WO2025043913A1 - 一种钠离子电池正极材料的制备方法和应用 - Google Patents

一种钠离子电池正极材料的制备方法和应用 Download PDF

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WO2025043913A1
WO2025043913A1 PCT/CN2023/134736 CN2023134736W WO2025043913A1 WO 2025043913 A1 WO2025043913 A1 WO 2025043913A1 CN 2023134736 W CN2023134736 W CN 2023134736W WO 2025043913 A1 WO2025043913 A1 WO 2025043913A1
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sodium
ion battery
positive electrode
electrode material
sodium ion
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English (en)
French (fr)
Inventor
孙杰
何健豪
李金懋
高佳慧
梅京
何中林
蔡望
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Hubei Rt Advanced Materials Group Co Ltd
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Hubei Rt Advanced Materials Group Co Ltd
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Priority to EP23833294.4A priority Critical patent/EP4539155A4/en
Priority to JP2023576019A priority patent/JP7850514B2/ja
Priority to KR1020247000129A priority patent/KR102919005B1/ko
Publication of WO2025043913A1 publication Critical patent/WO2025043913A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of sodium ion batteries, and more specifically, to a preparation method and application of a positive electrode material for a sodium ion battery.
  • lithium-ion batteries As the representative of secondary batteries with the best comprehensive performance, the commercialization of lithium-ion batteries can be traced back to the 1990s. After years of research, lithium-ion batteries have developed into a mature battery technology route. However, due to the abundance of lithium in the earth's crust, lithium-ion batteries are difficult to support the growing energy storage market. The working principle of sodium-ion batteries is similar to that of lithium-ion batteries, and sodium salt reserves are abundant and easy to mine, which makes them more advantageous in the large-scale application of subsequent energy storage fields.
  • Sodium ion batteries are mainly composed of positive electrodes, negative electrodes, electrolytes, diaphragms and accessory components. Among them, positive and negative electrode materials are the key to the performance of sodium ion battery systems, and positive electrode materials are particularly prominent.
  • Sodium ion battery positive electrode materials are divided into three categories: transition metal oxides, Prussian white/blue and polyanion types. Among them, polyanion sodium ion battery positive electrode materials have the advantages of stable structure and small volume change during charging and discharging. Among the polyanion sodium ion battery positive electrode materials, iron-based sodium batteries have the advantages of lowest cost and non-toxicity.
  • sodium iron pyrophosphate Na 4 Fe 3 (PO 4 ) 2 P 2 O 7
  • 129 mAh/g high theoretical capacity
  • excellent cycle performance low volume expansion (about 4%).
  • the high-temperature solid phase method using the grinding-spraying-sintering process route is the most effective production method for preparing secondary battery positive electrode materials.
  • the raw materials used are unevenly mixed at the microscopic level, resulting in the generation of impurities sodium iron phosphate and sodium iron pyrophosphate, making the crystal phase purity of the prepared positive electrode material low.
  • the above shortcomings seriously limit the subsequent application of the sodium iron phosphate pyrophosphate positive electrode material.
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the present invention proposes a preparation method and application of a positive electrode material for a sodium ion battery.
  • the sodium ion battery positive electrode material has high crystal phase purity, higher compaction density and energy density.
  • the preparation method has a simple process flow and is suitable for large-scale industrial production.
  • an embodiment of the present invention provides a method for preparing a positive electrode material for a sodium ion battery, the preparation method comprising: dispersing a sodium source compound, ferric hydrogen phosphate hydrate and a carbon source compound in water in a certain proportion, stirring and mixing to obtain a dispersion; placing the dispersion in a sand mill and sand milling for a certain period of time to obtain a slurry; drying the sand milled slurry to obtain a powdered precursor; sintering and crushing the powdered precursor to obtain the sodium ion battery positive electrode material.
  • the sodium source compound is one or more of sodium formate, sodium acetate, sodium citrate, sodium oxalate, sodium chloride, sodium nitrate and sodium sulfate.
