阅读说明：本技术 一种水系钠离子电池负极材料的制备方法 (Preparation method of cathode material of water-based sodium-ion battery ) 是由 韩建涛 徐月 张爱文 于 2019-10-15 设计创作，主要内容包括：本发明涉及蓄电池技术领域,且公开了一种水系钠离子电池负极材料的制备方法,包括以下步骤,使用合金钛片作为金属负极基板,并使用打磨抛光设备去除表面氧化膜,再使用折弯设备进行统一塑形,形成负极基板组,制备纯相NaTi<Sub>2</Sub>(PO<Sub>4</Sub>)<Sub>3</Sub>的粉末原料,使用聚合物前驱体法制备出NaTi<Sub>2</Sub>(PO<Sub>4</Sub>)<Sub>3</Sub>的固体有机聚合物树脂,将制备的固体有机聚合物树脂在300-500℃环境下进行5-10分钟煅烧。该水系钠离子电池负极材料的制备方法,相比于直接使用蒽醌有机聚合物作为负极材料,在6C倍率充放电条件下,循环20000次后的剩余容量仍能大于90％,且成本更低,与直接使用纯相NaTi<Sub>2</Sub>(PO<Sub>4</Sub>)<Sub>3</Sub>覆盖在负极基板上进行压制使用对比,但可逆容量可提升一倍,具有更好的导电性,在相同成本中具有更高的性价比。(The invention relates to the technical field of storage batteries and discloses a preparation method of a cathode material of a water system sodium ion battery 2 (PO 4 ) 3 The method for preparing NaTi by using polymer precursor 2 (PO 4 ) 3 The solid organic polymer resin of (1) is calcined at the temperature of 300-500 ℃ for 5-10 minutes. Compared with the method for directly using the anthraquinone organic polymer as the negative electrode material, the preparation method of the water-based sodium-ion battery negative electrode material can still ensure that the residual capacity after the cycle of 20000 times can be still kept under the condition of 6C-rate charge and dischargeMore than 90 percent, lower cost and direct use of pure phase NaTi 2 (PO 4 ) 3 The coating is covered on a negative electrode substrate for pressing and using comparison, but reversible capacity can be doubled, and the coating has better conductivity and higher cost performance in the same cost.)

1. A preparation method of a cathode material of a water system sodium-ion battery is characterized by comprising the following steps:

1) using an alloy titanium sheet as a metal negative electrode substrate, removing a surface oxidation film by using polishing equipment, and uniformly shaping by using bending equipment to form a negative electrode substrate group;

2) preparation of pure phase NaTi₂(PO₄)₃The powder raw material of (1);

preparation of NaTi by using polymer precursor method₂(PO₄)₃The solid organic polymer resin of (4);

calcining the prepared solid organic polymer resin at the temperature of 300-500 ℃ for 5-10 minutes, and screening and filtering out internal impurities to obtain pure-phase NaTi₂(PO₄)₃The powder raw material of (1);

3) mixing pure phase NaTi₂(PO₄)₃The powder raw material of (a) is poured into a mixing device and added to pure phase NaTi₂(PO₄)₃In the powder raw material (a) 7: 1, adding activated carbon particles with the particle diameter of less than 0.1 mm by weight, mixing for 10-12 minutes by using a mixing device, adding a binder with the mixture ratio of 1:45 after mixing for 4 minutes, and mixing again until the mixing time is 10-12 minutes to obtain a pasty mixture;

4) adding hydrogen evolution inhibitor and anthraquinone-containing organic polymer into the paste mixture, and mixing again at constant temperature of 90-100 deg.C for 5-8 min to obtain paste mixture;

5) covering the paste mixture prepared in the step 4) on a titanium sheet substrate to form a covering film with the thickness of two millimeters, sleeving a nano non-woven fabric outside the covering film, and drying and compacting by using drying and pressing equipment to uniformly cover the surface of the titanium sheet substrate;

6) and (3) combining the plurality of negative electrode plate groups at equal intervals to obtain the cathode material of the water-based sodium-ion battery.

