WO2022227669A1 - Iron phosphate precursor and preparation method therefor and application thereof - Google Patents

Iron phosphate precursor and preparation method therefor and application thereof Download PDF

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WO2022227669A1
WO2022227669A1 PCT/CN2021/142593 CN2021142593W WO2022227669A1 WO 2022227669 A1 WO2022227669 A1 WO 2022227669A1 CN 2021142593 W CN2021142593 W CN 2021142593W WO 2022227669 A1 WO2022227669 A1 WO 2022227669A1
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iron
iron phosphate
phosphate
source
preparation
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PCT/CN2021/142593
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French (fr)
Chinese (zh)
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李玲
李长东
阮丁山
唐盛贺
秦存鹏
殷磊
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to HU2200339A priority Critical patent/HUP2200339A1/en
Publication of WO2022227669A1 publication Critical patent/WO2022227669A1/en

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    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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 invention belongs to the field of lithium ion battery materials, and in particular relates to an iron phosphate precursor and a preparation method and application thereof.
  • lithium iron phosphate occupies a large position in the battery matching of new energy special vehicles (including new energy logistics vehicles, new energy sanitation vehicles, and other special vehicles for new energy) due to its high safety. Proportion. Lithium iron phosphate has the advantages of good safety performance, long cycle life, environmental protection and safety, low manufacturing cost and high energy density, especially good safety performance.
  • the electrochemical performance of the positive electrode material of lithium iron phosphate battery is relatively stable. During the charging and discharging process, the structure of the battery is not easy to change, and there is very little combustion and explosion. Even under special conditions such as short circuit, overcharge, extrusion, and acupuncture, it is still relatively stable. Safety.
  • Iron phosphate is the precursor of lithium iron phosphate.
  • the commonly used synthesis method of iron phosphate is the precipitation method, that is, ferrous sulfate, hydrogen peroxide and ammonium dihydrogen phosphate are reacted to form iron phosphate precipitation.
  • the reaction process also requires ammonia water to control pH.
  • the whole process of the reaction method is complicated to operate, takes a long time, and generates a large amount of ammonia nitrogen wastewater, which is difficult to treat and increases the difficulty of environmental protection.
  • high compaction density iron phosphate is also a development direction, so corresponding high compaction iron phosphate precursors are required.
  • the tap density of the current iron phosphate precursor is not high, generally not more than 1.0 g/cm 3 .
  • the specific surface area of the current iron phosphate precursor is also relatively high, usually about 50m 2 /g. In order to reduce the specific surface area, most iron phosphate manufacturers use high temperature above 800 °C and prolong the sintering time to melt the iron phosphate, thereby making it anhydrous.
  • the specific surface area of iron phosphate is about 1.5-3m 2 /g, so as to reduce the internal pores of iron phosphate, but this process leads to increased energy consumption, and also causes serious sintering and agglomeration of materials, and the subsequent crushing process is difficult. Greatly reduce the production efficiency of enterprises.
  • the present invention discloses an environment-friendly and simple synthesis method, thereby preparing an iron phosphate precursor with high compaction density and low specific surface area.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • the present invention provides an iron phosphate precursor and its preparation method and application.
  • the iron phosphate precursor has high compacted density and low specific surface area, the tapped density can reach 1 g/cm 3 , and the specific surface area is less than 3 m 2 /g .
  • the present invention adopts the following technical solutions:
  • An iron phosphate precursor the microscopic morphology of the iron phosphate precursor is spherical, the particle size D50 is 10-20 ⁇ m, the specific surface area is 1-3 m 2 /g, and the tap density is 1-1.5 g/cm 3 .
  • the iron phosphate precursor is mainly prepared from the following raw materials: an iron source and a phosphorus source; the molar ratio of the iron element in the iron source and the phosphorus element in the phosphorus source is (0.95-1.02):1; the iron phosphate
  • the precursor carries two crystal waters.
  • the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate.
