技术领域technical field
本发明属于钠离子电池技术领域，涉及一种橄榄石型NaFePO4钠离子电池正极材料的制备方法。The invention belongs to the technical field of sodium ion batteries, and relates to a preparation method of an olivine-typeNaFePO4 sodium ion battery cathode material.
背景技术Background technique
近年来，由于环境问题日益严重，能源危机，新能源的开发利用与储能技术的发展现已成为人类共同面对的问题。锂离子电池因其优异的性能，已经广泛应用于便携式数码产品。未来，锂离子电池因长使用寿命，高比能量等优点而受到储能领域工作者的重视。然而，锂离子电池应用于储能领域还面临着一些挑战。首先，地球上锂源储量是有限的，金属锂的价格会随着锂离子电池大规模应用而逐渐上升，其次，开发出理想的电极材料进一步提高其性能显得尤为重要。In recent years, due to the increasingly serious environmental problems and the energy crisis, the development and utilization of new energy and the development of energy storage technology have become common problems faced by mankind. Lithium-ion batteries have been widely used in portable digital products because of their excellent performance. In the future, lithium-ion batteries will be valued by workers in the energy storage field due to their long service life and high specific energy. However, the application of lithium-ion batteries in the field of energy storage still faces some challenges. First of all, the reserves of lithium sources on the earth are limited, and the price of metal lithium will gradually rise with the large-scale application of lithium-ion batteries. Secondly, it is particularly important to develop ideal electrode materials to further improve their performance.
与锂处在同一主族的钠，与锂有着相似的化学性质。钠离子电池与锂离子电池有着相似的原理，重要的是钠在地球上的储量远高于锂。目前，许多关于钠离子正极材料的研究工作被相继报道，如NaxCoO2，Na0.44MnO2，Na0.6MnO2，NaCrO2，NaxVO2，Na3V2(PO4)3，Na3V2(PO4)2F3，Na3V2O2(PO4)2F，Na2FePO4F，NaFeF3等，但这些正极材料的性能仍然不能满足钠离子电池的工业化应用的要求。因此，开发出理想的电极材料是钠离子电池工业化的关键。Sodium, which is in the same main group as lithium, has similar chemical properties to lithium. Sodium-ion batteries share a similar principle to lithium-ion batteries, and the important thing is that sodium is much more abundant on Earth than lithium. At present, many research works on sodium ion cathode materials have been reported successively, such as Nax CoO2 , Na0.44 MnO2 , Na0.6 MnO2 , NaCrO2 , Nax VO2 , Na3 V2 (PO4 )3 , Na3 V2 (PO4 )2 F3 , Na3 V2 O2 (PO4 )2 F, Na2 FePO4 F, NaFeF3 , etc., but the performance of these cathode materials still cannot meet the industrial application requirements of sodium ion batteries. Require. Therefore, the development of ideal electrode materials is the key to the industrialization of sodium-ion batteries.
铁基正极材料橄榄石型(olivine)LiFePO4作为锂离子电池正极材料，已经得到广泛的应用。相对于LiFePO4，橄榄石型(olivine)NaFePO4也可以作为钠离子电池正极材料。由于Na+的半径比Li+大，使得NaFePO4主要有maricite和olivine两种晶型。由于晶体结构的差异，maricite型NaFePO4作为钠离子正极材料是没有活性的，而olivine型NaFePO4则具有活性。但是，maricite型NaFePO4却更加稳定。目前，通过一些热处理或者固相反应得到的NaFePO4主要为maricite型NaFePO4。因此，如何简单快速地制备橄榄石型(olivine)NaFePO4则显得尤为重要。The iron-based cathode material olivine LiFePO4 has been widely used as the cathode material for lithium-ion batteries. Compared with LiFePO4 , olivine NaFePO4 can also be used as anode material for sodium ion batteries. Since the radius of Na+ is larger than that of Li+ , NaFePO4 mainly has two crystal forms: maricite and olivine. Due to the difference in crystal structure, maricite-type NaFePO4 is inactive as a sodium ion cathode material, while olivine-type NaFePO4 is active. However, maricite type NaFePO4 is more stable. At present, the NaFePO4 obtained by some heat treatment or solid state reaction is mainly maricite type NaFePO4 . Therefore, how to prepare olivine-type (olivine) NaFePO4 simply and quickly is particularly important.
发明内容Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种以无定型纳米FePO4为原料，快速简单地制备橄榄石型NaFePO4钠离子电池正极材料的方法。The object of the present invention is to provide a kind of use amorphous nano-FePO as raw material in order to overcome the defect that above-mentioned prior art exists, the method for preparing olivine typeNaFePO4 sodium- ion battery cathode material quickly and simply.