  • the amount of the carbon source added is 10wt%-55wt% of the amount of the ferric hydrogen phosphate hydrate added.
  • the carbon source compound is one or more of vaseline, stearic acid, sucrose, ascorbic acid, formaldehyde, acetaldehyde, n-butyraldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, soluble starch, glucose, polyethylene glycol, maltose, cyclodextrin, carbon nanotubes, acetylene black and graphene.
  • the sanding method of the sand mill includes one of disc type, pin type and turbine type; the particle size of the slurry after sanding is controlled to be 0.1 ⁇ m ⁇ DN50 ⁇ 5 ⁇ m.
  • the drying method may be one or more of air drying, vacuum drying, freeze drying and spray drying.
  • the sintering conditions include sintering atmosphere, sintering temperature and sintering time
  • the sintering atmosphere includes one or a mixed atmosphere of nitrogen, argon and helium
  • the sintering temperature is 450-700°C
  • the heating rate is 1-3°C/min
  • the sintering time is 6-24h.
  • the pulverization method can be one or both of mechanical pulverization and air flow pulverization.
  • an embodiment of the present invention provides a sodium ion battery, comprising the sodium ion battery positive electrode material provided in the first aspect above.
  • the method for preparing the positive electrode material for a sodium ion battery uses a raw material of iron hydrogen phosphate hydrate (Fe 3 (HPO 4 ) 4 ⁇ H 2 O) with a fixed iron-phosphorus ratio as a precursor during the preparation process, thereby eliminating the influence of the processing process on the designed raw material ratio at the microscopic level, ensuring the uniformity of the raw materials, and making the prepared positive electrode material for a sodium ion battery have high crystal phase purity, better crystallinity, better electrochemical performance, and higher compaction density and energy density.
  • the preparation method has a simple process flow and is suitable for application in large-scale industrial production.
  • FIG1 is a flow chart of a method for preparing a positive electrode material for a sodium ion battery provided in an embodiment of the present invention.
  • FIG. 2 is a SEM image of the sodium ion battery positive electrode material prepared in Example 1 of the present invention.
  • FIG3 is an XRD diagram of the sodium ion battery positive electrode material prepared in Example 1 of the present invention.
  • FIG4 is a graph showing the first charge and discharge curve of a button-type half-cell assembled with the sodium ion battery positive electrode material prepared in Example 1 of the present invention at 0.1C.
  • FIG. 5 is an XRD diagram of the sodium ion battery positive electrode material prepared in Example 2 of the present invention.
  • FIG6 is a graph showing the first charge and discharge curves of a button-type half-cell assembled with the sodium ion battery positive electrode material prepared in Example 2 of the present invention at 0.1C.
  • FIG. 7 is an XRD diagram of the sodium ion battery positive electrode material prepared in Example 3 of the present invention.
  • FIG8 is a graph showing the first charge and discharge curve of a button-type half-cell assembled with the sodium ion battery positive electrode material prepared in Example 3 of the present invention at 0.1C.
  • the embodiment of the present invention provides a method for preparing a sodium ion battery positive electrode material and its application, which is used to prepare a sodium ion battery positive electrode material with high crystal phase purity, high compaction density and high energy density.
  • the sodium ion battery positive electrode material of the present invention is a sodium ferric phosphate pyrophosphate positive electrode material, and its chemical formula is Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 .
  • the sodium ion battery prepared based on the sodium ion battery positive electrode material of the present invention has good battery cycle performance and stability.
  • the first embodiment of the present invention provides a method for preparing a positive electrode material for a sodium ion battery.
  • the steps include:
  • Step S1 dispersing a sodium source compound, ferric hydrogen phosphate hydrate and a carbon source compound in water in a certain proportion and stirring and mixing to obtain a dispersion;
  • the sodium source compound can be one or more of sodium formate, sodium acetate, sodium citrate, sodium oxalate, sodium chloride, sodium nitrate and sodium sulfate.
