance of the electrode material in the aqueous solution and the energy density of the battery.
  • this application selects Na x MnO 2 as the electrode material and sets the sodium ion concentration in the electrolyte to 0.5-6 mol ⁇ L -1 , so that the application
  • the installed symmetrical water-based sodium ion battery has a higher energy density and a higher long-cycle cycle capacity retention rate.
  • the electrolyte used in this application is an aqueous electrolyte, which has significant advantages such as low cost, clean and efficient, and high safety.
  • this application has raw materials With significant advantages such as low price and high energy density, this application provides a new type of energy storage method and a type of symmetrical water-based sodium ion battery electrode material, which provides a reference for the development and utilization of large-scale energy storage in the future.
  • the conductive agent and the adhesive are selected from relatively common materials, so the source is relatively wide and easy to obtain, which can reduce the production of symmetrical water-based sodium to a certain extent.
  • the cost of ion batteries are selected from relatively common materials, so the source is relatively wide and easy to obtain, which can reduce the production of symmetrical water-based sodium to a certain extent.
  • Fig. 1 is a charge-discharge curve diagram of Example 1 of the present application at a current density of 1C;
  • Example 2 is a cyclic voltammetry curve diagram of Example 2 of the present application at a scanning speed of 0.5 mV/s;
  • Figure 3 is a long-period cycle curve diagram of Example 3 of the present application at a current density of 10C;
  • Fig. 4 is a long-period cycle curve diagram of Comparative Example 1 of the present application at a current density of 10C.
  • This embodiment relates to a symmetrical aqueous sodium ion battery, specifically a three-electrode system battery, including a positive electrode current collector, a negative electrode current collector, a positive electrode material layer, and a negative electrode material layer, wherein the positive electrode material layer is coated on On the positive electrode current collector, the negative electrode material layer is coated on the negative electrode current collector, and electrolyte is filled between the positive electrode material layer and the negative electrode material layer, and the electrolyte includes sodium salt and a solvent.
  • the battery of this embodiment is a three-electrode system, and Zn 2+ /Zn is the reference electrode.
  • the positive electrode material layer and the negative electrode material layer are made of Na 0.44 MnO 2 electrode active material, conductive carbon (super P), and polytetrafluoroethylene (PTFE) binder mixed in a mass ratio of 8:1:1 Prepared, the electrolyte is a 2mol/L Na 2 SO 4 solution.
  • This embodiment relates to a symmetrical water-based sodium ion battery.
  • the electrode active material used in this embodiment is Na 0.22 MnO 2
  • the electrolyte is a 6 mol/L NaOH solution.
  • This embodiment relates to a symmetrical water-based sodium ion battery.
  • the electrode active material used in this embodiment is Na 0.66 MnO 2
  • the electrolyte is 0.5 mol/L NaNO 3 Solution.
  • This comparative example relates to a symmetrical water-based sodium ion battery.
  • the difference between this comparative example and implementation 2 is that the electrolyte used in this example is a 7 mol/L NaOH solution.
  • This comparative example relates to a symmetrical water-based sodium ion battery based on Na 2 VTi(PO 4 ) 3 as the material.
  • the difference between this comparative example and Example 1 is that the electrode active material used in this comparative example is Na 2 VTi (PO 4 ) 3 , the electrolyte is 1mol/L Na 2 SO 4 , and the reference electrode is Ag/AgCl (0.197V vs. NHE).
  • Example 1 The symmetrical sodium ion battery provided in Example 1 was tested, and its charge and discharge curve at a current density of 120mA/g was obtained. As shown in Figure 1, it can be seen that there are multiple charge and discharge of the sodium ion battery of Example 1. Voltage platform, discharge capacity is 68.1mAh/g, average discharge voltage is about 1.40V.
  • Example 2 The symmetrical sodium ion battery provided in Example 2 was tested, and its cyclic voltammetry curve at a scanning speed of 0.5 mV/s was obtained. As shown in Figure 2, it can be clearly seen that there are many pairs of redox peaks, indicating that Na 0.22 MnO 2 undergoes a multi-step phase transition process during the insertion or extraction of Na + ions.
