WO2024254736A1 - 一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片 - Google Patents

一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片 Download PDF

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WO2024254736A1
WO2024254736A1 PCT/CN2023/099705 CN2023099705W WO2024254736A1 WO 2024254736 A1 WO2024254736 A1 WO 2024254736A1 CN 2023099705 W CN2023099705 W CN 2023099705W WO 2024254736 A1 WO2024254736 A1 WO 2024254736A1
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Prior art keywords
positive electrode
prussian blue
electrode material
blue positive
sodium
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French (fr)
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李爱霞
谢英豪
余海军
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/099705 priority Critical patent/WO2024254736A1/zh
Priority to CN202380009555.XA priority patent/CN116964000B/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present invention relates to the technical field of positive electrode materials, and in particular to a Prussian blue positive electrode material and a preparation method thereof and a Prussian blue positive electrode sheet.
  • lithium-ion batteries have been widely used in the field of new energy vehicles.
  • the reserves of lithium resources in the earth's crust are very limited, which seriously limits the sustainable development and large-scale application of lithium-ion batteries.
  • sodium resources are abundant and low in cost, and sodium and lithium are in the same main group with similar chemical properties.
  • sodium-ion batteries have great potential and advantages in sustainable development and large-scale application.
  • Sodium-ion batteries are driven by concentration differences.
  • sodium ions pass through the electrolyte from the positive electrode to the negative electrode.
  • sodium ions pass through the electrolyte from the negative electrode to the positive electrode.
  • the charging and discharging process maintains a high degree of reversibility.
  • Prussian blue positive electrode materials there are two major problems with Prussian blue positive electrode materials. One is that the consistency of the particles is poor. This is because in the process of synthesizing Prussian blue positive electrode materials by coprecipitation, soluble metal salts react with sodium ferrocyanide and rapidly nucleate and grow. The second is that Prussian blue positive electrode materials are prone to water absorption during storage, which will lead to a decrease in the crystallinity and volume expansion of the Prussian blue positive electrode materials, affecting the electrochemical performance and stability.
  • the purpose of this article is to overcome the shortcomings of the above-mentioned prior art and provide a Prussian blue positive electrode material and a preparation method thereof and a Prussian blue positive electrode sheet; the Prussian blue positive electrode material has good storage stability, is not easy to absorb moisture, and the particle size of the Prussian blue positive electrode material is small and has good electrical properties.
  • a method for preparing a Prussian blue positive electrode material comprising the following steps:
  • the sodium ferrocyanide solution, the hydrophobic liquid, and the surfactant are mixed until no phase separation occurs to obtain a precursor microemulsion;
  • the Prussian blue microemulsion is subjected to aging treatment, solid-liquid separation, washing and drying to obtain the Prussian blue positive electrode material.
  • a Prussian blue cathode material is prepared by a microemulsion method, and the formed water-in-oil microemulsion can effectively control the particle size of the Prussian blue cathode material.
  • the surface of the water-in-oil Prussian blue cathode material is coated with an oil film, which can prevent the dried Prussian blue cathode material from absorbing water and has good storage stability.
  • the hydrophobic liquid is at least one of a hydrophobic liquid phase organic substance and a hydrophobic ionic liquid.
  • the boiling point of the hydrophobic liquid phase organic matter is higher than that of water.
  • the hydrophobic liquid phase organic matter is at least one of n-octane, n-decane, toluene, isooctanoic acid triglyceride, n-hexadecane, and xylene
  • the hydrophobic ionic liquid is at least one of 1-propyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-octyl-3-methylimidazolium hexafluorophosphate.
  • the above materials are selected as the hydrophobic liquid to form a uniform oil film on the surface of the Prussian blue positive electrode material.
  • the sodium ferrocyanide solution is prepared by dissolving sodium ferrocyanide in water
  • the transition metal salt solution is prepared by dissolving a transition metal salt in water.