  • the phosphorus source is phosphoric acid.
  • the iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate.
  • the iron source is iron nitrate.
  • a preparation method of an iron phosphate precursor comprising the following steps:
  • ferric phosphate slurry is filtered to obtain ferric phosphate precipitation
  • the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate.
  • the phosphorus source is phosphoric acid.
  • the iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate.
  • the iron source is one of iron powder, iron sheet, ferrous chloride, ferrous sulfate or ferrous acetate
  • an oxidant needs to be added after the iron source and the phosphorus source are mixed, and the oxidant is At least one of hydrogen peroxide, sodium peroxide and ammonium persulfate; more preferably hydrogen peroxide.
  • the iron source is iron nitrate.
  • the molar ratio of iron element and phosphorus element in the molten metal is (0.95-1.02):1, more preferably (0.965-0.99):1.
  • the substance used for adjusting the pH to -1 to 2.5 is sulfuric acid.
  • the pH is -0.2 to 1.0.
  • the stirring speed is 300-500 r/min, more preferably 350-450 r/min.
  • the temperature is raised to a temperature of 70-100°C, more preferably 80-95°C.
  • the drying temperature is 60-110°C, more preferably 90-100°C.
  • the washing times are 3-10 times.
  • the invention also provides the application of the iron phosphate precursor in the preparation of lithium ion batteries.
  • the present invention is by selecting ferric iron as iron source, then phosphoric acid is added to the ferric iron solution, and by controlling pH and reaction temperature, the morphology and particle size distribution of primary particles of iron phosphate are controlled, and the above-mentioned use adds phosphoric acid to ferric phosphate.
  • the initial pH of the system is very low, and then the reaction temperature is controlled at 70-100 ° C, which can form spherical dense primary particles and stack in an orderly manner.
  • Ferric phosphate water, the tap density of the ferric phosphate dihydrate is high, up to 1-1.5/cm 3 .
  • the specific surface area of the iron phosphate dihydrate prepared by the present invention is 1-3m 2 /g, because the specific surface area of the iron phosphate dihydrate is low, therefore, the required dehydration temperature in the post-processing operation is low, the energy consumption is low, and the production cost is low And the production efficiency is high, at the same time, the prepared iron phosphate has good processing performance, strong process controllability, simple and convenient operation, and is suitable for large-scale industrial production; and the synthesis process is simple and has no environmental protection problem, and does not need to treat ammonia nitrogen-containing wastewater.
  • Fig. 1 is the SEM image of the iron phosphate dihydrate of the embodiment of the present invention 1;
  • Fig. 2 is the XRD figure of the iron phosphate dihydrate of the embodiment of the present invention 1;
  • the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
  • the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
  • the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
  • the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
  • the preparation of the iron phosphate precursor of this comparative example includes the following steps:
  • a low-temperature preparation iron phosphate technological process comprises the following steps:
  • ferric phosphate dihydrate with large particle size, small specific surface area and large TD was prepared by the method of Examples 1-4 of the present invention.
  • the specific surface area of the ferric phosphate dihydrate prepared in Example 1-2 is lower than that of Comparative Example 1 and commercially available ferric phosphate, the energy consumption of subsequent calcination is lower, the particle size is larger than that of Comparative Example 1 and commercially available ferric phosphate, and vibration The solid density is much higher than that of Comparative Examples 1-2.
  • the reaction temperature of comparative example 1 is too low, need to add alkali to promote precipitation, adding alkali liquor precipitation can affect the primary particle stacking effect obtained, the primary particle stacking is not the same, will affect the specific surface area and compaction density of iron phosphate dihydrate.
  • Comparative Example 1 sodium salt wastewater is also generated, and the sodium salt wastewater needs to be treated.
  • the reaction temperature of Comparative Example 2 was too low to form a precipitate.