本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
一种橄榄石型NaFePO4钠离子电池正极材料的制备方法，该方法以无定形纳米FePO4作为活性物质，制成电极材料，再通过电化学方法，使得钠离子嵌入无定形纳米FePO4中，进而将无定形纳米FePO4转化为橄榄石型NaFePO4，具体包括以下步骤：A preparation method of an olivine-typeNaFePO4 sodium ion battery positive electrode material, the method uses amorphous nano- FePO4 as an active material to make an electrode material, and then uses an electrochemical method to make sodium ions embedded in the amorphous nano- FePO4, Further, the amorphous nano-FePO4 is converted into olivine-type NaFePO4 , which specifically includes the following steps:
(1)将无定形纳米FePO4与导电剂加入球磨罐中，球磨2-8h，再向球磨罐中加入乙醇作为分散剂，球磨2-8h，干燥，即制得活性物质；(1) Add amorphous nano- FePO4 and conductive agent into the ball milling tank, ball milling for 2-8h, then add ethanol as a dispersant in the ball milling tank, ball milling for 2-8h, and dry to obtain the active material;
(2)称取步骤(1)制得的活性物质，并与粘结剂混合，充分搅拌，制成浆液，并涂覆在纽扣电池正极壳上，在3MPa的压力下保压2-4min，充分压实，并于100-110℃下真空干燥10-12h，即制得负载有电极材料的纽扣电池正极壳；(2) Weigh the active material obtained in step (1), mix it with the binder, stir it fully to make a slurry, and coat it on the button battery positive shell, and keep the pressure for 2-4min under the pressure of 3MPa, Fully compact and vacuum-dry at 100-110°C for 10-12 hours to obtain a button battery positive shell loaded with electrode materials;
(3)在充有氩气的手套箱中，以金属钠片为负极，以负载有电极材料的纽扣电池正极壳为正极，并与电解液、隔膜共同组装成纽扣电池；(3) In a glove box filled with argon gas, the metal sodium sheet is used as the negative electrode, and the positive electrode shell of the button battery loaded with the electrode material is used as the positive electrode, and the button battery is assembled together with the electrolyte and the diaphragm;
(4)通过电化学方法，对步骤(3)组装成的纽扣电池以0.1C倍率进行5-20次恒流充放电循环，然后以0.01-0.05C倍率放电，待放电结束后，将纽扣电池置于手套箱中，拆卸，取出纽扣电池正极壳上的电极材料，清洗，以去除电极材料表面残留的电解液，再进行超声分散，并于70-80℃下干燥后，即制得橄榄石型NaFePO4钠离子电池正极材料。(4) Perform 5-20 constant current charge-discharge cycles at a rate of 0.1C for the button cell assembled in step (3) by electrochemical means, and then discharge at a rate of 0.01-0.05C. After the discharge is completed, replace the button cell Put it in a glove box, disassemble it, take out the electrode material on the positive electrode shell of the button battery, wash it to remove the residual electrolyte on the surface of the electrode material, then carry out ultrasonic dispersion, and dry it at 70-80°C to obtain olivine Type NaFePO4 sodium ion battery cathode material.
步骤(1)所述的无定形纳米FePO4与导电剂的质量比为(60-70):30，并且所述的导电剂由石墨与炭黑混合而成，其中，石墨与炭黑的质量比为4:6，所述的分散剂为乙醇。The mass ratio of amorphous nano-FePO described in step (1 ) to conductive agent is (60-70): 30, and described conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black The ratio is 4:6, and the dispersant is ethanol.
所述的无定形纳米FePO4的粒径为10-100nm，比表面为60-100m2/g，振实密度为1.1-1.4g/cm3。The particle size of the amorphous nano FePO4 is 10-100nm, the specific surface is 60-100m2 /g, and the tap density is 1.1-1.4g/cm3 .
步骤(2)所述的活性物质与粘结剂的质量比为(88-92)：8。The mass ratio of the active material to the binder in step (2) is (88-92):8.
步骤(2)所述的粘结剂为电池级聚四氟乙烯。The binder described in step (2) is battery grade polytetrafluoroethylene.
步骤(2)所述的纽扣电池正极壳为焊有不锈钢网的2016型纽扣电池正极壳。The button battery positive shell described in step (2) is a 2016 button battery positive shell welded with a stainless steel mesh.
步骤(3)所述的电解液的溶质为NaClO4，该NaClO4的浓度为1mol/L，并且 所述的电解液的溶剂为碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，所述的隔膜为电池级玻璃纤维毡。The solute of the electrolytic solution described in step (3) is NaClO4 , the concentration of the NaClO4 is 1mol/L, and the solvent of the electrolytic solution is ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1. mixed solvent, and the separator is battery-grade glass fiber felt.
步骤(4)所述的恒流充放电循环的条件为：控制温度为25℃，设定电流为0.1C，电压为1.5-4.2V。The conditions of the constant current charging and discharging cycle described in step (4) are: the control temperature is 25°C, the set current is 0.1C, and the voltage is 1.5-4.2V.
步骤(4)所述的清洗的条件为：采用碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，冲洗电极材料表面3-4次。The cleaning conditions described in step (4) are: use a mixed solvent of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1 to rinse the surface of the electrode material for 3-4 times.
步骤(4)所述的超声分散的条件为：将清洗后的电极材料置于乙醇溶剂中，控制超声频率为30000-40000Hz，超声20-30min，将电极材料完全分散在乙醇溶剂中。The conditions for the ultrasonic dispersion in step (4) are as follows: place the cleaned electrode material in an ethanol solvent, control the ultrasonic frequency to 30000-40000 Hz, ultrasonically 20-30 min, and completely disperse the electrode material in the ethanol solvent.