2. The method for preparing the anode material of the aqueous sodium-ion battery according to claim 1, characterized in that: the hydrogen evolution inhibitor is polytetrafluoroethylene, and the weight ratio of the hydrogen evolution inhibitor to the paste mixture in the step 4) is 1: 20.

3. The method for preparing the anode material of the aqueous sodium-ion battery according to claim 1, characterized in that: the weight ratio of the anthraquinone organic polymer to the paste mixture in the step 4) is 2:5, and the reversible capacity of the negative electrode material prepared in the step 6) can reach 126-154 mA.h/g under the condition of 5A/g current density.

Technical Field

The invention relates to the technical field of storage batteries, in particular to a preparation method of a cathode material of a water-based sodium-ion battery.

Background

With the development of smart power grids and the continuous refreshing of market shares of renewable energy sources (including solar energy, wind energy, novel clean energy internal combustion engines, fuel cell technologies and the like), more requirements are put on large-scale secondary energy storage technologies, market people predict that the demand of the global fixed energy storage market will exceed 150 billion dollars by 2020, energy storage devices from thousands of watt-hours to hundreds of megawatt-hours are required no matter distributed energy storage or centralized energy storage, the current universal energy storage modes comprise pumped storage and battery energy storage, the pumped storage is greatly limited by geographical conditions, general regions do not have installation conditions, the battery energy storage is flexible and variable, and is the first choice of future energy storage The safety of the short-service-life box is not enough, the improvement of the existing battery, such as the technologies of a low-cost lithium ion battery, an advanced lead-acid battery box large-scale high-temperature sodium-sulfur battery and the like, tries to make the best of the advantages and avoid the disadvantages so as to meet the requirements of the future energy storage market, but the reserve of lithium resources is limited, and even if all the enriched lithium resources in the world are used for manufacturing the battery, the reserve of the lithium resources cannot meet one tenth of the energy storage requirements; lead and other heavy metal pollution puzzles human beings all the time, an effective method for thoroughly avoiding heavy metal toxicity cannot be found in a short time, the lead-acid battery is completely replaced by the lead-acid battery in countries and regions of European Union and the like according to the agenda, and the regulation for additionally imposing taxes on the lead-acid battery in China is recently issued; the high-temperature battery also meets a plurality of technical problems at present, the potential safety hazard problem needs to be broken through, and the water system sodium ion battery can overcome a series of defects of the existing battery in a customer-service manner, so that the requirements of people are met.

The traditional preparation method of the cathode material of the aqueous sodium-ion battery usually directly uses pure-phase NaTi₂(PO₄)₃Covering on the negative electrode substrate for pressing, the reversible capacity can reach 40-50 mA.h/g, and can release 70% reversible capacity at high rate of 100C, but the conductivity is poor, carbon coating is needed to improve the conductivity, the cost is greatly increased, while anthraquinone organic polymer is directly used as the negative electrode material, the reversible capacity can reach 217 mA.h/g under the condition of 5A/g current density, but the cycle 3 is thatThe capacity retention rate is reduced to 91% after 00 times, so a preparation method of the cathode material of the water-based sodium-ion battery is provided to solve the problem.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a preparation method of a cathode material of a water system sodium ion battery, which has the advantages of low cost and the like, solves the problem that the traditional preparation method of the cathode material of the water system sodium ion battery usually directly uses pure-phase NaTi₂(PO₄)₃The reversible capacity of the material can reach 40-50 mA.h/g when the material is coated on a negative electrode substrate for pressing, 70% of reversible capacity can be released at a high rate of 100C, but the conductivity is poor, carbon coating is needed to improve the conductivity, the cost is greatly increased, and the anthraquinone organic polymer is directly used as a negative electrode material, although the reversible capacity can reach 217 mA.h/g under the condition of 5A/g current density, the capacity retention rate can be reduced to 91% after the material is cycled for 300 times.