  • Fig. 1 is the SEM image of the iron phosphate dihydrate of Example 1 of the present invention; it can be seen from Fig. 1 that the embodiment has prepared spherical particle iron phosphate with good sphericity
  • Fig. 2 is the iron phosphate dihydrate of Example 1 of the present invention XRD pattern; from the XRD pattern in Figure 2, it can be seen that the preparation obtained in Example 1 is pure-phase iron phosphate dihydrate.
  • 3 is the SEM image of the iron phosphate dihydrate of Comparative Example 1 of the present invention; it can be seen from FIG. 3 that Comparative Example 1 is an iron phosphate formed by agglomeration of fine primary particles, so the specific surface area of the iron phosphate of Comparative Example 1 is large.

Abstract

The present invention relates to the field of lithium-ion battery materials. Disclosed are an iron phosphate precursor and a preparation method therefor and an application thereof. The iron phosphate precursor has spherical micromorphology, a particle size D50 of 10-20 μm, a specific surface area of 1-3 m2/g, and a tap density of 1-1.5 g/cm3. In the present invention, ferric iron is selected as an iron source, phosphoric acid is then added into a ferric iron solution, and the morphology and particle size distribution of iron phosphate primary particles are controlled by controlling the pH and reaction temperature. The mode of adding phosphoric acid into ferric iron salt makes initial pH of a system very low, the reaction temperature is then controlled to be 70-100°C, spherical dense primary particles can be formed, sequentially stacked, and dried to obtain iron phosphate dihydrate having a low specific surface area and no internal voids, and the iron phosphate dihydrate has a high tap dense up to 1-1.5/cm3.

Description

一种磷酸铁前驱体及其制备方法和应用A kind of iron phosphate precursor and its preparation method and application 技术领域technical field
本发明属于锂离子电池材料领域，具体涉及一种磷酸铁前驱体及其制备方法和应用。The invention belongs to the field of lithium ion battery materials, and in particular relates to an iron phosphate precursor and a preparation method and application thereof.
背景技术Background technique
随着新能源汽车市场的火热，磷酸铁锂以其安全性较高，在新能源专用车(包含新能源物流车、新能源环卫车、新能源其他专用车)的电池配套中占据了较大比例。磷酸铁锂具有安全性能好、循环寿命长、环保安全、制造成本低、能量密度较高等优势，特别是啊安全性能好。磷酸铁锂电池正极材料电化学性能比较稳定，在充放电过程中，电池的结构不易发生变化，极少出现燃烧爆炸，即使在短路、过充、挤压、针刺等特殊条件下，依然比较安全。With the popularity of the new energy vehicle market, lithium iron phosphate occupies a large position in the battery matching of new energy special vehicles (including new energy logistics vehicles, new energy sanitation vehicles, and other special vehicles for new energy) due to its high safety. Proportion. Lithium iron phosphate has the advantages of good safety performance, long cycle life, environmental protection and safety, low manufacturing cost and high energy density, especially good safety performance. The electrochemical performance of the positive electrode material of lithium iron phosphate battery is relatively stable. During the charging and discharging process, the structure of the battery is not easy to change, and there is very little combustion and explosion. Even under special conditions such as short circuit, overcharge, extrusion, and acupuncture, it is still relatively stable. Safety.