  • the molar ratio of the sodium ferrocyanide to the transition metal salt is 1:(1-2); the concentration of the sodium ferrocyanide in the sodium ferrocyanide solution is 0.01-0.5 mol/L, the concentration of the transition metal salt in the transition metal salt solution is 0.01-0.5 mol/L, and the transition metal salt is at least one of a divalent iron salt, a cobalt salt, and a manganese salt.
  • the amount of the transition metal salt introduced needs to be excessive to a certain extent to avoid defects in the prepared product particles.
  • the volume ratio of the hydrophobic liquid to the aqueous solution is 100:(5-10), and the aqueous solution is a mixture of the sodium ferrocyanide solution and the transition metal salt solution.
  • the aqueous solution is a mixture of the sodium ferrocyanide solution, the transition metal salt solution, and the auxiliary solution;
  • the auxiliary solution is a mixed aqueous solution of an antioxidant and a sodium supplement, and the concentration of the antioxidant in the auxiliary solution is 0.01-0.05 mol/L, and the concentration of the sodium supplement in the auxiliary solution is 0.01-0.05 mol/L.
  • the antioxidant is at least 1% of sodium citrate, ascorbic acid, and sodium thiosulfate.
  • At least one of the sodium supplements is at least one of sodium chloride, sodium carbonate, sodium acetate, sodium thiosulfate, and sodium citrate.
  • the molar ratio of the sodium supplement to the sodium ferrocyanide is (0.3-1.1):1.
  • Adding the above antioxidant and sodium supplement can improve the electrical properties of the Prussian blue positive electrode material.
  • the Prussian blue positive electrode material is used in a positive electrode sheet, its first discharge specific capacity and cycle performance are significantly better.
  • the molar volume ratio of the surfactant to the hydrophobic liquid is 0.3-0.5 mol/L.
  • the above-mentioned limitation on the ratio of the surfactant to the hydrophobic liquid can obtain a stable Prussian blue microemulsion.
  • the surfactant is a lipophilic surfactant
  • the lipophilic surfactant includes at least one of octylphenol polyoxyethylene ether, sodium di(2-ethylhexyl) succinate sulfonate (AOT), dodecylphenol polyoxyethylene ether, dodecyl glycidyl ether, ethylene glycol fatty acid ester, and sorbitan sesquioleate.
  • the rate at which the transition metal salt solution is added to the precursor microemulsion is 20 to 50 mL/h, and the addition process is carried out under a protective atmosphere, which is one of a nitrogen atmosphere and a helium atmosphere. Controlling the addition rate of the transition metal salt solution within the above range can improve the stability of the Prussian blue microemulsion, avoid its excessive reaction with sodium ferrocyanide, and form a positive electrode material with more uniform particles.
  • the Prussian blue microemulsion is stirred at 60-100° C. for 10-60 min and then aged.
  • the present invention also discloses a Prussian blue positive electrode material prepared by the method and a Prussian blue positive electrode sheet prepared by the Prussian blue positive electrode material.
  • the preparation method of the Prussian blue positive electrode sheet comprises the following steps:
  • the positive electrode active material, the conductive agent and the binder are prepared into a slurry in a mass ratio of (85-98): (1-5): (2-10), and the slurry is coated on a current collector to obtain the Prussian blue positive electrode sheet.
  • the coating density of the slurry on the current collector is 10-50 mg/cm 2
  • the current collector is one of aluminum foil, titanium mesh, carbon paper, and carbon cloth.
  • step (1) laser heating is performed, and the laser power density is 1-10 kW/cm 2 .
  • Laser heating and cooling rates are fast, and the Prussian blue positive electrode material can be sintered quickly by laser heating, with little effect on the particle size, and the oil film on the surface of the material can be quickly removed.
  • the carbon material obtained by decomposing the oil film can form a carbon network between the particles, and has better conductivity than directly adding a conductive agent to mix.
  • Prussian blue cathode material is prepared by microemulsion method, and the formed water-in-oil microemulsion can effectively control the particle size of Prussian blue cathode material.
  • the surface of the material obtained by microemulsion method is coated with oil film, which can prevent the cathode material from absorbing water during storage.