  • the amount of the carbon source added is 10wt%-55wt% of the amount of ferric hydrogen phosphate hydrate added;
  • the carbon source compound can be one or more of vaseline, stearic acid, sucrose, ascorbic acid, formaldehyde, acetaldehyde, n-butyraldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, soluble starch, glucose, polyethylene glycol, maltose, cyclodextrin, carbon nanotubes, acetylene black and graphene.
  • Step S2 placing the dispersion in a sand mill and sand grinding for a certain period of time to obtain a slurry
  • the sand mill has a sand grinding method including a disc type, a pin type, and a turbine type.
  • the particle size of the slurry after sand grinding is controlled within 0.1 ⁇ m ⁇ DN50 ⁇ 5 ⁇ m.
  • Step S3 drying the sand-milled slurry to obtain a powdered precursor
  • the drying method may be one or more of air drying, vacuum drying, freeze drying and spray drying.
  • Step S4 Sintering and crushing the powdered precursor to obtain the sodium ion battery positive electrode material.
  • the sintering conditions include sintering atmosphere, sintering temperature and sintering time.
  • the sintering atmosphere includes one or a mixture of nitrogen, argon and helium; the sintering temperature can be 450-700°C, and the heating rate can be 1-3°C/min; the sintering time can be 6-24h.
  • the pulverization method can be one or both of mechanical pulverization and air flow pulverization.
  • the method for preparing the positive electrode material for a sodium ion battery adopts a raw material of hydrogen phosphate iron hydrate ( Fe3 ( HPO4 ) 4 ⁇ H2O ) with a fixed iron-phosphorus ratio as a precursor during the preparation process, thereby eliminating the influence of the processing process on the designed raw material ratio at the microscopic level, ensuring the uniformity of the raw materials, and making the prepared positive electrode material for a sodium ion battery have high crystal phase purity, better crystallinity, better electrochemical performance, and higher compaction density and energy density.
  • the sodium ion battery prepared based on the positive electrode material for a sodium ion battery of the present invention has good battery cycle performance and stability. At the same time, the preparation method has a simple process flow and is suitable for application in large-scale industrial production.
  • This embodiment provides a method for preparing a positive electrode material for a sodium ion battery.
  • the positive electrode material for a sodium ion battery prepared in this embodiment is a Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material, and the method comprises the following steps:
  • FIG2 is a SEM image of the Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 cathode material prepared in this example;
  • FIG3 is an XRD diagram of the Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material prepared in this example.
  • acetylene black and PVDF prepared in this embodiment are mixed and homogenized in a mass ratio of 70:20:10, the black slurry is coated on aluminum foil using a 150 ⁇ m four-sided preparation device, and then the film is vacuum dried in a vacuum drying oven at 110°C for 6h. Then, a punching machine is used to punch the dried electrode film into a circular sheet with a uniform radius, which is the positive electrode sheet.
  • the diaphragm is a glass fiber membrane
  • a button half-cell is assembled in a glove box with a water and oxygen content of less than 0.01ppm.
  • the test results are shown in Figure 4. When the current density is 0.1C and the voltage range is 2.0-4.0V, its discharge capacity reaches 109.7mAh/g.
  • This embodiment provides a method for preparing a positive electrode material for a sodium ion battery.
  • the positive electrode material for a sodium ion battery prepared in this embodiment is a Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material, and the method comprises the following steps:
  • FIG5 is an XRD diagram of the Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material prepared in this example.
  • the Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 cathode material prepared in this example, acetylene black and PVDF were mixed in a mass ratio of 70:20:10. After adding an appropriate amount of NMP to the mixture in a ratio of , the black slurry was coated on aluminum foil using a 150 ⁇ m four-sided preparation device, and then the film was vacuum dried in a vacuum drying oven at 110°C for 6h. Then a punching machine was used to punch the dried electrode film into round pieces with the same radius, which were the positive electrode pieces.
  • This embodiment provides a method for preparing a positive electrode material for a sodium ion battery.