磷酸铁是磷酸铁锂的前驱体，目前，磷酸铁常用的合成方法是沉淀法，即用硫酸亚铁、双氧水、磷酸二氢铵反应生成磷酸铁沉淀，反应过程还需要氨水调控pH。该反应方法整个流程操作繁琐、耗时较长并且会产生大量的氨氮废水，废水处理困难，增加环保难度。另一方面，随着对高能量密度的需求，高压实密度磷酸铁也是发展方向，因此需要相应的高压实磷酸铁前驱体。但是目前的磷酸铁前驱体振实密度都不高，一般都不超过1.0g/cm 3。还有目前的磷酸铁前驱体的比表面积也比较高，通常在50m 2/g左右，为了降低比表面积，多数磷酸铁厂家通过高温800℃以上并延长烧结时间使得磷酸铁熔融，进而使得无水磷酸铁的比表面积在1.5～3m 2/g左右，以此来减少磷酸铁内部孔洞，但该工艺导致能耗升高的同时，还会使得物料烧结、结块严重，后续破碎工序难度大，大大降低了企业生产效率。 Iron phosphate is the precursor of lithium iron phosphate. At present, the commonly used synthesis method of iron phosphate is the precipitation method, that is, ferrous sulfate, hydrogen peroxide and ammonium dihydrogen phosphate are reacted to form iron phosphate precipitation. The reaction process also requires ammonia water to control pH. The whole process of the reaction method is complicated to operate, takes a long time, and generates a large amount of ammonia nitrogen wastewater, which is difficult to treat and increases the difficulty of environmental protection. On the other hand, with the demand for high energy density, high compaction density iron phosphate is also a development direction, so corresponding high compaction iron phosphate precursors are required. However, the tap density of the current iron phosphate precursor is not high, generally not more than 1.0 g/cm 3 . In addition, the specific surface area of the current iron phosphate precursor is also relatively high, usually about 50m 2 /g. In order to reduce the specific surface area, most iron phosphate manufacturers use high temperature above 800 °C and prolong the sintering time to melt the iron phosphate, thereby making it anhydrous. The specific surface area of iron phosphate is about 1.5-3m 2 /g, so as to reduce the internal pores of iron phosphate, but this process leads to increased energy consumption, and also causes serious sintering and agglomeration of materials, and the subsequent crushing process is difficult. Greatly reduce the production efficiency of enterprises.
为解决上述问题，本发明公开了一种环保简便的合成方法，从而制备一种具有高压实密度和低比表面积的磷酸铁前驱体。In order to solve the above problems, the present invention discloses an environment-friendly and simple synthesis method, thereby preparing an iron phosphate precursor with high compaction density and low specific surface area.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明一种磷酸铁前驱体及其制备方法和应用，该磷酸铁前驱体具有高压实密度和低比表面积，振实密度可达1g/cm 3，比表面积小于3m 2/g。 The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides an iron phosphate precursor and its preparation method and application. The iron phosphate precursor has high compacted density and low specific surface area, the tapped density can reach 1 g/cm 3 , and the specific surface area is less than 3 m 2 /g .
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种磷酸铁前驱体，所述磷酸铁前驱体的微观形貌呈球状且粒径D50为10-20μm，比表面积为1-3m 2/g，振实密度为1-1.5g/cm 3。 An iron phosphate precursor, the microscopic morphology of the iron phosphate precursor is spherical, the particle size D50 is 10-20 μm, the specific surface area is 1-3 m 2 /g, and the tap density is 1-1.5 g/cm 3 .
优选地，所述磷酸铁前驱体主要由以下原料制得：铁源和磷源；所述铁源中铁元素和磷源中磷元素的摩尔比为(0.95～1.02):1；所述磷酸铁前驱体带两个结晶水。Preferably, the iron phosphate precursor is mainly prepared from the following raw materials: an iron source and a phosphorus source; the molar ratio of the iron element in the iron source and the phosphorus element in the phosphorus source is (0.95-1.02):1; the iron phosphate The precursor carries two crystal waters.
优选地，所述磷源为磷酸、亚磷酸、次磷酸钠、磷酸二氢铵或磷酸铵中的至少一种。Preferably, the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate.
更优选地，所述磷源为磷酸。More preferably, the phosphorus source is phosphoric acid.
优选地，所述铁源为铁粉、铁皮、氯化亚铁、氯化铁、硫酸亚铁、硝酸铁或醋酸亚铁中的一种。Preferably, the iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate.
更优选地，所述铁源为硝酸铁。More preferably, the iron source is iron nitrate.