从反应机理来看，采用本发明方法制备活性NaFePO4过程中，不需要经过高温处理，原料纳米FePO4在转化为NaFePO4后，材料的粒径并不会发生变化，这能有效保持活性物质的大比表面积特点，有利于降低阻抗，保证材料在充放电过程中的电化学过程；另外，在本发明的电化学转化过程中，主要是在钠离子嵌入-迁出过程进行的同时，实现材料的结构转化，所得到的橄榄石结构中形成的晶面取向更有利于钠离子后续的嵌入-迁出。与目前现有技术相比，采用LiFePO4的钠离子置换，由于置换平衡原因，不可能实现Li-Na的完全置换，必然会残留部分LiFePO4，这会降低材料的利用率。另外，目前通过固相合成方法制备得到的NaFePO4，大部分是Maricite结构的NaFePO4，其电化学活性很低，更是无法达到很高的电化学性能。From the point of view of reaction mechanism, adopt the method of the present invention to prepare activeNaFePO in the process, do not need through high temperature treatment, after raw material nanometerFePO is converted intoNaFePO , the particle size of material will not change, and this can effectively keep active substance The characteristics of the large specific surface area are beneficial to reduce the impedance and ensure the electrochemical process of the material in the charging and discharging process; in addition, in the electrochemical conversion process of the present invention, it is mainly at the same time that the sodium ion intercalation-migration process is carried out. The structural transformation of the material, the crystal plane orientation formed in the obtained olivine structure is more conducive to the subsequent intercalation and emigration of sodium ions. Compared with the current existing technology, the replacement of sodium ions with LiFePO4 is impossible to achieve complete replacement of Li-Na due to the replacement balance, and some LiFePO4 will inevitably remain, which will reduce the utilization rate of materials. In addition, most of the NaFePO4 prepared by the solid phase synthesis method is NaFePO4 with a Maricite structure, and its electrochemical activity is very low, and it cannot achieve high electrochemical performance.
与现有技术相比，本发明以无定型纳米FePO4为原料，原料来源丰富，廉价，制备方法简单，无需高温热处理，制得的NaFePO4正极材料的结构为橄榄石型结构，这种结构具有很高的电化学活性，作为钠离子电池正极材料表现出优异的电化学性能，例如，循环性能方面，在0.1C条件下，制成的NaFePO4的首次放电比容量为147.9mAh/g，达到理论容量的90.8％，循环120次以后，仍然能够达到131.3mAh/g，而且库伦效率接近100％；倍率性能方面，在0.2C、0.5C、1.0C放电倍率下，制成的NaFePO4的放电比容量分别达到118.6mAh/g、90.7mAh/g及63.1mAh/g。Compared with the prior art, the present invention uses amorphous nano- FePO4 as raw material, the source of raw material is abundant, cheap, the preparation method is simple, no high-temperature heat treatment is required, and the structure of the obtainedNaFePO4 cathode material is an olivine-type structure. It has high electrochemical activity and exhibits excellent electrochemical performance as a cathode material for sodium-ion batteries. For example, in terms of cycle performance, the first discharge specific capacity of the preparedNaFePO4 is 147.9mAh/g at 0.1C, Reaching 90.8% of the theoretical capacity, after 120 cycles, it can still reach 131.3mAh/g, and the coulombic efficiency is close to 100%. In terms of rate performance, at 0.2C, 0.5C, and 1.0C discharge rates, the prepared NaFePO4 The discharge specific capacities reached 118.6mAh/g, 90.7mAh/g and 63.1mAh/g respectively.
附图说明Description of drawings
图1为本发明制得的NaFePO4的XRD图谱；Fig. 1 is theNaFePO that the present invention makes XRD collection of illustrative plates;
图2为本发明制得的NaFePO4的高倍透射电镜图谱；Fig.2 is the NaFePO that the present invention makes High magnification transmission electron microscope collection of images;
图3为本发明制得的NaFePO4的选择区域电子衍射图谱；Fig. 3 is the NaFePO that the present invention makesThe selected area electron diffraction spectrum;
图4为本发明制得的NaFePO4的电子能谱图；Fig.4 is the NaFePO that the present invention makes The electron energy spectrogram;
图5为本发明制得的NaFePO4的循环伏安曲线图谱；Fig.5 is the NaFePO that the present invention makes The cyclic voltammetry curve collection of lines;
图6为本发明制得的NaFePO4的循环测试图；Fig. 6 is theNaFePO that the present invention makes Circular test figure;
图7为本发明制得的NaFePO4的倍率测试图；Fig. 7 is the NaFePO that the present invention makes4The ratio test figure;
具体实施方式detailed description
下面结合附图和具体实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.