  • the positive electrode material for a sodium ion battery prepared in this embodiment is a Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material, and the method comprises the following steps:
  • FIG. 7 is an XRD diagram of the Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 positive electrode material prepared in this example.
  • acetylene black and PVDF prepared in this embodiment are mixed with an appropriate amount of NMP in a mass ratio of 70:20:10, the black slurry is coated on aluminum foil using a 150 ⁇ m four-sided preparation device, and then the film is vacuum dried in a vacuum drying oven at 110°C for 6h. Then, a punching machine is used to punch the dried electrode film into a circular sheet with a uniform radius, which is the positive electrode sheet.
  • the test results are shown in Figure 8. When the current density is 0.1C and the voltage range is 2.0-4.0V, its discharge capacity reaches 110.5mAh/g.
  • a second aspect of the present invention provides a sodium ion battery, which includes a sodium ion battery positive electrode material prepared by the preparation method provided by the first aspect of the present invention.
  • the preparation method and application of the positive electrode material for sodium ion batteries adopts the raw material hydrogen phosphate hydrate ( Fe3 ( HPO4 ) 4 ⁇ H2O ) with a fixed iron-phosphorus ratio as a precursor during the preparation process, thereby eliminating the influence of the processing process on the designed raw material ratio at the microscopic level, ensuring the uniformity of the raw materials, and making the prepared positive electrode material for sodium ion batteries have high crystal phase purity, better crystallinity, better electrochemical performance, and higher compaction density and energy density.
  • the battery has good battery cycle performance and stability.