  • FIG1 is a flow chart of the preparation of the Prussian blue positive electrode sheet described in this article.
  • the materials used in the examples and comparative examples can be obtained through commercial channels.
  • Antioxidants Ascorbic acid, commercially available
  • Sodium supplement sodium citrate, commercially available.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that, in step (3), 4 mL of transition metal salt solution is added dropwise to the precursor microemulsion.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that in step (2), the volume of the sodium ferrocyanide solution and the auxiliary agent solution is 2 mL respectively, and in step (3), the volume of the transition metal salt solution is 4 mL.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that in step (2), the volume of the sodium ferrocyanide solution and the auxiliary agent solution is 4 mL respectively, and in step (3), the volume of the transition metal salt solution is 4 mL.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that, in step (2), the content of AOT is 0.05 mol.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that, in step (2), the content of AOT is 0.03 mol.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that, in step (2), the content of AOT is 0.07 mol.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that the rate of dripping the transition metal salt solution into the precursor microemulsion is 20 mL/h.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that the rate of dripping the transition metal salt solution into the precursor microemulsion is 50 mL/h.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that the rate of dripping the transition metal salt solution into the precursor microemulsion is 60 mL/h.
  • An embodiment of the Prussian blue positive electrode material described herein is different from Embodiment 1 only in that in step (2), no auxiliary agent solution is added.
  • a Prussian blue positive electrode material wherein the Prussian blue positive electrode material is different from that of Example 1 only in that n-decane and AOT are not added in step (2).
  • a Prussian blue positive electrode material wherein the Prussian blue positive electrode material is different from that of Example 1 only in that in step (2), n-decane is not added.
  • Effect Examples 1 to 12 are the Prussian blue positive electrode sheets described herein, which are prepared from the Prussian blue positive electrode materials described in Examples 1 to 12, respectively, and the specific preparation methods are as follows:
  • the Prussian blue cathode material was sintered for 2 min at 600°C by laser heating, with a laser power density of 3 kW/cm 2 to obtain a cathode active material;
  • the positive electrode active material, the conductive agent and the binder are prepared into a slurry at a mass ratio of 90:3:8, and the slurry is coated on the current collector aluminum foil at a coating density of 30 mg/cm 2 , and dried to obtain the Prussian Blue positive electrode.
  • Effect Comparative Examples 1-2 are Prussian blue positive electrode sheets prepared from Comparative Examples 1-2, and the preparation method thereof is the same as that of Effect Examples 1-12.
  • Prussian blue positive electrode sheets The Prussian blue positive electrode sheets described in Examples 1 to 12 and Comparative Examples 1 to 2 were formed into sodium ion half-cells, and their initial discharge specific capacity and discharge specific capacity after 200 cycles under 0.1C were tested respectively. The water content of the material was tested using a Karl Fischer titrator, and the cutoff temperature for the water content test was 200°C. The test results are shown in Table 1.
  • the particle size of the Prussian blue cathode material prepared by the method described in this article can be maintained within 100nm, the particle uniformity is high, and the intrusion of water can be effectively prevented. After 30 days, the moisture content of the product changes little. During the charge and discharge cycle, the initial discharge specific capacity can basically reach more than 140mAh/g. At the same time, after 200 cycles at a rate of 0.1C, it can still basically maintain more than 135mAh/g, and the electrochemical performance is excellent.