实施例1：Example 1:
无定型纳米FePO4与导电剂(石墨(上海产，AR)：炭黑(上海产，AR)＝4:6)按质量比为62:30混合加入到球磨罐中，行星式球磨机干磨两小时，然后用酒精作为分散剂湿磨两小时，得到的活性物质在恒温干燥箱中干燥。称取15mg活性材料与PTFE(日本产，电池级)(质量比92:8)混合成浆液，涂在焊有不锈钢网的2016型纽扣电池正极壳上。压实后置于真空干燥箱中，100℃条件下烘12h，然后在充Ar2手套箱中，以金属Na(上海产，CP)片为负极，电解液为1mol/L的NaClO4(上海产，AR)(溶解在体积比为1：1的EC(天津产，AR)/DMC(上海产，AR)中)，以玻璃毡纤维(福建龙泉产，电池级)为隔膜，组装成2016型纽扣电池。Amorphous nano FePO4 and conductive agent (graphite (produced in Shanghai, AR): carbon black (produced in Shanghai, AR) = 4:6) are mixed in the ball mill jar according to the mass ratio of 62:30, and the planetary ball mill is dry-milled twice Hours, and then use alcohol as a dispersant to wet grind for two hours, and the active substance obtained is dried in a constant temperature drying oven. Weigh 15 mg of active material and mix it with PTFE (made in Japan, battery grade) (mass ratio 92:8) to form a slurry, and apply it on the positive shell of the 2016 button battery welded with stainless steel mesh. After compaction, put it in a vacuum drying oven, bake it at 100°C for 12 hours, and then place it in an Ar2- filled glove box with a metal Na (produced in Shanghai, CP) sheet as the negative electrode, and the electrolyte as 1mol/LNaClO4 (Shanghai produced, AR) (dissolved in EC (produced in Tianjin, AR)/DMC (produced in Shanghai, AR) with a volume ratio of 1:1), with glass felt fiber (produced in Longquan, Fujian, battery grade) as a separator, assembled into a 2016 type button battery.
用Land电池测试系统(中国，武汉)进行恒流充放电测试10个循环，测试温度控制在恒温25℃，测试电压为1.5-4.2V之间。然后在手套箱(米开罗那)中，将正极材料从纽扣电池中取出，用EC/DMC清洗三次，除去电极表面残留的电解质。然后将电极放在酒精溶剂中，超声20min，使得电极上的正极材料完全分散在酒精中，然后在70℃条件下烘干。这样，NaFePO4正极材料就得到了。The Land battery test system (Wuhan, China) was used to conduct a constant current charge and discharge test for 10 cycles, the test temperature was controlled at a constant temperature of 25°C, and the test voltage was between 1.5-4.2V. Then in the glove box (Michelona), the positive electrode material was taken out from the button cell and washed three times with EC/DMC to remove the residual electrolyte on the electrode surface. Then the electrode was placed in an alcohol solvent, ultrasonicated for 20 minutes, so that the positive electrode material on the electrode was completely dispersed in the alcohol, and then dried at 70°C. In this way, the NaFePO4 cathode material is obtained.
图1是所合成的NaFePO4材料的XRD图谱，从图中可以看出，出现很强的橄榄石型NaFePO4的衍射峰。Figure 1 is the XRD spectrum of the synthesized NaFePO4 material, as can be seen from the figure, there is a strong diffraction peak of olivine-type NaFePO4 .
表1. NaFePO4晶格参数Table 1. NaFePO4 lattice parameters
图2-3则对应的是NaFePO4高倍透射电镜图和选择区域电子衍射图谱，从图中可以看出，高倍透射显示出明显的晶格条纹，电子衍射有明显的衍射环出现，说明无定型纳米FePO4材料在电化学过程中转变成NaFePO4微晶。Figure 2-3 corresponds to the NaFePO4 high-magnification transmission electron microscope image and selected area electron diffraction pattern. It can be seen from the figure that the high-magnification transmission shows obvious lattice fringes, and the electron diffraction has obvious diffraction rings, indicating that the amorphous The nano-FePO4 material transforms into NaFePO4 crystallites during the electrochemical process.
图4对应的是EDS图谱，其中的Na：Fe：P的比为1：1：1，结果表明这种电化学合成的方法合成出来的材料组成为NaFePO4。Figure 4 corresponds to the EDS spectrum, in which the ratio of Na:Fe:P is 1:1:1, and the result shows that the composition of the material synthesized by this electrochemical synthesis method is NaFePO4 .
将本实施例制成的Olivine-NaFePO4作为钠离子正极材料，称取15mg的NaFePO4与PTEF(92：8)混合成浆液，涂在焊有不锈钢网的2016型纽扣电池正极壳上。压实后置于真空干燥箱中，100℃条件下烘12h，然后在充Ar2手套箱中，以金属Na片为负极，电解液为1mol/L的NaClO4，以玻璃毡纤维为隔膜，组装成2016型纽扣电池。The Olivine-NaFePO4 produced in this example was used as the sodium ion positive electrode material, and 15 mg of NaFePO4 was weighed and mixed with PTEF (92:8) to form a slurry, and coated on the positive shell of the 2016 button battery welded with stainless steel mesh. After compaction, put it in a vacuum drying oven, bake at 100°C for 12 hours, and then place it in an Ar2 filled glove box with a metal Na sheet as the negative electrode, an electrolyte of 1 mol/L NaClO4 , and a glass felt fiber as a separator. Assembled into a 2016-style button cell.
在Land电池测试系统做恒流充放电测试。Do constant current charge and discharge test in Land battery test system.
在0.1C，0.2C，0.5C，1C不同倍率测试，电化学窗口为1.5V-4.2V。Tested at different rates of 0.1C, 0.2C, 0.5C, and 1C, the electrochemical window is 1.5V-4.2V.
图5为NaFePO4正极材料的循环伏安图，氧化还原峰电位分别为2.83V和2.43V，这个氧化还原峰电位很接近，结果表明出NaFePO4有优异的电化学可逆性。Figure 5 is the cyclic voltammogram of the NaFePO4 cathode material. The redox peak potentials are 2.83V and 2.43V respectively. The redox peak potentials are very close. The results show that NaFePO4 has excellent electrochemical reversibility.