一种磷酸铁前驱体的制备方法，包括以下步骤：A preparation method of an iron phosphate precursor, comprising the following steps:
S1、将铁源和磷源混合，调节pH为-1～2.5，得到金属液；S1. Mix the iron source and the phosphorus source, and adjust the pH to -1 to 2.5 to obtain molten metal;
S2、将所述金属液搅拌，升温，反应，得到磷酸铁浆料；S2, the molten metal is stirred, heated, and reacted to obtain iron phosphate slurry;
S3、将所述磷酸铁浆料过滤，得到磷酸铁沉淀；S3, the ferric phosphate slurry is filtered to obtain ferric phosphate precipitation;
S4、取所述磷酸铁沉淀洗涤，烘干，得到二水磷酸铁。S4, get described ferric phosphate precipitation washing, oven dry, obtain ferric phosphate dihydrate.
优选地，步骤S1中，所述磷源为磷酸、亚磷酸、次磷酸钠、磷酸二氢铵或磷酸铵中的至少一种。Preferably, in step S1, the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate.
更优选地，所述磷源为磷酸。More preferably, the phosphorus source is phosphoric acid.
优选地，步骤S1中，所述铁源为铁粉、铁皮、氯化亚铁、氯化铁、硫酸亚铁、硝酸铁或醋酸亚铁中的一种。Preferably, in step S1, the iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate.
优选地，当所述铁源为铁粉、铁皮、氯化亚铁、硫酸亚铁或醋酸亚铁中的一种时，所述铁源和磷源混合后还需添加氧化剂，所述氧化剂为双氧水、过氧化钠、过硫酸铵中的至少一种；进一步优选为双氧水。Preferably, when the iron source is one of iron powder, iron sheet, ferrous chloride, ferrous sulfate or ferrous acetate, an oxidant needs to be added after the iron source and the phosphorus source are mixed, and the oxidant is At least one of hydrogen peroxide, sodium peroxide and ammonium persulfate; more preferably hydrogen peroxide.
更优选地，所述铁源为硝酸铁。More preferably, the iron source is iron nitrate.
优选地，步骤S1中，所述金属液的铁元素和磷元素的摩尔比为(0.95～1.02)：1，进一步优选为(0.965-0.99)：1。Preferably, in step S1, the molar ratio of iron element and phosphorus element in the molten metal is (0.95-1.02):1, more preferably (0.965-0.99):1.
优选地，步骤S1中，所述调节pH为-1～2.5所使用的物质为硫酸。Preferably, in step S1, the substance used for adjusting the pH to -1 to 2.5 is sulfuric acid.
优选地，步骤S1中，所述pH为-0.2～1.0。Preferably, in step S1, the pH is -0.2 to 1.0.
优选地，步骤S2中，所述搅拌的速度为300-500r/min，进一步优选为350-450r/min。Preferably, in step S2, the stirring speed is 300-500 r/min, more preferably 350-450 r/min.
优选地，步骤S2中，所述升温到温度为70-100℃，进一步优选为80-95℃。Preferably, in step S2, the temperature is raised to a temperature of 70-100°C, more preferably 80-95°C.
优选地，步骤S4中，所述烘干的温度为60-110℃，进一步优选为90-100℃。Preferably, in step S4, the drying temperature is 60-110°C, more preferably 90-100°C.
优选地，步骤S4中，所述洗涤的次数为3-10次。Preferably, in step S4, the washing times are 3-10 times.
本发明还提供所述的磷酸铁前驱体在制备锂离子电池中的应用。The invention also provides the application of the iron phosphate precursor in the preparation of lithium ion batteries.