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Abstract

一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片，涉及正极材料技术领域，所述普鲁士蓝正极材料的制备方法包括如下步骤：将亚铁氰化钠溶液、疏水液体、表面活性剂混合至不发生相分离，得到前驱体微乳液；将过渡金属盐溶液加入所述前驱体微乳液中，搅拌，得到普鲁士蓝微乳液；对所述普鲁士蓝微乳液进行陈化处理、固液分离、洗涤、烘干，得到所述普鲁士蓝正极材料。该方法制备的普鲁士蓝正极材料不易吸水，具有良好的储存性能，并且所述普鲁士蓝正极材料具有良好的导电性。

Description

一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片 技术领域
本文涉及正极材料技术领域，尤其涉及一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片。
背景技术
在科技、工业快速发展的背景下，全世界越来越依赖化石能源，这导致了能源短缺和碳排放的量的持续增加，最终导致了严重的环境问题。可再生能源作为突破现有困境的一个重要手段，新能源汽车应运而生。随着新能源汽车的快速发展，新能源电池产业也被推向风口。锂离子电池作为一种优秀的电子储能器件，已经被广泛应用于新能源汽车领域。然而，锂资源在地壳中的储量十分有限，这严重限制了锂离子电池的持续发展和大规模应用。相比而言，钠资源储量丰富、成本低廉，并且钠与锂位于同一主族，化学性质相似。综上，钠离子电池在可持续发展和大规模应用上具有很大的潜力和优势。
钠离子电池通过浓度差驱动，在充电过程中，钠离子穿过电解液由正极进入负极，在放电时，钠离子穿过电解液由负极进入正极，充放电过程保持高度的可逆性。但是，目前普鲁士蓝正极材料存在两大难题，一是颗粒的一致性较差，这是因为在共沉淀法合成普鲁士蓝正极材料的过程中，可溶性的金属盐与亚铁氰化钠反应并迅速成核长大；二是普鲁士蓝正极材料在储存过程中易吸水，会导致普鲁士蓝正极材料结晶度降低和体积膨胀，影响电化学性能和稳定性。
发明内容
本文的目的在于克服上述现有技术的不足之处而提供一种普鲁士蓝正极材料及其制备方法与普鲁士蓝正极片；所述普鲁士蓝正极材料具有良好的储存稳定性，不易吸湿，并且所述普鲁士蓝正极材料的粒径较小，具有良好的电性能。
为实现上述目的，本文所采取的技术方案为：
一种普鲁士蓝正极材料的制备方法，所述制备方法包括如下步骤：
将亚铁氰化钠溶液、疏水液体、表面活性剂混合至不发生相分离，得到前驱体微乳液；
将过渡金属盐溶液加入所述前驱体微乳液中，搅拌，得到普鲁士蓝微乳液；
对所述普鲁士蓝微乳液进行陈化处理、固液分离、洗涤、烘干，得到所述普鲁士蓝正极材料。
本文通过微乳液法制备普鲁士蓝正极材料，形成的油包水型微乳液能够有效地控制普鲁士蓝正极材料的粒径。并且所述油包水型普鲁士蓝正极材料的表面包裹有油膜，可以阻止干燥后的普鲁士蓝正极材料吸水，具有良好的储存稳定性。
在一实施例中，所述疏水液体为疏水液相有机物、疏水离子液体中的至少一种。
在一实施例中，所述疏水液相有机物的沸点大于水。
在一实施例中，所述疏水液相有机物为正辛烷、正癸烷、甲苯、异辛酸三甘油酯、正十六烷、二甲苯中的至少一种，所述疏水离子液体为1-丙基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐中的至少一种。选用上述材料作为疏水液体可以在所述普鲁士蓝正极材料表面形成均匀的油膜。
在一实施例中，所述亚铁氰化钠溶液由亚铁氰化钠溶于水配制得到，所述过渡金属盐溶液由过渡金属盐溶于水配制得到。
在一实施例中，所述亚铁氰化钠和所述过渡金属盐的物质的量之比为1：(1～2)；所述亚铁氰化钠在所述亚铁氰化钠溶液中的浓度为0.01～0.5mol/L，所述过渡金属盐在所述过渡金属盐溶液中的浓度为0.01～0.5mol/L，所述过渡金属盐为二价铁盐、钴盐、锰盐中的至少一种。在本文方案中，过渡金属盐的引入量需要在一定程度上过量，避免制备的产品颗粒产生缺陷。