图6为NaFePO4正极材料在0.1C条件下的充放电循环图谱。NaFePO4的首次放电比容量为147.9mAh/g，达到理论容量的90.8％，循环120次以后，仍然能够达到131.3mAh/g，而且库伦效率接近100％。结果表明NaFePO4作为钠离子电池正极材料表现出优异点的循环性能和容量性能。Figure 6 is the charge-discharge cycle spectrum of the NaFePO4 cathode material at 0.1C. The initial discharge specific capacity of NaFePO4 is 147.9mAh/g, which is 90.8% of the theoretical capacity. After 120 cycles, it can still reach 131.3mAh/g, and the Coulombic efficiency is close to 100%. The results show that NaFePO4 exhibits excellent cycle performance and capacity performance as a cathode material for sodium-ion batteries.
由图7分析可知，NaFePO4正极材料在0.2C、0.5C、1.0C放电倍率下，放电比容量分别达到118.6mAh/g、90.7mAh/g、63.1mAh/g，结果表明，NaFePO4有着优异点的倍率性能。From the analysis in Figure 7, it can be seen that the discharge specific capacity of NaFePO4 cathode material reaches 118.6mAh/g, 90.7mAh/g, and 63.1mAh/g at 0.2C, 0.5C, and 1.0C discharge rates, respectively. The results show that NaFePO4 has excellent point magnification performance.
实施例2：Example 2:
本实施例橄榄石型NaFePO4钠离子电池正极材料的制备方法，具体包括以下步骤：The preparation method of the olivine typeNaFePO4 sodium ion battery cathode material of the present embodiment specifically comprises the following steps:
(1)将无定形纳米FePO4与导电剂加入球磨罐中，球磨2h，再向球磨罐中加入乙醇作为分散剂，继续球磨2h，干燥，即制得活性物质；(1) Amorphous nano- FePO and conductive agent are added in the ball milling tank, ball milling for 2h, then adding ethanol as a dispersant in the ball milling tank, continue ball milling for 2h, and dry to obtain the active material;
(2)称取步骤(1)制得的活性物质，并与粘结剂混合，充分搅拌，制成浆液，并涂覆在纽扣电池正极壳上，3MP的压力下保压3min，充分压实，并于100℃下 真空干燥12h，即制得负载有电极材料的纽扣电池正极壳；(2) Weigh the active material prepared in step (1), mix it with the binder, stir thoroughly to make a slurry, and coat it on the positive electrode shell of the button battery, hold the pressure for 3min under the pressure of 3MP, and fully compact it , and vacuum-dried at 100°C for 12 hours to obtain a button battery positive shell loaded with electrode materials;
(3)在充有氩气的手套箱中，以钠片为负极，负载有电极材料的纽扣电池正极壳为正极，并与电解液、隔膜共同组装成纽扣电池；(3) In a glove box filled with argon gas, the sodium sheet is used as the negative electrode, and the positive electrode shell of the button battery loaded with the electrode material is used as the positive electrode, and the button battery is assembled together with the electrolyte and the diaphragm;
(4)通过电化学方法，对步骤(3)组装成的纽扣电池以0.1C倍率进行20次恒流充放电循环，然后以0.01C倍率放电，待放电结束后，将纽扣电池置于手套箱中，拆卸，取出纽扣电池正极壳上的电极材料，清洗，以去除电极材料表面残留的电解液，再进行超声分散，并于70℃下干燥后，即制得橄榄石型NaFePO4钠离子电池正极材料。(4) Perform 20 constant current charge and discharge cycles at a rate of 0.1C for the button cell assembled in step (3) by electrochemical method, and then discharge at a rate of 0.01C. After the discharge is completed, put the button cell in the glove box During disassembly, take out the electrode material on the positive shell of the button battery, wash it to remove the residual electrolyte on the surface of the electrode material, and then carry out ultrasonic dispersion, and after drying at 70 ° C, the olivine-type NaFePO4 sodium ion battery is obtained Cathode material.
本实施例中，无定形纳米FePO4的粒径为100nm，比表面为60m2/g，振实密度为1.1g/cm3；纽扣电池正极壳为焊有不锈钢网的2016型纽扣电池正极壳。In this embodiment, the particle size of the amorphous nano- FePO is 100nm, the specific surface is 60m2/g , and the tap density is 1.1g/cm3 ; the button battery positive shell is a 2016 button battery positive shell welded with stainless steel mesh .
其中，步骤(1)中，无定形纳米FePO4与导电剂的质量比为60:30，并且导电剂由石墨与炭黑混合而成，其中，石墨与炭黑的质量比为4:6。Wherein, in step (1), the mass ratio of amorphous nano-FePO4 and conductive agent is60:30 , and conductive agent is mixed by graphite and carbon black, and wherein, the mass ratio of graphite and carbon black is 4:6.
步骤(2)中，活性物质与粘结剂的质量比为88：8，粘结剂为电池级聚四氟乙烯。In step (2), the mass ratio of the active material to the binder is 88:8, and the binder is battery-grade polytetrafluoroethylene.
