WO2024124693A1 - 一种普鲁士白正极材料及其制备方法和应用 - Google Patents

一种普鲁士白正极材料及其制备方法和应用 Download PDF

Info

Publication number
WO2024124693A1
WO2024124693A1 PCT/CN2023/078026 CN2023078026W WO2024124693A1 WO 2024124693 A1 WO2024124693 A1 WO 2024124693A1 CN 2023078026 W CN2023078026 W CN 2023078026W WO 2024124693 A1 WO2024124693 A1 WO 2024124693A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
solution
electrode material
prussian white
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/078026
Other languages
English (en)
French (fr)
Inventor
李爱霞
余海军
谢英豪
李长东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Publication of WO2024124693A1 publication Critical patent/WO2024124693A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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
    • 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 application belongs to the technical field of battery materials and relates to a Prussian white positive electrode material and a preparation method and application thereof.
  • Prussian white belongs to the Prussian blue class of compounds, also known as ferrous ferrocyanide, which is the reduction product of Prussian blue; because it contains high sodium (Prussian blue has only one sodium) and is white, it is called Prussian white, which is currently the most promising sodium-ion battery cathode material for commercial applications.
  • the Prussian white positive electrode material has a rigid lattice skeleton and large ion channels, which are easy to insert and extract sodium ions.
  • the theoretical specific capacity is as high as 170mAh/g, but its cycle stability performance is unsatisfactory; because Mn 3+ has the Jahn-Teller effect, the structure is easily distorted during the charge and discharge process, and the transition metal dissolution will also occur, causing the collapse of the crystal structure during long cycles.
  • CN114212804A discloses a Prussian white positive electrode material and a preparation method and application thereof.
  • the Prussian white positive electrode material has a cubic or quasi-cubic secondary grain morphology.
  • the secondary grains are formed by stacking primary grains.
  • the primary grains are cubic or quasi-cubic.
  • CN110002465A discloses a Prussian white analog positive electrode material, its preparation method and application.
  • the preparation method of the positive electrode material comprises the following steps: (1) obtaining an aqueous solution of K 4 Fe(CN) 6 , denoted as solution A; (2) obtaining a mixed aqueous solution of a transition metal salt of Mn and potassium citrate, denoted as solution B; (3) dropping the solution A into the solution B, continuing to heat and stir after the dropping is completed, aging for several hours, separating the solid from the liquid, collecting and washing the precipitate, and drying to obtain the Prussian white analog positive electrode material.
  • the synthesis of Prussian white materials is generally carried out in aqueous solution, and the crystals often contain crystal water, which affects the structural stability and electrochemical performance of the product.
  • the crystal water in the Prussian white material is removed. This method not only consumes a lot of energy, but also cannot completely remove the crystal water. In addition, it will also destroy the microstructure of the material. Therefore, it is urgent to develop a gentle method to reduce the impact of the crystal water released by the positive electrode material during the cyclic charge and discharge process on the material stability, while reducing the dissolution of metal manganese and improving its cycle stability.
  • the purpose of the present application is to provide a Prussian white positive electrode material and a preparation method and application thereof.
  • the crystal water released by the Prussian white positive electrode material described in the present application during the cyclic charge and discharge process will be intercepted by the SnF4 coated on the surface to generate an insoluble compound stannic acid ( SnO2 ⁇ nH2O ) which continues to coat the surface of the Prussian white material, thereby reducing the influence of the crystal water released during the cyclic charge and discharge process on the stability of the material.
  • the present application provides a Prussian white cathode material, wherein the Prussian white cathode material comprises a Mn II -PBA core and a SnF 4 coating layer disposed on the surface of the Mn II -PBA core.
  • a SnF4 coating layer is provided on the surface of the Prussian white positive electrode material described in the present application. Since fluorine has a large electronegativity (electronegativity of 4.0), it has a strong binding ability to manganese and can form an Mn-F bond with manganese, thereby inhibiting the dissolution of metallic manganese in the Prussian blue-white material during the charge and discharge process, thereby improving the cycle stability.
  • the mass fraction of the SnF 4 coating layer is 0.1-0.5%.
  • the present application provides a method for preparing the Prussian white positive electrode material as described in the first aspect, wherein the preparation method comprises the following steps:
  • the present application reduces the dissolution of Mn and the influence of crystal water in Prussian white on the material by spray coating the surface of Prussian white (Mn II -PBA) with tin fluoride (SnF 4 ).
  • the manganese source in step (1) includes any one of manganese sulfate, manganese chloride or manganese nitrate, or a combination of at least two of them.
  • the molar ratio of the manganese source to sodium citrate is 1:(3-5), for example: 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, etc.
  • the molar concentration of solution A in step (1) is 0.02-0.8 mol/L, for example, 0.02 mol/L, 0.05 mol/L, 0.1 mol/L, 0.5 mol/L or 0.8 mol/L.
  • the molar concentration of the solution B in step (1) is 0.02-0.8 mol/L, for example, 0.02 mol/L, 0.05 mol/L, 0.1 mol/L, 0.5 mol/L or 0.8 mol/L.
  • the mixing method in step (2) includes adding solution B dropwise into solution A.
  • reaction temperature is 30-40°C, for example, 30°C, 32°C, 35°C, 38°C or 40°C.
  • reaction time is 6 to 10 hours, for example: 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, etc.
  • reaction is followed by aging, centrifugation, filtration and washing.
  • the spray coating device in step (3) includes a DJY-A-40V multifunctional mixer.
  • the spray coating is followed by drying.
  • the drying temperature is 90-120°C, for example, 90°C, 95°C, 100°C, 110°C or 120°C.
  • the drying time is 8 to 12 hours, for example: 8 hours, 9 hours, 10 hours, 11 hours or 12 hours. h etc.
  • the present application provides a positive electrode plate, wherein the positive electrode plate comprises the Prussian white positive electrode material as described in the first aspect.
  • the present application provides a sodium ion battery, wherein the sodium ion battery comprises the positive electrode plate as described in the third aspect.
  • the capacity retention rate of the Prussian white positive electrode material described in the present application can reach more than 91% after 100 cycles at 0.1C.
  • This embodiment provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • This embodiment provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • This embodiment provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • Solution B was added dropwise to solution A and reacted at 35°C for 8 h. After stirring, aging, centrifugation, After filtering and washing, the mixture is dried at 100°C to obtain a Prussian white precursor;
  • This comparative example provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • This comparative example provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • solution A Dissolve manganese sulfate and sodium citrate in deionized water to obtain solution A with a concentration of 0.4 mol/L;
  • the molar ratio of sodium citrate to manganese salt is 4:1;
  • This comparative example provides a Prussian white positive electrode material, and the preparation method of the Prussian white positive electrode material is as follows:
  • the Prussian white material prepared in the above embodiment is used as the positive electrode, metallic sodium is used as the negative electrode, glass fiber is used as the separator, NaPF 6 propylene carbonate/ethyl methyl carbonate solution is used as the electrolyte, and 3% by weight of fluorinated ethylene carbonate is added to the above electrolyte to assemble a button battery with a voltage range of 2 to 4V.
  • the charge and discharge test is carried out at 0.1C.
  • the capacity retention rate after 100 cycles is shown in Table 1:
  • the capacity retention rate of the Prussian white positive electrode material described in the present application after 100 cycles at 0.1C can reach more than 91%.
  • Example 1 By comparing Example 1 with Examples 4-5, it can be seen that in the Prussian white positive electrode material described in the present application, the mass proportion of the SnF4 coating layer will affect its performance. If the mass proportion of the SnF4 coating layer is too high, the gram capacity of the material will be reduced, resulting in a small improvement in the capacity retention rate of the material; if the mass proportion of the SnF4 coating layer is too low, a uniform coating layer cannot be formed on the surface of the positive electrode material, and the crystal water released during the cyclic charge and discharge process cannot be fully intercepted and the dissolution of manganese cannot be inhibited, resulting in an insignificant improvement in the cycle performance.
  • Example 1 By comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be seen that all Examples of the present application were subjected to charge and discharge tests at 0.1C, and the capacity retention rate after 100 cycles was better than the capacity retention rate of all comparative examples, indicating that the capacity retention rate of Prussian white coated with SnF 4 was higher than that of Prussian white not coated with SnF 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本申请提供了一种普鲁士白正极材料及其制备方法和应用，所述普鲁士白正极材料包括MnII-PBA内核和设置于所述MnII-PBA内核表面的SnF4包覆层，本申请所述普鲁士白正极材料在循环充放电过程中释放的结晶水会被表面包覆的SnF4拦截，生成不溶化合物锡酸(SnO2·nH2O)继续包覆在普鲁士白材料表面，从而降低了循环充放电过程中释放的结晶水对材料稳定性的影响。