在一实施例中，所述疏水液体和水溶液的体积比为100：(5～10)，所述水溶液为所述亚铁氰化钠溶液和所述过渡金属盐溶液的混合液。此外，当所述前驱体微乳液中还含有助剂溶液时，所述水溶液为所述亚铁氰化钠溶液、所述过渡金属盐溶液、所述助剂溶液的混合液；所述助剂溶液为抗氧化剂和补钠剂的混合水溶液，所述抗氧剂在所述助剂溶液中的浓度为0.01～0.05mol/L，所述补钠剂在所述助剂溶液中的浓度为0.01～0.05mol/L。对疏水液体和水溶液的体积比作上述限定可以保证制得的普鲁士蓝正极材料表面形成的油膜均匀致密，不易吸湿。
在一实施例中，所述抗氧化剂为柠檬酸钠、抗坏血酸、硫代硫酸钠中的至 少一种，所述补钠剂为氯化钠、碳酸钠、乙酸钠、硫代硫酸钠、柠檬酸钠中的至少一种。
在一实施例中，所述补钠剂和所述亚铁氰化钠的物质的量之比为(0.3～1.1)：1。
添加上述抗氧化剂和补钠剂可以改善所述普鲁士蓝正极材料的电性能，当将所述普鲁士蓝正极材料应用于正极片中时，其首次放电比容量以及循环性能均明显更优。
在一实施例中，所述表面活性剂和所述疏水液体的物质的量体积比为0.3～0.5mol/L。对表明活性剂和疏水液体的配比作上述限定可以得到稳定的普鲁士蓝微乳液。
在一实施例中，所述表面活性剂为亲油型表面活性剂，所述亲油型表面活性剂包含辛基酚聚氧乙烯醚、二(2-乙基己基)琥珀酸酯磺酸钠(AOT)、十二烷基酚聚氧乙烯醚、十二烷基缩水甘油醚、乙二醇脂肪酸酯、失水山梨醇倍半油酸酯中的至少一种。
在一实施例中，所述过渡金属盐溶液加入所述前驱体微乳液中的速率为20～50mL/h，所述加入过程在保护气氛下进行，所述保护气氛为氮气气氛、氦气气氛中的一种。控制过渡金属盐溶液的加入速率在上述范围内可以提高普鲁士蓝微乳液的稳定性，避免其与亚铁氰化钠过快反应，形成颗粒更均匀的正极材料。
在一实施例中，所述普鲁士蓝微乳液在60～100℃下搅拌10～60min后再进行陈化处理。
同时，本文还公开了一种由所述方法制备而成的普鲁士蓝正极材料以及由所述普鲁士蓝正极材料制备而成的普鲁士蓝正极片，所述普鲁士蓝正极片的制备方法包括如下步骤：
(1)将所述普鲁士蓝正极材料在500～800℃下烧结0.5～5min，得到正极活性材料；
(2)将所述正极活性材料与导电剂、粘结剂按质量比(85～98)：(1～5)：(2～10)配制成浆料，将所述浆料涂覆于集流体上，得到所述普鲁士蓝正极片。
在一实施例中，所述浆料在所述集流体上的涂覆密度为10～50mg/cm2，所述集流体为铝箔、钛网、碳纸、碳布中的一种。
在一实施例中，步骤(1)中，利用激光加热，激光功率密度为1～10kW/cm2。激光加热速率和冷却速率快，利用激光加热可以快速对所述普鲁士蓝正极材料进行烧结处理，对颗粒尺寸影响不大，可以快速去除材料表面的油膜，油膜分解得到的碳材料可以在颗粒之间形成碳网，相比于直接加入导电剂混合，导电性更好。
相比于现有技术，本文的有益效果为：
本文通过微乳液法制备普鲁士蓝正极材料，形成的油包水型微乳液能够有效地控制普鲁士蓝正极材料的粒径。另外，利用微乳液法得到的材料表面包裹有油膜，可以阻止正极材料在储存过程中吸水。
附图说明
图1为本文所述普鲁士蓝正极片的制备流程图。
具体实施方式
为更好地说明本文的目的、技术方案和优点，下面将结合附图和具体实施例对本文作进一步说明。
实施例及对比例中所用材料如无特殊说明，均可通过商业途径获得。
以下实施例及对比例中使用的材料信息如下：
抗氧化剂：抗坏血酸，市售；
补钠剂：柠檬酸钠，市售。
实施例1
本文所述普鲁士蓝正极材料的一种实施例，本实施例所述普鲁士蓝正极材料的制备方法如下：
(1)将亚铁氰化钠溶解于去离子水中，得到亚铁氰化钠浓度为0.1mol/L的亚铁氰化钠溶液；将氯化亚铁溶解于去离子水中，得到氯化亚铁浓度为0.1mol/L的过渡金属盐溶液，将抗氧化剂和补钠剂溶解于去离子水中，得到抗氧化剂浓度为0.01mol/L、补钠剂浓度为0.05mol/L的助剂溶液；
(2)将3mL亚铁氰化钠溶液、100mL正癸烷、3mL助剂溶液和0.04molAOT滴加混合，直至两相混合均匀且不发生相分离，得到前驱体微乳液；
(3)持续搅拌所述前驱体微乳液，以30mL/h的速率将3mL过渡金属盐溶 液滴加至所述前驱体微乳液中，滴加过程在氮气气氛中进行，滴加完全后再搅拌20min，得到普鲁士蓝微乳液；
(4)将普鲁士蓝微乳液在80℃、氮气气氛下持续搅拌30min，随后陈化、经固液分离、纯水洗涤、干燥，得到所述普鲁士蓝正极材料。
实施例2