  • the preparation method has a simple process flow and is suitable for application in large-scale industrial production.

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Abstract

提供了一种钠离子电池正极材料的制备方法，制备方法包括：将钠源化合物、磷酸氢铁水合物和碳源化合物按照一定比例分散于水中搅拌混合，得到分散液；将分散液置于砂磨机中砂磨一定时间，获得浆料；将砂磨后的浆料进行干燥，得到粉末状前驱体；将粉末状前驱体烧结粉碎后，得到钠离子电池正极材料。通过制备方法制备的钠离子电池正极材料晶体相纯度高，拥有更高的压实密度及能量密度。基于钠离子电池正极材料制备的钠离子电池具有良好的电池循环性能和稳定性。同时制备方法工艺流程简单，适于大规模工业生产中应用。

Description

一种钠离子电池正极材料的制备方法和应用 技术领域
本发明涉及钠离子电池技术领域，更具体地，尤其涉及一种钠离子电池正极材料的制备方法和应用。
背景技术
作为当前综合性能最优异的二次电池代表，锂离子电池的商业化最早可以追溯至20世纪90年代。经过多年的研究，锂离子电池已经发展为成熟的电池技术路线。然而受锂元素地壳丰度限制，锂离子电池难以支撑目前日益增长的储能市场。钠离子电池工作原理和锂离子电池工作原理类似，且钠盐储量丰富，开采简单，在后续储能领域大规模应用方向更具优势。
钠离子电池主要由正极、负极、电解质、隔膜及附属部件构成。其中，正负极材料是影响钠离子电池体系性能的关键，而正极材料尤为突出。钠离子电池正极材料分为过渡金属氧化物、普鲁士白/蓝以及聚阴离子型三大类。其中聚阴离子型钠离子电池正极材料具有充放电时结构稳定、体积变化小的优点。在聚阴离子型钠离子电池正极材料中铁基钠电池具有最低的成本且无毒的优点，其中磷酸焦磷酸铁钠(Na4Fe3(PO4)2P2O7)为铁基钠电中的最具潜力的正极材料，其具有低成本、环境友好、高理论容量(129mAh/g)、循环性能优异和低体积膨胀(约4％)的优点。
目前采用研磨-喷雾-烧结工艺路线的高温固相法是制备二次电池正极材料最具效益的生产方法。然而，由于加工过程的影响，采用该工艺路线制备磷酸焦磷酸铁钠时，所用原料在微观层面混合不均，从而导致杂质磷酸铁钠和焦磷酸铁钠的产生，使得制备出的正极材料的晶体相纯度较低，上述缺点严重限制了该磷酸焦磷酸铁钠正极材料的后续应用。
发明内容
鉴于以上内容，本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出了一种钠离子电池正极材料的其制备方法和应用。通过本发明制备方法制备 的钠离子电池正极材料晶体相纯度高，并且拥有更高的压实密度及能量密度。同时该制备方法工艺流程简单，适于大规模工业生产中应用。
为此，第一方面，本发明实施例提供了一种钠离子电池正极材料的制备方法，所述制备方法包括：将钠源化合物、磷酸氢铁水合物和碳源化合物按照一定比例分散于水中搅拌混合，得到分散液；将所述分散液置于砂磨机中砂磨一定时间，获得浆料；将砂磨后的浆料进行干燥，得到粉末状前驱体；将所述粉末状前驱体烧结粉碎后，得到所述钠离子电池正极材料。
优选地，所述分散液中钠源化合物与所述磷酸氢铁水合物的加入量按照摩尔比n(Na)：n(Fe)＝4:3加入。
优选地，所述钠源化合物为甲酸钠、乙酸钠、柠檬酸钠、草酸钠、氯化钠、硝酸钠以及硫酸钠中的一种或多种。
优选地，所述碳源加入量为所述磷酸氢铁水合物加入量的10wt％-55wt％。
优选地，所述碳源化合物为凡士林、硬脂酸、蔗糖、抗坏血酸、甲醛、乙醛、正丁醛、乳酸、柠檬酸、苹果酸、乙二酸、己二酸、可溶性淀粉、葡萄糖、聚乙二醇、麦芽糖、环糊精、碳纳米管、乙炔黑以及石墨烯中的一种或多种。
优选地，所述砂磨机的砂磨方式包括盘式、棒销式、涡轮式中的一种；砂磨后的浆料粒径控制在0.1μm<DN50<5μm。
优选地，所述干燥方法可以为鼓风干燥、真空干燥、冷冻干燥、喷雾干燥中的一种或多种。
优选地，所述烧结条件包括烧结气氛、烧结温度以及烧结时间，所述烧结气氛包括氮气、氩气、氦气中的一种或几种混合气氛；所述烧结温度为450-700℃，升温速率为1-3℃/min；所述烧结时间为6-24h。
优选地，所述粉碎方法可以为机械粉碎、气流粉碎中的一种或两种。
第二方面，本发明实施例提供了一种钠离子电池，包括上述第一方面提供的钠离子电池正极材料。