Description

一种普鲁士白正极材料及其制备方法和应用 技术领域
本申请属于电池材料技术领域，涉及一种普鲁士白正极材料及其制备方法和应用。
背景技术
钠离子电池具有安全性好、成本低、资源丰富、环境友好等优点，非常适合大量储能。普鲁士白属于普鲁士蓝类化合物，又名亚铁氰化亚铁，是普鲁士蓝的还原产物；由于含有高钠(普鲁士蓝只有一个钠)，呈现白色，所以成为普鲁士白，是目前最具有商业应用前景的钠离子电池正极材料。
普鲁士白正极材料具备刚性的晶格骨骼和大的离子通道，易于钠离子的脱嵌，理论比容量高达170mAh/g，但其循环稳定性能却差强人意；因为Mn3+具有Jahn-Teller效应，在充放电过程中结构容易发生扭曲，同时也会发生过渡金属的溶解，在长循环过程中造成晶体结构的塌陷。
CN114212804A公开了一种普鲁士白正极材料及其制备方法与应用，所述普鲁士白正极材料为立方形或类立方形的二次晶粒形貌，所述二次晶粒由一次晶粒堆积而成，所述一次晶粒为立方形或类立方形。
CN110002465A公开了一种普鲁士白类似物正极材料、其制备方法和应用。该正极材料的制备方法包括如下步骤：(1)获取K4Fe(CN)6的水溶液，记为溶液A；(2)获取Mn的过渡金属盐和柠檬酸钾的混合水溶液，记为溶液B；(3)将所述溶液A滴加至所述溶液B中，滴加完毕之后继续加热搅拌，并陈化数小时，固液分离，收集并洗涤沉淀，干燥后得到所述普鲁士白类似物正极材料。
普鲁士白类材料合成一般在水溶液中进行，晶体中往往含有结晶水，这影响了产物的结构稳定性和电化学性能。目前，主要是采用高温、高真空烘烤使 普鲁士白材料中的结晶水脱出，这种方法不仅耗能高，而且结晶水也不能完全去除，此外也会破坏材料的微结构。因此，亟需开发一种温和的方法降低正极材料在循环充放电过程中释放的结晶水对材料稳定性的影响，同时降低金属锰的溶解，提高其循环稳定性。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种普鲁士白正极材料及其制备方法和应用，本申请所述普鲁士白正极材料在循环充放电过程中释放的结晶水会被表面包覆的SnF4拦截，生成不溶化合物锡酸(SnO2·nH2O)继续包覆在普鲁士白材料表面，从而降低了循环充放电过程中释放的结晶水对材料稳定性的影响。
为达到此申请目的，本申请采用以下技术方案：
第一方面，本申请提供了一种普鲁士白正极材料，所述普鲁士白正极材料包括MnII-PBA内核和设置于所述MnII-PBA内核表面的SnF4包覆层。
本申请所述普鲁士白正极材料表面设置SnF4包覆层，由于氟的电负性很大(电负性为4.0)，对锰的束缚能力强，能够与锰形成Mn-F键，从而抑制普鲁士蓝白材料在充放电过程中金属锰的溶出，进而提高循环稳定性。
可选地，以所述普鲁士白正极材料的质量为100％计，所述SnF4包覆层的质量分数为0.1～0.5％。
第二方面，本申请提供了一种如第一方面所述的普鲁士白正极材料的制备方法，其中，所述制备方法包括以下步骤：
(1)将锰源、柠檬酸钠和去离子水混合得到溶液A，将亚铁氰化钠与去离子水混合得到溶液B；
(2)将溶液A与溶液B混合，反应得到普鲁士白前驱体；
(3)将SnF4溶于乙醇中得到溶液C，使用溶液C对步骤(2)得到的普鲁士白前驱体进行喷雾包覆，得到所述普鲁士白正极材料。
本申请通过对普鲁士白(MnII-PBA)表面进行氟化锡(SnF4)喷雾包覆，降低了Mn的溶解，并且减少了普鲁士白内结晶水对材料的影响。
可选地，步骤(1)所述锰源包括硫酸锰、氯化锰或硝酸锰中的任意一种或至少两种的组合。
可选地，所述锰源和柠檬酸钠的摩尔比为1:(3～5)，例如：1:3、1:3.5、1:4、1:4.5或1:5等。