  • Example 3 The symmetrical sodium ion battery provided in Example 3 was tested, and its long-period cycle curve at a current density of 1200mA/g was obtained. As shown in Figure 3, it can be seen that the reversible capacity of the battery in the first week is 35.1 mAh/g. After 500 cycles of cycles, the capacity retention rate was 67%.
  • the symmetrical sodium ion battery provided by Comparative Example 1 was tested, and its long-period cycle curve at a current density of 1200mA/g was obtained. As shown in Figure 4, it can be seen that the reversible capacity of the battery in the first week is 41.1mAh/g. After 200 weeks of cycling, the capacity retention rate was 49%.

Abstract

The present invention relates to the field of electrochemical energy storage, and in particular, to a symmetrical aqueous sodium ion battery. The electrode material used in a positive electrode material layer and a negative electrode material layer of the battery is NaxMnO2 (x=0.22-0.66). The electrolyte of the battery is an aqueous solution of sodium salt, and the concentration of sodium ions in the electrolyte is 0.5-6 mol•L-1. By selecting NaxMnO2 as the electrode material and setting the concentration of sodium ions in the electrolyte to be 0.5-6 mol•L-1, the symmetrical aqueous sodium-ion battery of the present application has higher energy density which can reach more than 40 Wh/kg.

Description

一种对称型水系钠离子电池Symmetrical water-based sodium ion battery 技术领域Technical field
本申请涉及电化学储能领域，例如涉及一种对称型水系钠离子电池。This application relates to the field of electrochemical energy storage, for example, to a symmetrical aqueous sodium ion battery.
背景技术Background technique
随着太阳能、风能和其他类型的可再生能源被纳入电网并建设智能电网，储能技术已成为优化能源利用的关键。钠离子电池是一种反应原理与锂离子电池相似的二次电池，由于其在原材料储量和价格方面更具有优势，因此其具备用于储能***的潜在可能性。With the integration of solar, wind and other types of renewable energy into the grid and the construction of smart grids, energy storage technology has become the key to optimizing energy utilization. The sodium ion battery is a secondary battery with a reaction principle similar to that of the lithium ion battery. Due to its advantages in raw material reserves and price, it has the potential to be used in energy storage systems.
钠离子电池通常包括正极集流体、负极集流体、正极电极材料层、负极电极材料层、电解液，其中，正极电极材料层涂布在正极集流体上，负极电极材料层涂布在负极集流体上，电解液灌注在正极电极材料层与负极电极材料层之间，电解液包括钠盐以及溶剂。A sodium ion battery usually includes a positive electrode current collector, a negative electrode current collector, a positive electrode material layer, a negative electrode material layer, and an electrolyte. The positive electrode material layer is coated on the positive electrode current collector, and the negative electrode material layer is coated on the negative electrode current collector. Above, the electrolyte is poured between the positive electrode material layer and the negative electrode material layer, and the electrolyte includes sodium salt and a solvent.
一般的钠离子电池都是非对称型电池，即其正极电极材料层与负极电极材料层所选用的电极材料不同，故对于非对称型电池而言，在生产的过程中涉及正负极两种电极材料层的制备，而对称型电池和非对称型电池的储能机理一致，且由于其正极电极材料与负极电极材料层所选用的电极材料相同，故在生产时只需生产一种电极材料层即可，且由于其中一个电极在充放电过程中的体积变化可由相对的电极进行抵消，因此，出于降低成本的考虑，对称型钠离子逐渐成为研发热点。General sodium ion batteries are asymmetric batteries, that is, the electrode material used for the positive electrode material layer and the negative electrode material layer are different, so for asymmetric batteries, the production process involves both positive and negative electrodes. The preparation of the material layer, and the energy storage mechanism of the symmetric battery and the asymmetric battery is the same, and because the positive electrode material is the same as the negative electrode material layer, only one electrode material layer needs to be produced during production. That is, and because the volume change of one electrode during charging and discharging can be offset by the opposite electrode, symmetrical sodium ions have gradually become a research and development hotspot for the sake of cost reduction.