相对于现有技术，本发明的有益效果如下：With respect to the prior art, the beneficial effects of the present invention are as follows:
1.本发明通过选择三价铁作为铁源，再将磷酸加入三价铁溶液中，并通过控制pH和反应温度来控制磷酸铁一次粒子的形貌和粒度分布，上述采用将磷酸加入三价铁盐的方式，使得体系初始的pH很低，再将反应温度控制在70-100℃，可形成球状密实的一次粒子并有序堆叠，干燥后，可得到比表面积低和内部无空隙的二水磷酸铁，该二水磷酸铁的振实密度高，可达1-1.5/cm 3。 1. the present invention is by selecting ferric iron as iron source, then phosphoric acid is added to the ferric iron solution, and by controlling pH and reaction temperature, the morphology and particle size distribution of primary particles of iron phosphate are controlled, and the above-mentioned use adds phosphoric acid to ferric phosphate. In the method of iron salt, the initial pH of the system is very low, and then the reaction temperature is controlled at 70-100 ° C, which can form spherical dense primary particles and stack in an orderly manner. Ferric phosphate water, the tap density of the ferric phosphate dihydrate is high, up to 1-1.5/cm 3 .
2.本发明制备的二水磷酸铁的比表面积为1-3m 2/g，由于二水磷酸铁的比表面积低，因此，后加工工序中所需脱水温度低，能耗低、生产成本低且生产效率高，同时，制得的磷酸铁的加工性能好，工艺可控性强，操作简便，适合于大规模工业化生产；而且该合成工艺简单且不存在环保问题，无需处理含氨氮废水。 2. the specific surface area of the iron phosphate dihydrate prepared by the present invention is 1-3m 2 /g, because the specific surface area of the iron phosphate dihydrate is low, therefore, the required dehydration temperature in the post-processing operation is low, the energy consumption is low, and the production cost is low And the production efficiency is high, at the same time, the prepared iron phosphate has good processing performance, strong process controllability, simple and convenient operation, and is suitable for large-scale industrial production; and the synthesis process is simple and has no environmental protection problem, and does not need to treat ammonia nitrogen-containing wastewater.
附图说明Description of drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, wherein:
图1为本发明实施例1的二水磷酸铁的SEM图；Fig. 1 is the SEM image of the iron phosphate dihydrate of the embodiment of the present invention 1;
图2为本发明实施例1的二水磷酸铁的XRD图；Fig. 2 is the XRD figure of the iron phosphate dihydrate of the embodiment of the present invention 1;
图3为本发明对比例1的二水磷酸铁的SEM图。3 is a SEM image of the iron phosphate dihydrate of Comparative Example 1 of the present invention.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
实施例1Example 1
本实施例的磷酸铁前驱体的制备方法，包括以下步骤：The preparation method of the iron phosphate precursor of the present embodiment comprises the following steps:
S1、选择硝酸铁和磷酸分别作为铁源和磷源，按铁源中铁元素和磷酸中磷元素摩尔比为0.965:1，将磷酸加入硝酸铁中，用硫酸调节pH为0，配置Fe 3+浓度为50g/L的金属液； S1. Select ferric nitrate and phosphoric acid as the iron source and phosphorus source, respectively. According to the molar ratio of iron in the iron source and phosphorus in phosphoric acid as 0.965:1, add phosphoric acid to the ferric nitrate, adjust the pH to 0 with sulfuric acid, and configure Fe 3+ Liquid metal with a concentration of 50g/L;
S2、将50L金属液加入反应釜中，在400r/min下升温到90℃，反应10h，得到浆液；S2. Add 50L of molten metal into the reaction kettle, heat up to 90°C at 400r/min, and react for 10h to obtain a slurry;
S3、将浆液过滤，得到滤渣，再用纯水进行反复洗涤滤渣3遍，得到洗涤后滤渣；S3, the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
S4、将所得滤渣在100℃下烘干，烘干过程需要翻转几次，即得到二水磷酸铁前驱体。S4, drying the obtained filter residue at 100° C., and the drying process needs to be turned over several times to obtain the iron phosphate dihydrate precursor.