可选地，步骤(1)所述溶液A的摩尔浓度为0.02～0.8mol/L，例如：0.02mol/L、0.05mol/L、0.1mol/L、0.5mol/L或0.8mol/L等。
可选地，步骤(1)所述溶液B的摩尔浓度为0.02～0.8mol/L，例如：0.02mol/L、0.05mol/L、0.1mol/L、0.5mol/L或0.8mol/L等。
可选地，步骤(2)所述混合的方式包括将溶液B滴加入溶液A。
相应的，所述反应的温度为30～40℃，例如：30℃、32℃、35℃、38℃或40℃等。
可选地，所述反应的时间为6～10h，例如：6h、7h、8h、9h或10h等。
可选地，所述反应后进行陈化、离心、过滤和洗涤。
可选地，步骤(3)所述喷雾包覆的装置包括DJY-A-40V多功能混合机。
可选地，所述喷雾包覆后进行干燥处理。
可选地，所述干燥处理的温度为90～120℃，例如：90℃、95℃、100℃、110℃或120℃等。
可选地，所述干燥处理的时间为8～12h，例如：8h、9h、10h、11h或12 h等。
第三方面，本申请提供了一种正极极片，所述正极极片包含如第一方面所述的普鲁士白正极材料。
第四方面，本申请提供了一种钠离子电池，所述钠离子电池包含如第三方面所述的正极极片。
相对于现有技术，本申请具有以下有益效果：
(1)本申请所述普鲁士白正极材料在循环充放电过程中，普鲁士白材料中的结晶水会释放出去，这些结晶水会被表面包覆的SnF4拦截，因为SnF4和水相遇会生成不溶化合物锡酸(SnO2·nH2O)继续包覆在普鲁士白材料表面。
(2)本申请所述普鲁士白正极材料在0.1C下循环100次后的容量保持率可达91％以上。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
本实施例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
(1)将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.02mol/L；所述柠檬酸钠和锰盐的摩尔比为4:1，将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.02mol/L；
(2)将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、过滤、洗涤后在100℃下烘干，得到普鲁士白前驱体；
(3)将SnF4溶于50mL乙醇中，将溶液置于喷雾包覆设备中对步骤(1)中制得的普鲁士白进行喷雾包覆；随后，将喷雾包覆后的混合物置于100℃中干燥10h；所述喷雾包覆设备为DJY-A-40V多功能混合机；所述普鲁士白正极材料中，所述SnF4包覆层的质量分数0.1％。
实施例2
本实施例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
(1)将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.4mol/L；所述柠檬酸钠和锰盐的摩尔比为4:1，将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.4mol/L；
(2)将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、过滤、洗涤后在100℃下烘干，得到普鲁士白前驱体；