但是，现有的对称型钠离子电池中电解液的溶剂通常选用的都是有机溶剂，此类电池虽然能量密度较高，但是由于有机溶剂易燃易爆，在生产和使用过程中会造成爆燃事故，有安全性问题的缺陷，且由于有机溶剂电解液通常有毒， 故也容易对环境造成污染，不利于环境保护。However, the electrolyte solvents in the existing symmetrical sodium ion batteries are usually organic solvents. Although this type of battery has high energy density, organic solvents are flammable and explosive, which can cause deflagration during production and use. Accidents have safety issues, and because organic solvent electrolytes are generally toxic, they are also likely to cause environmental pollution, which is not conducive to environmental protection.
若采用水作为电解液的溶剂，则可以解决有机溶剂易燃易***的问题，但是由于水的电化学窗口的限制，大大制约了电极材料的选择，目前也有研究者报道了对称型水系钠离子电池，他们采用Na 2VTi(PO 4) 3、Na 3MnTi(PO 4) 3等材料进行研究，正负极分别利用V 4+/V 3+和Ti 4+/Ti 3+、Mn 3+/Mn 2+和Ti 4+/Ti 3+的氧化还原反应实现电能的储存和利用，经过检测此二者的能量密度分别为30Wh/kg和40Wh/kg，可见，对称型水系钠离子电池具有一定的发展前景，但是由于对成型水系钠离子电池的电极材料需要具备较宽的电压平台和合适的电化学窗口，因此可供选择的电极材料并不多见。 If water is used as the solvent of the electrolyte, the problem of flammability and explosion of organic solvents can be solved. However, due to the limitation of the electrochemical window of water, the choice of electrode materials is greatly restricted. At present, some researchers have reported symmetrical aqueous sodium ions. For batteries, they use Na 2 VTi(PO 4 ) 3 , Na 3 MnTi(PO 4 ) 3 and other materials for research. The positive and negative electrodes use V 4+ /V 3+ and Ti 4+ /Ti 3+ , Mn 3+ respectively. The oxidation-reduction reaction of /Mn 2+ and Ti 4+ /Ti 3+ realizes the storage and utilization of electric energy. After testing, the energy densities of the two are 30Wh/kg and 40Wh/kg, respectively. It can be seen that the symmetrical aqueous sodium ion battery has Certain development prospects, but due to the need to have a wide voltage platform and a suitable electrochemical window for electrode materials for forming water-based sodium ion batteries, there are not many electrode materials to choose from.
发明内容Summary of the invention
因此，本申请要解决的技术问题包括克服现有技术中的水系对称型钠离子电池中由于水的电化学窗口的限制，导致可供用作水系钠离子电池的电极材料的选择性较小的缺陷，从而提供一种对称型水系钠离子电池。Therefore, the technical problem to be solved by this application includes overcoming the limitation of the electrochemical window of water in the water-based symmetrical sodium ion battery in the prior art, which leads to the defect of low selectivity as the electrode material of the water-based sodium ion battery. , Thereby providing a symmetrical water-based sodium ion battery.
为解决上述技术问题，本申请采用的技术方案为：To solve the above technical problems, the technical solution adopted in this application is:
Na xMnO 2(x＝0.22-0.66)在对称型水系钠离子电池中的用途。 Use of Na x MnO 2 (x=0.22-0.66) in symmetrical water-based sodium ion batteries.
Na xMnO 2(x＝0.22-0.66)作为电极材料在对称型水系钠离子电池中的用途。 Use of Na x MnO 2 (x=0.22-0.66) as an electrode material in a symmetrical aqueous sodium ion battery.
一种对称型水系钠离子电池，所述电池的正极电极材料层与负极电极材料层所使用的电极材料均为Na xMnO 2(x＝0.22-0.66)。 A symmetrical water-based sodium ion battery, wherein the electrode materials used for the positive electrode material layer and the negative electrode material layer of the battery are both Na x MnO 2 (x=0.22-0.66).
可选地，所述电池的正极电极材料层与所述负极电极材料层均由包括电极材料、导电剂以及粘接剂的材料组成。Optionally, both the positive electrode material layer and the negative electrode material layer of the battery are composed of materials including electrode materials, conductive agents, and binders.