本发明实施例提供的钠离子电池正极材料的制备方法在制备过程中采用具有固定铁磷比的原料磷酸氢铁水合物(Fe3(HPO4)4·H2O)作为前驱体，消除了加工过程在微观层面对设计原料配比的影响，保证了原料的均一性，使得制备出的钠离子电池正极材料晶体相纯度高，拥有更好的结晶性，电化学性能更佳，并且拥有更高的压实密度及能量密度。同时该制备方法工艺流程简单，适于大规模工业生产中应用。
附图说明
图1为本发明实施例提供的钠离子电池正极材料的制备方法流程图。
图2为本发明的实施例1制备得到的钠离子电池正极材料的SEM图。
图3为本发明的实施例1制备得到的钠离子电池正极材料的XRD图。
图4为本发明的实施例1制备得到的钠离子电池正极材料组装的扣式半电池在0.1C下的首次充放电曲线图。
图5为本发明的实施例2制备得到的钠离子电池正极材料的XRD图。
图6为本发明的实施例2制备得到的钠离子电池正极材料组装的扣式半电池在0.1C下的首次充放电曲线图。
图7为本发明的实施例3制备得到的钠离子电池正极材料的XRD图。
图8为本发明的实施例3制备得到的钠离子电池正极材料组装的扣式半电池在0.1C下的首次充放电曲线图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
下文的公开提供了许多不同的实施例或例子用来实现本发明的不同结构。为了简化本发明的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本发明。此外，本发明可以在不同例子中重复参考数字和/或字母。这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施例和/或设置之间的关系。此外，本发明提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的可应用于性和/或其他材料的使用。
本发明实施例提供一种钠离子电池正极材料的制备方法和应用，用于制备一种高晶体相纯度、高压实密度、高能量密度的钠离子电池正极材料。本发明所述钠离子电池正极材料为磷酸焦磷酸铁纳正极材料，其化学式为Na4Fe3(PO4)2P2O7。基于本发明所述钠离子电池正极材料制备的钠离子电池具有良好的电池循环性能和稳定性。
如图1所示，本发明第一方面实施例提供一种钠离子电池正极材料的制备方法， 包括如下步骤：
步骤S1：将钠源化合物、磷酸氢铁水合物和碳源化合物按照一定比例分散于水中搅拌混合，得到分散液；
在本发明实施例中，所述磷酸氢铁水合物的化学式为Fe3(HPO4)4·H2O，所述分散液中钠源化合物与所述磷酸氢铁水合物的加入量按照摩尔比n(Na)：n(Fe)＝4:3加入。
其中，所述钠源化合物可以为甲酸钠、乙酸钠、柠檬酸钠、草酸钠、氯化钠、硝酸钠以及硫酸钠中的一种或多种。
所述碳源加入量为磷酸氢铁水合物加入量的10wt％-55wt％；所述碳源化合物可以为凡士林、硬脂酸、蔗糖、抗坏血酸、甲醛、乙醛、正丁醛、乳酸、柠檬酸、苹果酸、乙二酸、己二酸、可溶性淀粉、葡萄糖、聚乙二醇、麦芽糖、环糊精、碳纳米管、乙炔黑以及石墨烯中的一种或多种。
步骤S2：将所述分散液置于砂磨机中砂磨一定时间，获得浆料；
其中，所述砂磨机的砂磨方式包括盘式、棒销式、涡轮式中的一种。砂磨后的浆料粒径控制在0.1μm<DN50<5μm。
步骤S3：将砂磨后的浆料进行干燥，得到粉末状前驱体；
其中，所述干燥方法可以为鼓风干燥、真空干燥、冷冻干燥、喷雾干燥中的一种或多种。
步骤S4：将所述粉末状前驱体烧结粉碎后，得到所述钠离子电池正极材料。
其中，所述烧结条件包括烧结气氛、烧结温度以及烧结时间。所述烧结气氛包括氮气、氩气、氦气中的一种或几种混合气氛；所述烧结温度可以为450-700℃，升温速率为1-3℃/min；所述烧结时间可以为6-24h。所述粉碎方法可以为机械粉碎、气流粉碎中的一种或两种。
本发明实施例提供的钠离子电池正极材料的制备方法在制备过程中采用具有固定铁磷比的原料磷酸氢铁水合物(Fe3(HPO4)4·H2O)作为前驱体，消除了加工过程在微观层面对设计原料配比的影响，保证了原料的均一性，使得制备出的钠离子电池正极材料晶体相纯度高，拥有更好的结晶性，电化学性能更佳，并且拥有更高的压实密度及能量密度。基于本发明所述钠离子电池正极材料制备的钠离子电池具有良好的电池循环性能和稳定性。同时该制备方法工艺流程简单，适于大规模工业生产中应用。