(3)将SnF4溶于50mL乙醇中，将溶液置于喷雾包覆设备中对步骤(1)中制得的普鲁士白进行喷雾包覆；随后，将喷雾包覆后的混合物置于100℃中干燥10h；所述喷雾包覆设备为DJY-A-40V多功能混合机；所述普鲁士白正极材料中，所述SnF4包覆层的质量分数0.3％。
实施例3
本实施例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
(1)将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.8mol/L；所述柠檬酸钠和锰盐的摩尔比为4:1，将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.8mol/L；
(2)将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、 过滤、洗涤后在100℃下烘干，得到普鲁士白前驱体；
(3)将SnF4溶于50mL乙醇中，将溶液置于喷雾包覆设备中对步骤(1)中制得的普鲁士白进行喷雾包覆；随后，将喷雾包覆后的混合物置于100℃中干燥10h；所述喷雾包覆设备为DJY-A-40V多功能混合机；所述普鲁士白正极材料中，所述SnF4包覆层的质量分数0.5％。
实施例4
本实施例与实施例1区别仅在于，制得普鲁士白正极材料中，所述SnF4包覆层的质量分数0.05％，其他条件与参数与实施例1完全相同。
实施例5
本实施例与实施例1区别仅在于，制得普鲁士白正极材料中，所述SnF4包覆层的质量分数0.6％，其他条件与参数与实施例1完全相同。
对比例1
本对比例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
a.将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.02mol/L；所述柠檬酸钠和锰盐的摩尔比为4:1；
b.将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.02mol/L；
c.将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、过滤、洗涤后在100℃下烘干，得到普鲁士白材料。
对比例2
本对比例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
a.将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.4mol/L； 所述柠檬酸钠和锰盐的摩尔比为4:1；
b.将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.4mol/L；
c.将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、过滤、洗涤后在100℃下烘干，得到普鲁士白材料。
对比例3
本对比例提供了一种普鲁士白正极材料，所述普鲁士白正极材料的制备方法如下：
a.将硫酸锰和柠檬酸钠溶于去离子水中，得到溶液A，浓度为0.8mol/L；所述柠檬酸钠和锰盐的摩尔比为4:1；
b.将亚铁氰化钠溶于去离子水中得到溶液B，浓度为0.8mol/L；
c.将B溶液滴入A溶液中，在35℃中反应8h，经过搅拌、陈化、离心、过滤、洗涤后在100℃下烘干，得到普鲁士白材料。
性能测试：
将上述实施例制得的普鲁士白材料作为正极，以金属钠为负极，玻璃纤维为隔膜，NaPF6的碳酸丙烯酯/碳酸甲乙酯溶液为电解液，并加入上述电解液重量为3％的氟化碳酸乙烯酯，装配纽扣电池，电压范围2～4V，在0.1C下进行充放电测试，经过100次循环后的容量保持率结果如表1所示：
表1