可选地，所述电极材料、导电剂以及粘接剂的混合比例为按质量比为8:1:1。Optionally, the mixing ratio of the electrode material, conductive agent, and adhesive is 8:1:1 by mass ratio.
可选地，所述导电剂为导电炭(super P)、导电石墨、碳纳米管中的至少一种。Optionally, the conductive agent is at least one of conductive carbon (super P), conductive graphite, and carbon nanotubes.
可选地，所述粘接剂为聚四氟乙烯(PTFE)、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、聚丙烯酸钠(PAAS)、海藻酸钠中的至少一种。Optionally, the adhesive is at least one of polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), sodium polyacrylate (PAAS), and sodium alginate .
可选地，所述电池包括：Optionally, the battery includes:
正极电极片，其包括正极集流体以及涂覆在所述正极集流体上的正极电极材料层；A positive electrode sheet, which includes a positive current collector and a positive electrode material layer coated on the positive current collector;
以及，负极电极片，其包括负极集流体以及涂覆在所述负极集流体上的负极电极材料层；所述正极电极片与所述负极电极片之间灌注有电解液。And, a negative electrode sheet, which includes a negative electrode current collector and a negative electrode material layer coated on the negative electrode current collector; an electrolyte is poured between the positive electrode sheet and the negative electrode sheet.
可选地，所述电池的电解液为钠盐的水溶液，所述电解液中钠离子浓度为0.5-6mol·L -1。 Optionally, the electrolyte of the battery is an aqueous solution of sodium salt, and the concentration of sodium ions in the electrolyte is 0.5-6 mol·L -1 .
可选地，所述钠盐为硫酸钠、氢氧化钠、氯化钠或硝酸钠中的至少一种。Optionally, the sodium salt is at least one of sodium sulfate, sodium hydroxide, sodium chloride or sodium nitrate.
本申请技术方案，具有如下优点：The technical solution of this application has the following advantages:
1.本申请提供的对称型水系钠离子电池，Na xMnO 2具有多种晶体形态、结构和物理性能，故Na xMnO 2具有优异的稳定性和电化学性能，且此类嵌钠化合物具有较宽的工作电压区间和多个充放电电压平台，其中的Na含量可调节度高(x为0.22-0.66)，不同钠丰度的Na xMnO 2具有不同的电化学势，故通过选用Na xMnO 2构建水系对称型钠离子电池，在充放电过程中，锰与其氧化态和还原态之间转化时会产生几个高电压和低电压平台，从而使得位于正负极的Na xMnO 2会分别形成贫钠态Na xMnO 2(0.22≤x≤0.44)和富钠态Na xMnO 2(0.66≤x≤0.44)，进而可以利用贫钠态Na xMnO 2(0.22≤x≤0.44)和富钠态Na xMnO 2(0.66≤x≤0.44)之间的电化学势差来成功构建水系对称型钠离子电池，本申请选择Na xMnO 2(x＝0.22-0.66)构建完全对称的水系钠离子电池，扩展了对称型水系钠离子电池的电极材料的选择多样性。 1. In the symmetrical aqueous sodium ion battery provided by this application, Na x MnO 2 has a variety of crystal forms, structures and physical properties, so Na x MnO 2 has excellent stability and electrochemical performance, and this type of sodium intercalation compound has Wide working voltage range and multiple charge-discharge voltage platforms, the Na content is highly adjustable (x is 0.22-0.66), Na x MnO 2 with different sodium abundance has different electrochemical potential, so by selecting Na x MnO 2 constructs a water-based symmetrical sodium-ion battery. During the charging and discharging process, the conversion between manganese and its oxidation state and reduction state will generate several high voltage and low voltage platforms, so that Na x MnO 2 located at the positive and negative poles Sodium-poor state Na x MnO 2 (0.22≤x≤0.44) and sodium-rich state Na x MnO 2 (0.66≤x≤0.44) are formed respectively, and then sodium-poor state Na x MnO 2 (0.22≤x≤0.44) can be used and an electrochemical reaction between 2 (0.66≤x≤0.44) Na x MnO sodium rich state potential difference successfully constructed symmetrical aqueous sodium ion battery, the present application selection Na x MnO 2 (x = 0.22-0.66 ) constructed fully symmetrical The water-based sodium ion battery expands the selection diversity of electrode materials for symmetrical water-based sodium ion batteries.