以下结合一些具体的实施例，对采用本发明的钠离子电池正极材料的制备方法的 具体过程和效果进行进一步地详细说明，但并不限制于本发明的保护范围。
实施例1
本实施例提供一种钠离子电池正极材料的制备方法，本实施例制备的钠离子电池正极材料为Na4Fe3(PO4)2P2O7正极材料，包括以下步骤：
称取1mol的磷酸氢铁水合物和4mol硝酸钠，并将其分散于去离子水中，称取质量为磷酸氢铁水合物添加质量20％的葡萄糖加入上述去离子水中，搅拌混合后得到分散液。将上述分散液进行砂磨，当分散液中固体颗粒粒度DN50＝0.2μm时停止研磨，获得浆料。将上述研磨后的浆料进行喷雾干燥，得到粉末状前驱体。将所得粉末状前驱体放置于氮气气氛中，以2℃/min升温至500℃，保温18h，待物料冷却破碎后即得Na4Fe3(PO4)2P2O7钠离子电池正极材料。
图2为本实施例制备的Na4Fe3(PO4)2P2O7正极材料的SEM图；
图3为本实施例制备的Na4Fe3(PO4)2P2O7正极材料的XRD图。
将本实施例制备的Na4Fe3(PO4)2P2O7正极材料、乙炔黑、PVDF按质量比70:20:10的比例加入适量NMP混合匀浆后，使用150μm四面制备器将黑色浆料涂覆在铝箔上，然后将该膜在110℃真空干燥箱中真空干燥6h。再使用冲片机将干燥后的电极膜冲为半径一致的圆片即为正极极片。以金属钠为负极极片，隔膜为玻璃纤维膜，电解液为NaPF6/EC+DEC+DMC(EC:DEC:DMC＝1:1:1体积比)，在水氧含量小于0.01ppm的手套箱中组装成扣式半电池。测试结果如图4所示，在电流密度为0.1C，电压范围为2.0-4.0V时，其放电容量达到109.7mAh/g。
实施例2
本实施例提供一种钠离子电池正极材料的制备方法，本实施例制备的钠离子电池正极材料为Na4Fe3(PO4)2P2O7正极材料，包括以下步骤：
称取1mol的磷酸氢铁水合物和4mol的氯化钠，并将其分散于去离子水中，称取质量为磷酸氢铁水合物添加质量30％的葡萄糖加入上述去离子水中，搅拌混合后得到分散液。将上述分散液进行砂磨，当分散液中固体颗粒粒度DN50＝3.0μm时停止研磨，获得浆料。将上述研磨后的浆料进行喷雾干燥，得到粉末状前驱体。将所得粉末状前驱体放置于氮气气氛中，以2℃/min升温至550℃，保温16h，待物料冷却破碎后即得Na4Fe3(PO4)2P2O7钠离子电池正极材料。
图5为本实施例制备的Na4Fe3(PO4)2P2O7正极材料的XRD图。
将本实施例制备的Na4Fe3(PO4)2P2O7正极材料、乙炔黑、PVDF按质量比70:20:10 的比例加入适量NMP混合匀浆后，使用150μm四面制备器将黑色浆料涂覆在铝箔上，然后将该膜在110℃真空干燥箱中真空干燥6h。再使用冲片机将干燥后的电极膜冲为半径一致的圆片即为正极极片。以金属钠为负极极片，隔膜为玻璃纤维膜，电解液为NaPF6/EC+DEC+DMC(EC:DEC:DMC＝1:1:1体积比)，在水氧含量小于0.01ppm的手套箱中组装成扣式半电池。测试结果如图6所示，在电流密度为0.1C，电压范围为2.0-4.0V时，其放电容量达到112.9mAh/g。
实施例3
本实施例提供一种钠离子电池正极材料的制备方法，本实施例制备的钠离子电池正极材料为Na4Fe3(PO4)2P2O7正极材料，包括以下步骤：
称取1mol的磷酸氢铁水合物和4mol的乙酸钠，并将其分散于去离子水中，称取质量为磷酸氢铁水合物添加质量25％的葡萄糖加入上述去离子水中，搅拌混合后得到分散液。将上述分散液进行砂磨，当分散液中固体颗粒粒度DN50＝4.6μm时停止研磨，获得浆料。将上述研磨后的浆料进行喷雾干燥，得到粉末状前驱体。将所得粉末状前驱体放置于氮气气氛中，以5℃/min升温至600℃，保温12h，待物料冷却破碎后即得Na4Fe3(PO4)2P2O7钠离子电池正极材料。
图7为本实施例制备的Na4Fe3(PO4)2P2O7正极材料的XRD图。
将本实施例制备的Na4Fe3(PO4)2P2O7正极材料、乙炔黑、PVDF按质量比70:20:10的比例加入适量NMP混合匀浆后，使用150μm四面制备器将黑色浆料涂覆在铝箔上，然后将该膜在110℃真空干燥箱中真空干燥6h。再使用冲片机将干燥后的电极膜冲为半径一致的圆片即为正极极片。以金属钠为负极极片，隔膜为玻璃纤维膜，电解液为NaPF6/EC+DEC+DMC(EC:DEC:DMC＝1:1:1体积比)，在水氧含量小于0.01ppm的手套箱中组装成扣式半电池。测试结果如图8所示，在电流密度为0.1C，电压范围为2.0-4.0V时，其放电容量达到110.5mAh/g。