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(3)中，将4mL过渡金属盐溶液滴加至所述前驱体微乳液中。
实施例3
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，亚铁氰化钠溶液、助剂溶液的体积分别为2mL，步骤(3)中，过渡金属盐溶液的体积为4mL。
实施例4
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，亚铁氰化钠溶液、助剂溶液的体积分别为4mL，步骤(3)中，过渡金属盐溶液的体积为4mL。
实施例5
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，所述AOT的含量为0.05mol。
实施例6
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，所述AOT的含量为0.03mol。
实施例7
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，所述AOT的含量为0.07mol。
实施例8
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅 在于，以疏水离子液体1-丙基-3-甲基咪唑六氟磷酸盐替代正癸烷。
实施例9
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，所述过渡金属盐溶液滴加至所述前驱体微乳液中的速率为20mL/h。
实施例10
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，所述过渡金属盐溶液滴加至所述前驱体微乳液中的速率为50mL/h。
实施例11
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，所述过渡金属盐溶液滴加至所述前驱体微乳液中的速率为60mL/h。
实施例12
本文所述普鲁士蓝正极材料的一种实施例，本实施例与实施例1的区别仅在于，步骤(2)中，未添加助剂溶液。
对比例1
一种普鲁士蓝正极材料，所述普鲁士蓝正极材料与实施例1的区别仅在于，步骤(2)中未添加正癸烷和AOT。
对比例2
一种普鲁士蓝正极材料，所述普鲁士蓝正极材料与实施例1的区别仅在于，步骤(2)中，未添加正癸烷。
效果例1～12
效果例1～12为本文所述普鲁士蓝正极片，分别由实施例1～12所述普鲁士蓝正极材料制备而成，具体制备方法如下：
(1)利用激光加热在600℃下对普鲁士蓝正极材料进行2min的短时烧结，激光功率密度为3kW/cm2，得到正极活性材料；
(2)将所述正极活性材料与导电剂、粘结剂按质量比90:3:8配置浆料，将所述浆料涂覆于集流体铝箔上，涂覆密度为30mg/cm2，干燥，得到所述普鲁士 蓝正极片。
效果对比例1～2
效果对比例1～2为由对比例1～2制备而成的普鲁士蓝正极片，其制备方法与效果例1～12相同。
性能测试
1、普鲁士蓝正极片的电性能：将效果例1～12和效果对比例1～2所述普鲁士蓝正极片组成为钠离子半电池，分别测试其在0.1C条件下的首次放电比容量和200次循环后的放电比容量。利用卡尔-费休水分仪测试材料含水量，水含量测试截止温度为200℃。测试结果见表1。
2、普鲁士蓝正极材料的颗粒尺寸。
表1

从表1可以看出，本文所述方法制备的普鲁士蓝正极材料颗粒尺寸可维持在100nm以内，颗粒均匀度高，可有效阻止水分入侵，在经过30天后产品的水分含量变化程度低，在进行充放电循环时初始放电比容量可基本达到140mAh/g以上，同时在0.1C倍率循环200次后仍基本可保持135mAh/g以上，电化学性能优异。
最后所应当说明的是，以上实施例仅用以说明本文的技术方案而非对本文保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本文的技术方案进行修改或者等同替换，但并不脱离本文技术方案的实质和范围。

Claims (15)

  1. 一种普鲁士蓝正极材料的制备方法，其特征在于，包括如下步骤：
    将亚铁氰化钠溶液、疏水液体、表面活性剂混合至不发生相分离，得到前驱体微乳液；