2.本申请提供的对称型水系钠离子电池，在水系钠离子电池中，由于水的 电化学窗口较窄，仅为1.23V，且在水体系中存在诸多副反应，如水析氢、电极材料的分解、材料与水和水中氧气发生副反应等，都会直接影响到电池的能量密度，本申请通过将电解液中的钠离子浓度设置为0.5-6mol·L -1，通过电解液中钠盐浓度的提高从而降低水的电化学活性，从而可以扩宽水的电化学稳定窗口，进而提高电极材料在水溶液中的电化学性能以及电池的能量密度，另外，钠盐浓度的提高也会带来电解液电导率的提升，从而提高电池的功率输出性能，故本申请通过选用Na xMnO 2作为电极材料，并将电解液中的钠离子浓度设置为0.5-6mol·L -1，从而使得本申请设置的对称型水系钠离子电池具有较高的能量密度，以及较高的长周期循环容量保持率。 2. In the symmetrical aqueous sodium ion battery provided by this application, the electrochemical window of water is only 1.23V due to the narrow electrochemical window of water, and there are many side reactions in the water system, such as hydrogen evolution from water, and electrode materials. Decomposition, side reactions of materials with water and oxygen in water, etc., will directly affect the energy density of the battery. In this application, the sodium ion concentration in the electrolyte is set to 0.5-6mol·L -1 and the sodium salt concentration in the electrolyte is determined The increase in the electrochemical activity of the water can reduce the electrochemical activity of the water, which can broaden the electrochemical stability window of the water, thereby improving the electrochemical performance of the electrode material in the aqueous solution and the energy density of the battery. In addition, the increase of the sodium salt concentration will also bring about electrolysis. The conductivity of the liquid is improved, thereby improving the power output performance of the battery. Therefore, this application selects Na x MnO 2 as the electrode material and sets the sodium ion concentration in the electrolyte to 0.5-6 mol·L -1 , so that the application The installed symmetrical water-based sodium ion battery has a higher energy density and a higher long-cycle cycle capacity retention rate.
3.本申请提供的对称型水系钠离子电池，由于正负极电极材料为同种材料，故在制备时只需制备一种电极片即可，制备工艺简单，易于实现大规模的生产，此外，相比于传统的有机系电池，本申请所采用的电解液为水系电解液，具有成本低、清洁高效、安全性高等显著优点；相比于目前已报道的同体系电池，本申请具有原材料价格低廉、能量密度高等显著优势，本申请提供了一种新型的储能方式和一类对称型水系钠离子电池电极材料，为未来大规模储能的开发和利用提供参考。3. In the symmetrical water-based sodium ion battery provided by this application, since the positive and negative electrode materials are the same kind of material, only one electrode sheet needs to be prepared during preparation, the preparation process is simple, and large-scale production is easy to realize. Compared with traditional organic batteries, the electrolyte used in this application is an aqueous electrolyte, which has significant advantages such as low cost, clean and efficient, and high safety. Compared with the currently reported batteries of the same system, this application has raw materials With significant advantages such as low price and high energy density, this application provides a new type of energy storage method and a type of symmetrical water-based sodium ion battery electrode material, which provides a reference for the development and utilization of large-scale energy storage in the future.
4.本申请提供的对称型水系钠离子电池，其中导电剂以及粘接剂均选用的是较为常见的材料，故其来源较为广泛，容易得到，从而可以在一定程度上降低制备对称型水系钠离子电池的成本。4. In the symmetrical water-based sodium ion battery provided by this application, the conductive agent and the adhesive are selected from relatively common materials, so the source is relatively wide and easy to obtain, which can reduce the production of symmetrical water-based sodium to a certain extent. The cost of ion batteries.