本发明第二方面实施例提供了一种钠离子电池，所述钠离子电池包括上述第一方面实施例提供的制备方法制备出的钠离子电池正极材料。
综上所述，本发明实施例提供的钠离子电池正极材料的制备方法和应用，在制备过程中采用具有固定铁磷比的原料磷酸氢铁水合物(Fe3(HPO4)4·H2O)作为前驱体，消除了加工过程在微观层面对设计原料配比的影响，保证了原料的均一性，使得制备出的钠离子电池正极材料晶体相纯度高，拥有更好的结晶性，电化学性能更佳，并且拥有更高的压实密度及能量密度。基于本发明所述钠离子电池正极材料制备的钠离子 电池具有良好的电池循环性能和稳定性。同时该制备方法工艺流程简单，适于大规模工业生产中应用。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”，或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管已经示出和描述了本发明的实施例，本领域的普通技术人员可以理解：在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由权利要求及其等同物限定。

Claims (10)

  1. 一种钠离子电池正极材料的制备方法，其特征在于，所述制备方法包括：
    将钠源化合物、磷酸氢铁水合物和碳源化合物按照一定比例分散于水中搅拌混合，得到分散液；
    将所述分散液置于砂磨机中砂磨一定时间，获得浆料；
    将砂磨后的浆料进行干燥，得到粉末状前驱体；
    将所述粉末状前驱体烧结粉碎后，得到所述钠离子电池正极材料。
  2. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述分散液中钠源化合物与所述磷酸氢铁水合物的加入量按照摩尔比n(Na)：n(Fe)＝4:3加入。
  3. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述钠源化合物为甲酸钠、乙酸钠、柠檬酸钠、草酸钠、氯化钠、硝酸钠以及硫酸钠中的一种或多种。
  4. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述碳源加入量为所述磷酸氢铁水合物加入量的10wt％-55wt％。
  5. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述碳源化合物为凡士林、硬脂酸、蔗糖、抗坏血酸、甲醛、乙醛、正丁醛、乳酸、柠檬酸、苹果酸、乙二酸、己二酸、可溶性淀粉、葡萄糖、聚乙二醇、麦芽糖、环糊精、碳纳米管、乙炔黑以及石墨烯中的一种或多种。
  6. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述砂磨机的砂磨方式包括盘式、棒销式、涡轮式中的一种；砂磨后的浆料粒径控制在0.1μm<DN50<5μm。
  7. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述干燥方法可以为鼓风干燥、真空干燥、冷冻干燥、喷雾干燥中的一种或多种。
  8. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述烧结条件包括烧结气氛、烧结温度以及烧结时间，所述烧结气氛包括氮气、氩气、氦气中的一种或几种混合气氛；所述烧结温度为450-700℃，升温速率为1-3℃/min；所述烧结时间为6-24h。
  9. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，所述粉 碎方法可以为机械粉碎、气流粉碎中的一种或两种。
  10. 一种钠离子电池，其特征在于，所述钠离子电池包括了如权利要求1-9任意一项所述制备方法制得的所述钠离子电池正极材料。
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CN120518050A (zh) * 2025-07-25 2025-08-22 四川大学 复合磷酸铁钠正极材料、前驱体及其制备方法、钠离子电池
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