    将过渡金属盐溶液加入所述前驱体微乳液中，搅拌，得到普鲁士蓝微乳液；
    对所述普鲁士蓝微乳液进行陈化处理、固液分离、洗涤、烘干，得到所述普鲁士蓝正极材料。
  2. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述疏水液体为疏水液相有机物、疏水离子液体中的至少一种；所述疏水液相有机物为正辛烷、正癸烷、甲苯、异辛酸三甘油酯、正十六烷、二甲苯中的至少一种，所述疏水离子液体为1-丙基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐中的至少一种。
  3. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述亚铁氰化钠溶液由亚铁氰化钠溶于水配制得到，所述过渡金属盐溶液由过渡金属盐溶于水配制得到；所述亚铁氰化钠和所述过渡金属盐的物质的量之比为1：(1～2)；所述亚铁氰化钠在所述亚铁氰化钠溶液中的浓度为0.01～0.5mol/L，所述过渡金属盐在所述过渡金属盐溶液中的浓度为0.01～0.5mol/L，所述过渡金属盐为二价铁盐、钴盐、锰盐中的至少一种。
  4. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述疏水液体和水溶液的体积比为100：(5～10)，所述水溶液为所述亚铁氰化钠溶液和所述过渡金属盐溶液的混合液。
  5. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述前驱体微乳液中还含有助剂溶液，所述助剂溶液为抗氧化剂和补钠剂的混合水溶液，所述抗氧剂在所述助剂溶液中的浓度为0.01～0.05mol/L，所述补钠剂在所述助剂溶液中的浓度为0.01～0.05mol/L。
  6. 如权利要求5所述普鲁士蓝正极材料的制备方法，其特征在于，所述疏 水液体和水溶液的体积比为100：(5～10)，所述水溶液为所述亚铁氰化钠溶液、所述过渡金属盐溶液、所述助剂溶液的混合液。
  7. 如权利要求5所述普鲁士蓝正极材料的制备方法，其特征在于，所述抗氧化剂为柠檬酸钠、抗坏血酸、硫代硫酸钠中的至少一种，所述补钠剂为氯化钠、碳酸钠、乙酸钠、硫代硫酸钠、柠檬酸钠中的至少一种。
  8. 如权利要求5所述普鲁士蓝正极材料的制备方法，其特征在于，所述补钠剂和所述亚铁氰化钠的物质的量之比为(0.3～1.1)：1。
  9. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述表面活性剂和所述疏水液体的物质的量体积比为0.3～0.5mol/L。
  10. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述表面活性剂为亲油型表面活性剂，所述亲油型表面活性剂包含辛基酚聚氧乙烯醚、二(2-乙基己基)琥珀酸酯磺酸钠、十二烷基酚聚氧乙烯醚、十二烷基缩水甘油醚、乙二醇脂肪酸酯、失水山梨醇倍半油酸酯中的至少一种。
  11. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述过渡金属盐溶液加入所述前驱体微乳液中的速率为20～50mL/h，所述加入过程在保护气氛下进行。
  12. 如权利要求1所述普鲁士蓝正极材料的制备方法，其特征在于，所述普鲁士蓝微乳液在60～100℃下搅拌10～60min后再进行陈化处理。
  13. 一种普鲁士蓝正极材料，其特征在于，由如权利要求1～12任一项所述方法制备而成。
  14. 一种普鲁士蓝正极片，其特征在于，由如权利要求13所述普鲁士蓝正极材料制备而成，包括如下步骤：
    将所述普鲁士蓝正极材料在500～800℃下烧结0.5～5min，得到正极活性材料；
    将所述正极活性材料与导电剂、粘结剂按质量比(85～98)：(1～5)：(2～10)配制成浆料，将所述浆料涂覆于集流体上，得到所述普鲁士蓝正极片。
  15. 如权利要求14所述普鲁士蓝正极片，其特征在于，所述浆料在所述集流体上的涂覆密度为10～50mg/cm2。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006256954A (ja) * 2005-02-17 2006-09-28 National Institute Of Advanced Industrial & Technology プルシアンブルー型金属錯体超微粒子、その分散液、及びそれらの製造方法