步骤(3)中，电解液的溶质为NaClO4，该NaClO4的浓度为1mol/L，溶剂为碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，隔膜为电池级玻璃纤维毡。In step (3), the solute of the electrolyte is NaClO4 , the concentration of the NaClO4 is 1mol/L, the solvent is a mixed solvent of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1, and the diaphragm is battery-grade glass Fiber felt.
步骤(4)中，清洗的条件为：采用碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，冲洗电极材料表面3次；超声分散的条件为：将清洗后的电极材料置于乙醇溶剂中，控制超声频率为40000Hz，超声20min，将电极材料完全分散在乙醇溶剂中。In step (4), the cleaning conditions are: use a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 to rinse the surface of the electrode material 3 times; the conditions for ultrasonic dispersion are: the cleaned electrode material Place in ethanol solvent, control the ultrasonic frequency to 40000 Hz, ultrasonic 20min, completely disperse the electrode material in ethanol solvent.
实施例3：Example 3:
本实施例橄榄石型NaFePO4钠离子电池正极材料的制备方法，具体包括以下步骤：The preparation method of the olivine typeNaFePO4 sodium ion battery cathode material of the present embodiment specifically comprises the following steps:
(1)将无定形纳米FePO4与导电剂加入球磨罐中，球磨4h，再向球磨罐中加入乙醇作为分散剂，继续球磨4h，干燥，即制得活性物质；(1 ) Amorphous nano FePO and conductive agent are added in the ball milling tank, ball milling for 4h, then adding ethanol in the ball milling tank as a dispersant, continuing ball milling for 4h, drying to obtain the active material;
(2)称取步骤(1)制得的活性物质，并与粘结剂混合，充分搅拌，制成浆液，并涂覆在纽扣电池正极壳上，3MP的压力下保压4min，充分压实，并于110℃下真空干燥10h，即制得负载有电极材料的纽扣电池正极壳；(2) Weigh the active material prepared in step (1), mix it with the binder, stir thoroughly to make a slurry, and coat it on the positive electrode shell of the button battery, hold the pressure for 4min under the pressure of 3MP, and fully compact it , and vacuum-dried at 110°C for 10 hours to obtain a button battery positive shell loaded with electrode materials;
(3)在充有氩气的手套箱中，以钠片为负极，负载有电极材料的纽扣电池正极壳为正极，并与电解液、隔膜共同组装成纽扣电池；(3) In a glove box filled with argon gas, the sodium sheet is used as the negative electrode, and the positive electrode shell of the button battery loaded with the electrode material is used as the positive electrode, and the button battery is assembled together with the electrolyte and the diaphragm;
(4)通过电化学方法，对步骤(3)组装成的纽扣电池以0.1C倍率进行15次恒流充放电循环，然后以0.05C倍率放电，待放电结束后，将纽扣电池置于手套箱中，拆卸，取出纽扣电池正极壳上的电极材料，清洗，以去除电极材料表面残留的电解液，再进行超声分散，并于80℃下干燥后，即制得橄榄石型NaFePO4钠离子电池正极材料。(4) Perform 15 constant current charge and discharge cycles at a rate of 0.1C for the button cell assembled in step (3) by electrochemical method, and then discharge at a rate of 0.05C. After the discharge is completed, put the button cell in the glove box During disassembly, take out the electrode material on the positive shell of the button battery, wash it to remove the residual electrolyte on the surface of the electrode material, and then carry out ultrasonic dispersion, and after drying at 80 ° C, the olivine-type NaFePO4 sodium ion battery is obtained Cathode material.
本实施例中，无定形纳米FePO4的粒径为10nm，比表面为100m2/g，振实密度为1.4g/cm3；纽扣电池正极壳为焊有不锈钢网的2016型纽扣电池正极壳。In this embodiment, the particle size of amorphous nano- FePO is 10nm, the specific surface is 100m2/g , and the tap density is 1.4g/cm3 ; the button battery positive shell is a 2016 button battery positive shell welded with stainless steel mesh .
其中，步骤(1)中，无定形纳米FePO4与导电剂的质量比为70:30，并且导电剂由石墨与炭黑混合而成，其中，石墨与炭黑的质量比为4:6。Wherein, in step (1), the mass ratio of amorphous nano- FePO4 and conductive agent is 70:30, and conductive agent is mixed by graphite and carbon black, and wherein, the mass ratio of graphite and carbon black is 4:6.
步骤(2)中，活性物质与粘结剂的质量比为90：8，粘结剂为电池级聚四氟乙烯。In step (2), the mass ratio of the active material to the binder is 90:8, and the binder is battery-grade polytetrafluoroethylene.
步骤(3)中，电解液的溶质为NaClO4，该NaClO4的浓度为1mol/L，溶剂为碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，隔膜为电池级玻璃纤维毡。In step (3), the solute of the electrolyte is NaClO4 , the concentration of the NaClO4 is 1mol/L, the solvent is a mixed solvent of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1, and the diaphragm is battery-grade glass Fiber felt.
步骤(4)中，清洗的条件为：采用碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，冲洗电极材料表面4次；超声分散的条件为：将清洗后的电极材料置于乙醇溶剂中，控制超声频率为30000Hz，超声30min，将电极材料完全分散在乙醇溶剂中。In step (4), the cleaning conditions are: use a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 to rinse the surface of the electrode material 4 times; the conditions for ultrasonic dispersion are: the cleaned electrode material Place in an ethanol solvent, control the ultrasonic frequency to 30000 Hz, and ultrasonicate for 30 minutes to completely disperse the electrode material in the ethanol solvent.