附图说明Description of the drawings
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific embodiments of this application or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the specific embodiments or the description of the prior art. Obviously, the appendix in the following description The drawings are some embodiments of the application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.
图1是本申请实施例1在1C电流密度下的充放电曲线图；Fig. 1 is a charge-discharge curve diagram of Example 1 of the present application at a current density of 1C;
图2是本申请实施例2在0.5mV/s的扫速下的循环伏安曲线图；2 is a cyclic voltammetry curve diagram of Example 2 of the present application at a scanning speed of 0.5 mV/s;
图3是本申请实施例3在10C电流密度下的长周期循环曲线图；Figure 3 is a long-period cycle curve diagram of Example 3 of the present application at a current density of 10C;
图4是本申请对比例1在10C电流密度下的长周期循环曲线图。Fig. 4 is a long-period cycle curve diagram of Comparative Example 1 of the present application at a current density of 10C.
具体实施方式Detailed ways
提供下述实施例是为了更好地进一步理解本申请，并不局限于所述最佳实施方式，不对本申请的内容和保护范围构成限制。The following examples are provided for a better understanding of this application, and are not limited to the best embodiments, and do not limit the content and protection scope of this application.
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。If the specific experimental steps or conditions are not indicated in the examples, it can be carried out according to the conventional experimental steps described in the literature in the field. The reagents or instruments used without the manufacturer's indication are all conventional reagent products that are commercially available.
实施例1Example 1
本实施例涉及一种对称型水系钠离子电池，具体为一种三电极体系电池，包括正极集流体、负极集流体、正极电极材料层以及负极电极材料层，其中，正极电极材料层涂布在正极集流体上，负极电极材料层涂布在负极集流体上，正极电极材料层与负极电极材料层之间灌注有电解液，电解液包括钠盐以及溶剂。This embodiment relates to a symmetrical aqueous sodium ion battery, specifically a three-electrode system battery, including a positive electrode current collector, a negative electrode current collector, a positive electrode material layer, and a negative electrode material layer, wherein the positive electrode material layer is coated on On the positive electrode current collector, the negative electrode material layer is coated on the negative electrode current collector, and electrolyte is filled between the positive electrode material layer and the negative electrode material layer, and the electrolyte includes sodium salt and a solvent.
本实施例的电池为三电极体系，Zn 2+/Zn为参比电极。其中，正极电极材料层及负极电极材料层均为由Na 0.44MnO 2电极活性物质、导电碳(super P)、聚四氟乙烯(PTFE)粘接剂按质量比8:1:1的比例混合制备而成，电解液为2mol/L的Na 2SO 4溶液。 The battery of this embodiment is a three-electrode system, and Zn 2+ /Zn is the reference electrode. Among them, the positive electrode material layer and the negative electrode material layer are made of Na 0.44 MnO 2 electrode active material, conductive carbon (super P), and polytetrafluoroethylene (PTFE) binder mixed in a mass ratio of 8:1:1 Prepared, the electrolyte is a 2mol/L Na 2 SO 4 solution.
实施例2Example 2
本实施例涉及一种对称型水系钠离子电池，本实施例与实施例1的区别在 于，本实施例中所使用的电极活性物质为Na 0.22MnO 2，电解液为6mol/L的NaOH溶液。 This embodiment relates to a symmetrical water-based sodium ion battery. The difference between this embodiment and Embodiment 1 is that the electrode active material used in this embodiment is Na 0.22 MnO 2 , and the electrolyte is a 6 mol/L NaOH solution.
实施例3Example 3
本实施例涉及一种对称型水系钠离子电池，本实施例与实施例1的区别在于，本实施例中所使用的电极活性物质为Na 0.66MnO 2，电解液为0.5mol/L的NaNO 3溶液。 This embodiment relates to a symmetrical water-based sodium ion battery. The difference between this embodiment and Embodiment 1 is that the electrode active material used in this embodiment is Na 0.66 MnO 2 , and the electrolyte is 0.5 mol/L NaNO 3 Solution.