(II) technical scheme

In order to achieve the purpose of low cost, the invention provides the following technical scheme: a preparation method of a cathode material of a water system sodium-ion battery comprises the following steps:

1) using an alloy titanium sheet as a metal negative electrode substrate, removing a surface oxidation film by using polishing equipment, and uniformly shaping by using bending equipment to form a negative electrode substrate group;

2) preparation of pure phase NaTi₂(PO₄)₃The powder raw material of (1);

preparation of NaTi by using polymer precursor method₂(PO₄)₃The solid organic polymer resin of (4);

calcining the prepared solid organic polymer resin at the temperature of 300-500 ℃ for 5-10 minutes, and screening and filtering out internal impurities to obtain pure-phase NaTi₂(PO₄)₃The powder raw material of (1);

3) mixing pure phase NaTi₂(PO₄)₃The powder raw materials are poured into a mixing deviceAnd is oriented to pure phase NaTi₂(PO₄)₃In the powder raw material (a) 7: 1, adding activated carbon particles with the particle diameter of less than 0.1 mm by weight, mixing for 10-12 minutes by using a mixing device, adding a binder with the mixture ratio of 1:45 after mixing for 4 minutes, and mixing again until the mixing time is 10-12 minutes to obtain a pasty mixture;

4) adding hydrogen evolution inhibitor and anthraquinone-containing organic polymer into the paste mixture, and mixing again at constant temperature of 90-100 deg.C for 5-8 min to obtain paste mixture;

5) covering the paste mixture prepared in the step 4) on a titanium sheet substrate to form a covering film with the thickness of two millimeters, sleeving a nano non-woven fabric outside the covering film, and drying and compacting by using drying and pressing equipment to uniformly cover the surface of the titanium sheet substrate;

6) and (3) combining the plurality of negative electrode plate groups at equal intervals to obtain the cathode material of the water-based sodium-ion battery.

Preferably, the hydrogen evolution inhibitor is polytetrafluoroethylene, and the weight ratio of the hydrogen evolution inhibitor to the paste mixture in the step 4) is 1: 20.

Preferably, the weight ratio of the anthraquinone organic polymer to the paste mixture in the step 4) is 2:5, and the reversible capacity of the negative electrode material prepared in the step 6) can reach 126-154 mA.h/g under the condition of current density of 5A/g.

(III) advantageous effects

Compared with the prior art, the invention provides a preparation method of a cathode material of a water-based sodium-ion battery, which has the following beneficial effects:

the preparation method of the cathode material of the water system sodium ion battery comprises the steps of using an alloy titanium sheet as a metal cathode substrate, removing a surface oxidation film by using polishing equipment, uniformly shaping by using bending equipment to form a cathode substrate group, and preparing NaTi by using a polymer precursor method₂(PO₄)₃The solid organic polymer resin is prepared by calcining the prepared solid organic polymer resin at the temperature of 500 ℃ for 5-10 minutes under the environment of 300-₂(PO₄)₃The powder of (1) is prepared by mixing pure phase NaTi₂(PO₄)₃The powder raw material of (a) is poured into a mixing device and added to pure phase NaTi₂(PO₄)₃In the powder raw material (a) 7: 1, adding activated carbon particles with the particle diameter of less than 0.1 mm by weight, mixing for 10-12 minutes by using a mixing device, adding a binder with the mixture ratio of 1:45 after mixing for 4 minutes, mixing again until the total mixing time is 10-12 minutes to obtain a paste mixture, adding a hydrogen evolution inhibitor and an anthraquinone-containing organic polymer into the paste mixture, mixing again at the constant temperature of 90-100 ℃, mixing for 5-8 minutes to obtain the paste mixture, covering the obtained paste mixture on a titanium sheet substrate to form a covering film with the thickness of two millimeters, covering a nano non-woven fabric outside the covering film, drying and compacting by using a drying and compacting device, uniformly covering the surface of the titanium sheet substrate, and combining a plurality of cathode plate groups at equal intervals to obtain the cathode material of the water system sodium ion battery, compared with the method of directly using anthraquinone organic polymer as the cathode material, the residual capacity after 20000 cycles is still more than 90% under the condition of 6C rate charge and discharge, the cost is lower, and pure-phase NaTi is directly used₂(PO₄)₃Compared with the use of covering on the negative electrode substrate for pressing, the cost is slightly higher, but the reversible capacity can be doubled, the conductivity is better, and the cost performance is higher in the same cost.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.