实施例4：Example 4:
本实施例橄榄石型NaFePO4钠离子电池正极材料的制备方法，具体包括以下步骤：The preparation method of the olivine typeNaFePO4 sodium ion battery cathode material of the present embodiment specifically comprises the following steps:
(1)将无定形纳米FePO4与导电剂加入球磨罐中，球磨5h，再向球磨罐中加入乙醇作为分散剂，继续球磨5h，干燥，即制得活性物质；(1 ) Amorphous nano FePO and conductive agent are added in the ball milling tank, ball milling for 5h, then adding ethanol in the ball milling tank as a dispersant, continuing ball milling for 5h, drying, that is, the active substance is obtained;
(2)称取步骤(1)制得的活性物质，并与粘结剂混合，充分搅拌，制成浆液，并涂覆在纽扣电池正极壳上，3MP的压力下保压2min，充分压实，并于100℃下真空干燥10h，即制得负载有电极材料的纽扣电池正极壳；(2) Weigh the active material prepared in step (1), mix it with the binder, stir thoroughly to make a slurry, and coat it on the positive electrode shell of the button battery, hold the pressure for 2min under the pressure of 3MP, and fully compact it , and vacuum-dried at 100°C for 10 hours to obtain a button battery positive shell loaded with electrode materials;
(3)在充有氩气的手套箱中，以钠片为负极，负载有电极材料的纽扣电池正极壳为正极，并与电解液、隔膜共同组装成纽扣电池；(3) In a glove box filled with argon gas, the sodium sheet is used as the negative electrode, and the positive electrode shell of the button battery loaded with the electrode material is used as the positive electrode, and the button battery is assembled together with the electrolyte and the diaphragm;
(4)通过电化学方法，对步骤(3)组装成的纽扣电池以0.1C倍率进行5次恒流充放电循环，然后以0.02C倍率放电，待放电结束后，将纽扣电池置于手套箱中，拆卸，取出纽扣电池正极壳上的电极材料，清洗，以去除电极材料表面残留的 电解液，再进行超声分散，并于75℃下干燥后，即制得橄榄石型NaFePO4钠离子电池正极材料。(4) Perform 5 constant current charge and discharge cycles at a rate of 0.1C for the button battery assembled in step (3) by electrochemical method, and then discharge at a rate of 0.02C. After the discharge is completed, put the button battery in the glove box During disassembly, take out the electrode material on the positive shell of the button battery, wash it to remove the residual electrolyte on the surface of the electrode material, and then carry out ultrasonic dispersion, and after drying at 75 ° C, the olivine-type NaFePO4 sodium ion battery is obtained Cathode material.
本实施例中，无定形纳米FePO4的粒径为60nm，比表面为80m2/g，振实密度为1.2g/cm3；纽扣电池正极壳为焊有不锈钢网的2016型纽扣电池正极壳。In this embodiment, the particle size of amorphous nano- FePO is 60nm, the specific surface is 80m2 /g, and the tap density is 1.2g/cm3 ; the button battery positive shell is a 2016 button battery positive shell welded with stainless steel mesh .
其中，步骤(1)中，无定形纳米FePO4与导电剂的质量比为64:30，并且导电剂由石墨与炭黑混合而成，其中，石墨与炭黑的质量比为4:6。Wherein, in step (1), the mass ratio of amorphous nano-FePO4 and conductive agent is64:30 , and conductive agent is mixed by graphite and carbon black, and wherein, the mass ratio of graphite and carbon black is 4:6.
步骤(2)中，活性物质与粘结剂的质量比为91：8，粘结剂为电池级聚四氟乙烯。In step (2), the mass ratio of the active material to the binder is 91:8, and the binder is battery-grade polytetrafluoroethylene.
步骤(3)中，电解液的溶质为NaClO4，该NaClO4的浓度为1mol/L，溶剂为碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，隔膜为电池级玻璃纤维毡。In step (3), the solute of the electrolyte is NaClO4 , the concentration of the NaClO4 is 1mol/L, the solvent is a mixed solvent of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1, and the diaphragm is battery-grade glass Fiber felt.
步骤(4)中，清洗的条件为：采用碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，冲洗电极材料表面3次；超声分散的条件为：将清洗后的电极材料置于乙醇溶剂中，控制超声频率为38000Hz，超声25min，将电极材料完全分散在乙醇溶剂中。In step (4), the cleaning conditions are: use a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 to rinse the surface of the electrode material 3 times; the conditions for ultrasonic dispersion are: the cleaned electrode material Place in an ethanol solvent, control the ultrasonic frequency to 38000 Hz, and ultrasonicate for 25 minutes to completely disperse the electrode material in the ethanol solvent.