对比例1Comparative example 1
本对比例涉及一种对称型水系钠离子电池，本对比例与实施2的区别之处在于，本实施例中所使用的电解液为7mol/L的NaOH溶液。This comparative example relates to a symmetrical water-based sodium ion battery. The difference between this comparative example and implementation 2 is that the electrolyte used in this example is a 7 mol/L NaOH solution.
对比例2Comparative example 2
本对比例涉及一种基于Na 2VTi(PO 4) 3为材料的对称型水系钠离子电池，本对比例与实施例1的区别在于，本对比例中所使用的电极活性材料为Na 2VTi(PO 4) 3，电解液为1mol/L的Na 2SO 4，参比电极为Ag/AgCl(0.197V vs.NHE)。 This comparative example relates to a symmetrical water-based sodium ion battery based on Na 2 VTi(PO 4 ) 3 as the material. The difference between this comparative example and Example 1 is that the electrode active material used in this comparative example is Na 2 VTi (PO 4 ) 3 , the electrolyte is 1mol/L Na 2 SO 4 , and the reference electrode is Ag/AgCl (0.197V vs. NHE).
试验例1Test example 1
对实施例1提供的对称型钠离子电池进行检测，获取其在120mA/g电流密度下的充放电曲线图，如图1所示，可以看出有实施例1的钠离子电池多个充放电电压平台，放电容量为68.1mAh/g，平均放电电压约为1.40V。The symmetrical sodium ion battery provided in Example 1 was tested, and its charge and discharge curve at a current density of 120mA/g was obtained. As shown in Figure 1, it can be seen that there are multiple charge and discharge of the sodium ion battery of Example 1. Voltage platform, discharge capacity is 68.1mAh/g, average discharge voltage is about 1.40V.
对实施例2提供的对称型钠离子电池进行检测，获取其在0.5mV/s扫描速度下的循环伏安曲线图，如图2所示，可以明显看出有多对氧化还原峰，说明Na 0.22MnO 2在Na +离子嵌入或脱出过程中经历了多步相转变过程。 The symmetrical sodium ion battery provided in Example 2 was tested, and its cyclic voltammetry curve at a scanning speed of 0.5 mV/s was obtained. As shown in Figure 2, it can be clearly seen that there are many pairs of redox peaks, indicating that Na 0.22 MnO 2 undergoes a multi-step phase transition process during the insertion or extraction of Na + ions.
对实施例3提供的对称型钠离子电池进行检测，获取其在1200mA/g电流密度下的长周期循环曲线图，如图3所示，可以看出电池首周可逆容量为35.1 mAh/g，经500周循环后，容量保持率为67％。The symmetrical sodium ion battery provided in Example 3 was tested, and its long-period cycle curve at a current density of 1200mA/g was obtained. As shown in Figure 3, it can be seen that the reversible capacity of the battery in the first week is 35.1 mAh/g. After 500 cycles of cycles, the capacity retention rate was 67%.
对对比例1提供的对称型钠离子电池进行检测，获取其在1200mA/g电流密度下的长周期循环曲线图，如图4所示，可以看出电池首周可逆容量为41.1mAh/g，经200周循环后，容量保持率为49％。The symmetrical sodium ion battery provided by Comparative Example 1 was tested, and its long-period cycle curve at a current density of 1200mA/g was obtained. As shown in Figure 4, it can be seen that the reversible capacity of the battery in the first week is 41.1mAh/g. After 200 weeks of cycling, the capacity retention rate was 49%.
试验例2Test example 2
对实施例1-3及对比例1-2提供的对称型钠离子电池进行检测，检测其在不同电流密度下的能量密度以及长周期循环性能，测试结果见表1。The symmetrical sodium ion batteries provided in Examples 1-3 and Comparative Examples 1-2 were tested, and their energy density and long-cycle cycle performance under different current densities were tested. The test results are shown in Table 1.
表1.各实施例及对比例的测试结果Table 1. Test results of each embodiment and comparative example
Figure PCTCN2020097375-appb-000001
Figure PCTCN2020097375-appb-000001
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本申请的保护范围之中。Obviously, the above-mentioned embodiments are merely examples for clear description, and are not intended to limit the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is unnecessary and impossible to list all the implementation methods here. The obvious changes or changes derived from this are still within the protection scope of this application.