由表1可以看出，由实施例1-3可得，本申请所述普鲁士白正极材料在0.1C下循环100次后的容量保持率可达91％以上。
由实施例1和实施例4-5对比可得，本申请所述普鲁士白正极材料中，SnF4包覆层的质量占比会影响其性能，若SnF4包覆层的质量占比过高，则会导致材料的克容量降低，使得材料的容量保持率提升不大；若SnF4包覆层的质量占比过低，则不能在正极材料表面形成均匀包覆层，并且导致不能充分拦截循环充放电过程中释放的结晶水和抑制锰的溶出，使得循环性能提升不明显。
由实施例1和对比例1、实施例2和对比例2、实施例3和对比例3对比可得，本申请所有实施例在0.1C下进行充放电测试，经过100次循环后的容量保持率优于所有对比例的容量保持率，说明经过SnF4包覆后的普鲁士白的容量保持率均高于没有经过SnF4包覆后的普鲁士白。这是因为普鲁士白材料在循环充放电过程中释放的结晶水会被表面包覆的SnF4拦截，生成不溶化合物锡酸(SnO2·nH2O)继续包覆在普鲁士白材料表面，从而降低了正极材料循环充放电过程中释放的结晶水对材料稳定性的影响。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (10)

  1. 一种普鲁士白正极材料，其中，所述普鲁士白正极材料包括MnII-PBA内核和设置于所述MnII-PBA内核表面的SnF4包覆层。
  2. 如权利要求1所述的普鲁士白正极材料，其中，以所述普鲁士白正极材料的质量为100％计，所述SnF4包覆层的质量分数为0.1～0.5％。
  3. 一种如权利要求1或2所述的普鲁士白正极材料的制备方法，其中，所述制备方法包括以下步骤：
    (1)将锰源、柠檬酸钠和去离子水混合得到溶液A，将亚铁氰化钠与去离子水混合得到溶液B；
    (2)将溶液A与溶液B混合，反应得到普鲁士白前驱体；
    (3)将SnF4溶于乙醇中得到溶液C，使用溶液C对步骤(2)得到的普鲁士白前驱体进行喷雾包覆，得到所述普鲁士白正极材料。
  4. 如权利要求3所述的制备方法，其中，步骤(1)所述锰源包括硫酸锰、氯化锰或硝酸锰中的任意一种或至少两种的组合；
    可选地，所述锰源和柠檬酸钠的摩尔比为1:(3～5)。
  5. 如权利要求3或4所述的制备方法，其中，步骤(1)所述溶液A的摩尔浓度为0.02～0.8mol/L。
  6. 如权利要求3-5任一项所述的制备方法，其中，步骤(1)所述溶液B的摩尔浓度为0.02～0.8mol/L。
  7. 如权利要求3-6任一项所述的制备方法，其中，步骤(2)所述混合的方式包括将溶液B滴加入溶液A；
    相应的，所述反应的温度为30～40℃；
    可选地，所述反应的时间为6～10h；
    可选地，所述反应后进行陈化、离心、过滤和洗涤。
  8. 如权利要求3-7任一项所述的制备方法，其中，步骤(3)所述喷雾包覆的装置包括DJY-A-40V多功能混合机；
    可选地，所述喷雾包覆后进行干燥处理；
    可选地，所述干燥处理的温度为90～120℃；
    可选地，所述干燥处理的时间为8～12h。
  9. 一种正极极片，其中，所述正极极片包含如权利要求1或2所述的普鲁士白正极材料。
  10. 一种钠离子电池，其中，所述钠离子电池包含如权利要求9所述的正极极片。
PCT/CN2023/078026 2022-12-12 2023-02-24 一种普鲁士白正极材料及其制备方法和应用 Ceased WO2024124693A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211597065.XA CN115863644A (zh) 2022-12-12 2022-12-12 一种普鲁士白正极材料及其制备方法和应用
CN202211597065.X 2022-12-12

Publications (1)

Publication Number Publication Date
WO2024124693A1 true WO2024124693A1 (zh) 2024-06-20

Family

ID=85672466

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/078026 Ceased WO2024124693A1 (zh) 2022-12-12 2023-02-24 一种普鲁士白正极材料及其制备方法和应用

Country Status (3)