实施例1所得二水磷酸铁产品的理化结果如下表1：The physical and chemical results of the obtained iron phosphate dihydrate product of embodiment 1 are as follows in Table 1:
表1Table 1
Figure PCTCN2021142593-appb-000001
Figure PCTCN2021142593-appb-000001
实施例2Example 2
本实施例的磷酸铁前驱体的制备方法，包括以下步骤：The preparation method of the iron phosphate precursor of the present embodiment comprises the following steps:
S1、选择硝酸铁和磷酸分别作为铁源和磷源，按铁源中铁元素和磷酸中磷元素摩尔比为0.965:1，将磷酸加入硝酸铁中，用硫酸调节pH为0，配置Fe 3+浓度为50g/L的金属液； S1. Select ferric nitrate and phosphoric acid as the iron source and phosphorus source, respectively. According to the molar ratio of iron in the iron source and phosphorus in phosphoric acid as 0.965:1, add phosphoric acid to the ferric nitrate, adjust the pH to 0 with sulfuric acid, and configure Fe 3+ Liquid metal with a concentration of 50g/L;
S2、将50L金属液加入反应釜中，在400r/min下升温到85℃，反应15h，得到浆液；S2. Add 50L of molten metal into the reaction kettle, heat up to 85°C at 400r/min, and react for 15h to obtain a slurry;
S3、将浆液过滤，得到滤渣，再用纯水进行反复洗涤滤渣3遍，得到洗涤后滤渣；S3, the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
S4、将所得滤渣在100℃下烘干，烘干过程需要翻转几次，即得到二水磷酸铁前驱体。S4, drying the obtained filter residue at 100° C., and the drying process needs to be turned over several times to obtain the iron phosphate dihydrate precursor.
实施例3Example 3
本实施例的磷酸铁前驱体的制备方法，包括以下步骤：The preparation method of the iron phosphate precursor of the present embodiment comprises the following steps:
S1、选择硫酸亚铁和磷酸分别作为铁源和磷源，按铁元素和磷酸元素摩尔比为 0.97:1，将磷酸加入硝酸铁中，并加入双氧水，用硫酸调节pH为0.5，配置Fe 3+浓度为56g/L的金属液； S1. Select ferrous sulfate and phosphoric acid as the iron source and phosphorus source respectively, according to the molar ratio of iron element and phosphoric acid element to be 0.97:1, add phosphoric acid to ferric nitrate, add hydrogen peroxide, adjust pH to 0.5 with sulfuric acid, and configure Fe 3 + Metal liquid with a concentration of 56g/L;
S2、将50L金属液加入反应釜中，在400r/min下升温到90℃，反应12h，得到浆液；S2. Add 50L of molten metal into the reaction kettle, heat up to 90°C at 400r/min, and react for 12h to obtain a slurry;
S3、将浆液过滤，得到滤渣，再用纯水进行反复洗涤滤渣3遍，得到洗涤后滤渣；S3, the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
S4、将所得滤渣在100℃下烘干，烘干过程需要翻转几次，即得到二水磷酸铁前驱体。S4, drying the obtained filter residue at 100° C., and the drying process needs to be turned over several times to obtain the iron phosphate dihydrate precursor.
实施例4Example 4
本实施例的磷酸铁前驱体的制备方法，包括以下步骤：The preparation method of the iron phosphate precursor of the present embodiment comprises the following steps:
S1、选择硝酸铁和磷酸分别作为铁源和磷源，按铁元素和磷酸元素摩尔比为0.97:1混合，用硫酸调节pH为0.5，将磷酸加入硝酸铁中，配置Fe 3+浓度为50g/L的金属液； S1. Select ferric nitrate and phosphoric acid as iron source and phosphorus source respectively, mix them according to the molar ratio of iron element and phosphoric acid element as 0.97:1, adjust pH to 0.5 with sulfuric acid, add phosphoric acid to ferric nitrate, and configure Fe 3+ concentration to 50g /L of molten metal;
S2、将50L金属液加入反应釜中，在400r/min下升温到95℃，反应10h，得到浆液；S2. Add 50L of molten metal into the reaction kettle, heat up to 95°C at 400r/min, and react for 10h to obtain a slurry;
S3、将浆液过滤，得到滤渣，再用纯水进行反复洗涤滤渣3遍，得到洗涤后滤渣；S3, the slurry is filtered to obtain a filter residue, and then the filter residue is repeatedly washed with pure water 3 times to obtain a washed filter residue;
S4、将所得滤渣在100℃下烘干，烘干过程需要翻转几次，即得到二水磷酸铁前驱体。S4, drying the obtained filter residue at 100° C., and the drying process needs to be turned over several times to obtain the iron phosphate dihydrate precursor.