Claims (10)

  1. 一种对称型水系钠离子电池，其中，所述电池的正极电极材料层与负极电极材料层所使用的电极材料均为Na xMnO 2，其中x＝0.22-0.66。 A symmetrical water-based sodium ion battery, wherein the electrode materials used in the positive electrode material layer and the negative electrode material layer of the battery are both Na x MnO 2 , where x = 0.22-0.66.
  2. 根据权利要求1所述的对称型水系钠离子电池，其中，所述电池包括：The symmetrical water-based sodium ion battery according to claim 1, wherein the battery comprises:
    正极，其包括正极集流体以及涂覆在所述正极集流体上的正极电极材料层；A positive electrode, which includes a positive electrode current collector and a positive electrode material layer coated on the positive electrode current collector;
    负极，其包括负极集流体以及涂覆在所述负极集流体上的负极电极材料层；和A negative electrode, which includes a negative current collector and a negative electrode material layer coated on the negative current collector; and
    电解液，其灌注在所述正极与所述负极之间。The electrolyte is poured between the positive electrode and the negative electrode.
  3. 根据权利要求2所述的对称型水系钠离子电池，其中，所述电解液为钠盐的水溶液，所述电解液中钠离子浓度为0.5-6mol·L -1。 The symmetrical aqueous sodium ion battery according to claim 2, wherein the electrolyte is an aqueous solution of sodium salt, and the concentration of sodium ions in the electrolyte is 0.5-6 mol·L -1 .
  4. 根据权利要求3所述的对称型水系钠离子电池，其中，所述钠盐包括硫酸钠、氢氧化钠、氯化钠或硝酸钠中的至少一种。The symmetrical aqueous sodium ion battery according to claim 3, wherein the sodium salt includes at least one of sodium sulfate, sodium hydroxide, sodium chloride, or sodium nitrate.
  5. 根据权利要求1-4中任一项所述的对称型水系钠离子电池，其中，所述电池的正极电极材料层与所述负极电极材料层均由包括所述电极材料、导电剂以及粘接剂的材料组成。The symmetrical water-based sodium ion battery according to any one of claims 1 to 4, wherein the positive electrode material layer and the negative electrode material layer of the battery are both composed of the electrode material, the conductive agent and the bonding agent. The material composition of the agent.
  6. 根据权利要求5所述的对称型水系钠离子电池，其中，在所述正极电极材料层中和所述负极电极材料层中，所述电极材料、导电剂以及粘接剂的混合比率均为按质量计8:1:1。The symmetrical water-based sodium ion battery according to claim 5, wherein, in the positive electrode material layer and the negative electrode material layer, the mixing ratio of the electrode material, the conductive agent, and the binder is according to The mass meter is 8:1:1.
  7. 根据权利要求5或6中所述的对称型水系钠离子电池，其中，所述导电剂包括导电炭、导电石墨、碳纳米管中的至少一种。The symmetrical aqueous sodium ion battery according to claim 5 or 6, wherein the conductive agent includes at least one of conductive carbon, conductive graphite, and carbon nanotubes.
  8. 根据权利要求5-7中任一项所述的对称型水系钠离子电池，其中，所述 粘接剂包括聚四氟乙烯、羧甲基纤维素钠、丁苯橡胶、聚丙烯酸钠、海藻酸钠中的至少一种。The symmetrical aqueous sodium ion battery according to any one of claims 5-7, wherein the binder comprises polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene butadiene rubber, sodium polyacrylate, alginic acid At least one of sodium.
  9. Na xMnO 2在对称型水系钠离子电池中的用途，其中x＝0.22-0.66。 The use of Na x MnO 2 in symmetrical aqueous sodium ion batteries, where x=0.22-0.66.
  10. Na xMnO 2作为电极材料在对称型水系钠离子电池中的用途，其中x＝0.22-0.66。 The use of Na x MnO 2 as an electrode material in a symmetrical aqueous sodium ion battery, where x=0.22-2.66.
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