Country Link
CN (1) CN115863644A (zh)
FR (1) FR3143210A1 (zh)
WO (1) WO2024124693A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008016233A (ja) * 2006-07-03 2008-01-24 Sony Corp 正極活物質およびその製造方法、並びに非水電解質二次電池
CN101156260A (zh) * 2005-04-15 2008-04-02 能原材公司 氟化合物包覆的二次锂电池阴极活性材料及其制备方法
CN107611404A (zh) * 2017-09-14 2018-01-19 上海汉行科技有限公司 一种普鲁士白复合材料及其制备方法和应用
CN108807950A (zh) * 2018-08-08 2018-11-13 河北省科学院能源研究所 氟化物修饰的富镍三元复合电极材料及其制备方法
CN109065847A (zh) * 2018-05-25 2018-12-21 浙江大学 一种普鲁士白复合材料及其制备方法和应用
CN112209409A (zh) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 一种快速制备钠离子电池正极材料普鲁士白的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110002465B (zh) 2019-03-29 2021-01-19 华中科技大学 一种普鲁士白类似物正极材料、其制备方法和应用
CN111252784B (zh) * 2020-01-22 2021-06-22 宇恒电池有限公司 一种锰基普鲁士白正极材料的制备方法及其在钠离子电池电极中的应用
CN114212804B (zh) 2021-12-15 2022-12-09 武汉理工大学 一种普鲁士白正极材料及其制备方法与应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101156260A (zh) * 2005-04-15 2008-04-02 能原材公司 氟化合物包覆的二次锂电池阴极活性材料及其制备方法
JP2008016233A (ja) * 2006-07-03 2008-01-24 Sony Corp 正極活物質およびその製造方法、並びに非水電解質二次電池
CN107611404A (zh) * 2017-09-14 2018-01-19 上海汉行科技有限公司 一种普鲁士白复合材料及其制备方法和应用
CN109065847A (zh) * 2018-05-25 2018-12-21 浙江大学 一种普鲁士白复合材料及其制备方法和应用
CN108807950A (zh) * 2018-08-08 2018-11-13 河北省科学院能源研究所 氟化物修饰的富镍三元复合电极材料及其制备方法
CN112209409A (zh) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 一种快速制备钠离子电池正极材料普鲁士白的方法

Also Published As

Publication number Publication date
FR3143210A1 (fr) 2024-06-14
CN115863644A (zh) 2023-03-28

Similar Documents

Publication Publication Date Title
CN114212803B (zh) 掺杂氟的普鲁士蓝类钠离子电池正极材料的制备方法
CN103500827B (zh) 锂离子电池及其多元正极材料、制备方法
CN106784790B (zh) 一种镍钴锰酸锂三元正极材料的制备方法
CN114805450A (zh) 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
CN110002465A (zh) 一种普鲁士白类似物正极材料、其制备方法和应用
CN103682321A (zh) 一种复合改性改善镍锰酸锂正极材料循环的方法
CN113830792A (zh) 一种无水普鲁士白材料、制备方法和应用
CN113428912B (zh) 一种四元正极材料及其制备方法和应用
CN110504447B (zh) 一种氟掺杂的镍钴锰前驱体及其制备方法与应用
WO2023226550A1 (zh) 高导电性磷酸铁锂的制备方法及其应用
WO2024130840A1 (zh) 一种改性三元正极材料及其制备方法和应用
CN113871589B (zh) 一种熔盐辅助钛酸锂包覆的富锂锰基正极材料及其制备方法
CN108975298A (zh) 球形水合磷酸铁盐晶体及其制备方法和磷酸铁锂以及电池正极材料和锂离子电池
CN105655144B (zh) 一种锂离子超级电容器富锂复合正极材料制备方法
CN112480424B (zh) 蒽醌-2,3-二羧酸钙配位聚合物作为锂离子电池正极材料的应用
CN118572236A (zh) 一种正极及将退役动力锂电池正极材料制备为钾离子电池普鲁士蓝类似物正极的回收方法
CN112678883B (zh) 一种表面富钴型低钴正极材料的制备方法
CN115611773B (zh) 一种补锂化合物及其制备方法、锂离子电池
US11942643B2 (en) Doped sodium vanadium phosphate and preparation method and application thereof
CN105742630A (zh) 一种α-ZnMoO4锂离子电池负极材料及其制备方法
CN104993108A (zh) 一种钛酸锂/锡复合负极材料的制备方法
CN115863644A (zh) 一种普鲁士白正极材料及其制备方法和应用
WO2024192746A1 (zh) 一种复合钠离子正极材料及其制备方法和应用
CN115784258A (zh) 一种锰基普鲁士蓝正极材料的制备方法
CN108483496A (zh) 一种二氧化钒纳米片状材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23901911

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23901911

Country of ref document: EP

Kind code of ref document: A1