实施例5：Example 5:
本实施例橄榄石型NaFePO4钠离子电池正极材料的制备方法，具体包括以下步骤：The preparation method of the olivine typeNaFePO4 sodium ion battery cathode material of the present embodiment specifically comprises the following steps:
(1)将无定形纳米FePO4与导电剂加入球磨罐中，球磨8h，再向球磨罐中加入乙醇作为分散剂，继续球磨8h，干燥，即制得活性物质；(1) Amorphous nano- FePO and conductive agent are added in the ball milling tank, ball milling for 8h, then adding ethanol as a dispersant in the ball milling tank, continuing ball milling for 8h, and drying to obtain the active material;
(2)称取步骤(1)制得的活性物质，并与粘结剂混合，充分搅拌，制成浆液，并涂覆在纽扣电池正极壳上，3MP的压力下保压3min，充分压实，并于105℃下真空干燥11h，即制得负载有电极材料的纽扣电池正极壳；(2) Weigh the active material prepared in step (1), mix it with the binder, stir thoroughly to make a slurry, and coat it on the positive electrode shell of the button battery, hold the pressure for 3min under the pressure of 3MP, and fully compact it , and vacuum-dried at 105°C for 11 hours to obtain a button battery positive shell loaded with electrode materials;
(3)在充有氩气的手套箱中，以钠片为负极，负载有电极材料的纽扣电池正极壳为正极，并与电解液、隔膜共同组装成纽扣电池；(3) In a glove box filled with argon gas, the sodium sheet is used as the negative electrode, and the positive electrode shell of the button battery loaded with the electrode material is used as the positive electrode, and the button battery is assembled together with the electrolyte and the diaphragm;
(4)通过电化学方法，对步骤(3)组装成的纽扣电池以0.1C倍率进行10次恒流充放电循环，然后以0.03C倍率放电，待放电结束后，将纽扣电池置于手套箱中，拆卸，取出纽扣电池正极壳上的电极材料，清洗，以去除电极材料表面残留的电解液，再进行超声分散，并于78℃下干燥后，即制得橄榄石型NaFePO4钠离子电池正极材料。(4) Perform 10 constant current charge-discharge cycles at a rate of 0.1C to the button cell assembled in step (3) by electrochemical method, and then discharge at a rate of 0.03C. After the discharge, put the button cell in the glove box During disassembly, take out the electrode material on the positive shell of the button battery, wash it to remove the residual electrolyte on the surface of the electrode material, and then carry out ultrasonic dispersion, and after drying at 78 ° C, the olivine-type NaFePO4 sodium ion battery is obtained Cathode material.
本实施例中，无定形纳米FePO4的粒径为40nm，比表面为95m2/g，振实密度 为1.3g/cm3；纽扣电池正极壳为焊有不锈钢网的2016型纽扣电池正极壳。In this embodiment, the particle size of the amorphous nano- FePO is 40nm, the specific surface is95m2 /g, and the tap density is 1.3g/cm3 ; the button battery positive shell is a 2016 button battery positive shell welded with stainless steel mesh .
其中，步骤(1)中，无定形纳米FePO4与导电剂的质量比为65:30，并且导电剂由石墨与炭黑混合而成，其中，石墨与炭黑的质量比为4:6。Wherein, in step (1), the mass ratio of amorphous nano-FePO4 and conductive agent is65:30 , and conductive agent is mixed by graphite and carbon black, and wherein, the mass ratio of graphite and carbon black is 4:6.
步骤(2)中，活性物质与粘结剂的质量比为89：8，粘结剂为电池级聚四氟乙烯。In step (2), the mass ratio of the active material to the binder is 89:8, and the binder is battery-grade polytetrafluoroethylene.
步骤(3)中，电解液的溶质为NaClO4，该NaClO4的浓度为1mol/L，溶剂为碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，隔膜为电池级玻璃纤维毡。In step (3), the solute of the electrolyte is NaClO4 , the concentration of the NaClO4 is 1mol/L, the solvent is a mixed solvent of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1, and the diaphragm is battery-grade glass Fiber felt.
步骤(4)中，清洗的条件为：采用碳酸乙烯酯与碳酸二甲酯按体积比为1:1的混合溶剂，冲洗电极材料表面3次；超声分散的条件为：将清洗后的电极材料置于乙醇溶剂中，控制超声频率为40000Hz，超声30min，将电极材料完全分散在乙醇溶剂中。In step (4), the cleaning conditions are: use a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 to rinse the surface of the electrode material 3 times; the conditions for ultrasonic dispersion are: the cleaned electrode material Place in an ethanol solvent, control the ultrasonic frequency to 40000 Hz, and ultrasonicate for 30 minutes to completely disperse the electrode material in the ethanol solvent.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510401813.6ACN105152154B (en) | 2015-07-09 | 2015-07-09 | A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material |
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| CN201510401813.6ACN105152154B (en) | 2015-07-09 | 2015-07-09 | A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material |
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| CN201510401813.6AActiveCN105152154B (en) | 2015-07-09 | 2015-07-09 | A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material |
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|---|---|---|---|---|
| CN109786744A (en)* | 2019-01-24 | 2019-05-21 | 中南大学 | A method for preparing sodium iron phosphate electrode by utilizing industrial by-product ferrous sulfate |
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| CN116145154A (en)* | 2022-12-16 | 2023-05-23 | 山东润雅纳能新能源科技有限公司 | A kind of cathode material of phosphate sodium ion battery and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006155941A (en)* | 2004-11-25 | 2006-06-15 | Kyushu Univ | Method for producing electrode active material |
| CN101442117B (en)* | 2008-12-22 | 2012-03-21 | 上海电力学院 | Method for preparing carbon-coating ferric phosphate lithium |
| Publication number | Publication date |
|---|---|
| CN105152154A (en) | 2015-12-16 |
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