CN101368928A (zh) * 2007-09-05 2009-02-18 浙江师范大学 反胶束法制备普鲁士蓝纳米粒子用于电化学分析
CN113054163A (zh) * 2021-03-11 2021-06-29 中国电力科学研究院有限公司 一种普鲁士蓝基钠离子全电池及其制备方法
CN114805450A (zh) * 2022-06-15 2022-07-29 国网智能电网研究院有限公司 一种高熵普鲁士蓝钠离子电池正极材料的制备方法及其应用

Family Cites Families (4)

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JP2004091645A (ja) * 2002-08-30 2004-03-25 Miyoshi Kasei Inc 表面処理された紺青被覆粉体及びその製造方法
CN115023829A (zh) * 2020-02-24 2022-09-06 辽宁星空钠电电池有限公司 一种低水分含量的普鲁士蓝钠离子电池正极材料及其制备方法和钠离子电池
CN114275762B (zh) * 2021-12-24 2023-10-27 广东钠壹新能源科技有限公司 一种氮掺杂硬碳钠离子电池负极材料及其制备方法
CN116247201A (zh) * 2023-02-24 2023-06-09 中国科学技术大学 一种钠离子电池用普鲁士蓝类正极材料及其制备方法及钠离子电池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006256954A (ja) * 2005-02-17 2006-09-28 National Institute Of Advanced Industrial & Technology プルシアンブルー型金属錯体超微粒子、その分散液、及びそれらの製造方法
CN101368928A (zh) * 2007-09-05 2009-02-18 浙江师范大学 反胶束法制备普鲁士蓝纳米粒子用于电化学分析
CN113054163A (zh) * 2021-03-11 2021-06-29 中国电力科学研究院有限公司 一种普鲁士蓝基钠离子全电池及其制备方法
CN114805450A (zh) * 2022-06-15 2022-07-29 国网智能电网研究院有限公司 一种高熵普鲁士蓝钠离子电池正极材料的制备方法及其应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HE GENGAHN E, QUAN TAO, CHUANG LIU, DI ZHANG, YUPING ZHOU, LIU RUIYUAN: "Mn2+?doped Prussian blue nanoparticles for T1?T2 dual?mode magnetic resonance imaging and photothermal therapy in vitro", JOURNAL OF SOUTHERN MEDICAL UNIVERSITY, vol. 41, no. 6, 1 January 2021 (2021-01-01), pages 909 - 915, XP093248002, ISSN: 1673-4254, DOI: 10.12122/j.issn.1673-4254.2021.06.14 *
LIU HUI: "Preparation and Properties Study on K-PBA and Na-PBA Magnet Nanomaterials", CHINA MASTER’S THESES FULL-TEXT DATABASE (BASIC SCIENCES), 1 May 2009 (2009-05-01), XP093248003, ISSN: 1674-0246 *

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