对比例1Comparative Example 1
本对比例的磷酸铁前驱体制备，包括以下步骤：The preparation of the iron phosphate precursor of this comparative example includes the following steps:
(1)选择硝酸铁和磷酸分别作为铁源和磷源，按铁元素和磷酸元素摩尔比为0.965:1，将磷酸加入硝酸铁中，用硫酸调节pH为0，配置Fe 3+浓度为50g/L的金属液，氢氧化钠溶解配置为碱性溶液； (1) Select ferric nitrate and phosphoric acid as iron source and phosphorus source respectively, according to the molar ratio of iron element and phosphoric acid element to be 0.965:1, add phosphoric acid to ferric nitrate, adjust pH to 0 with sulfuric acid, and configure Fe 3+ concentration to be 50g /L of metal liquid, sodium hydroxide is dissolved and configured as an alkaline solution;
(2)将50L金属液加入反应釜中，在400r/min下升温到45℃，氢氧化钠作为沉淀剂缓慢加入反应釜中，反应完成后陈化5-10h；(2) Add 50L of molten metal into the reaction kettle, heat up to 45°C at 400 r/min, slowly add sodium hydroxide as a precipitant to the reaction kettle, and age for 5-10h after the reaction is completed;
(3)陈化完成后，将浆液过滤，得到滤渣，再用纯水进行反复洗涤3遍，得到洗涤后滤渣；(3) after the aging is completed, the slurry is filtered to obtain a filter residue, which is then repeatedly washed 3 times with pure water to obtain a filter residue after the washing;
(4)将所得滤渣在100℃下烘干，烘干过程需要翻转几次，即得到二水磷酸铁前驱体。(4) drying the obtained filter residue at 100° C., and the drying process needs to be turned over several times to obtain the iron phosphate dihydrate precursor.
对比例1所得二水磷酸铁前驱体的理化结果如下表2：The physicochemical results of the obtained iron phosphate dihydrate precursor of Comparative Example 1 are as follows in Table 2:
表2Table 2
Fe％Fe% P％P% Fe/PFe/P BETBET D50D50 振实密度Tap density
28.7228.72 16.4516.45 0.96810.9681 43.143.1 5.525.52 0.60.6
对比例2Comparative Example 2
一种低温制备磷酸铁工艺过程，包括以下步骤：A low-temperature preparation iron phosphate technological process, comprises the following steps:
(1)选择硫酸亚铁和磷酸分别作为铁源和磷源，按铁元素和磷酸元素摩尔比为0.97:1，将磷酸加入硫酸亚铁中，并加入双氧水，配置Fe 3+浓度为56g/L的金属液； (1) Select ferrous sulfate and phosphoric acid as iron source and phosphorus source respectively, according to the molar ratio of iron element and phosphoric acid element to be 0.97:1, add phosphoric acid to ferrous sulfate, and add hydrogen peroxide, and configure Fe 3+ concentration to be 56g/ L of molten metal;
(2)将50L金属液加入反应釜中，在400r/min下升温到50℃，反应20h；(2) 50L of molten metal was added to the reaction kettle, heated to 50°C at 400r/min, and reacted for 20h;
(3)反应20h后，出来浆液几乎保持金属液的颜色，将浆液过滤，几乎得不到滤渣，即几乎没有合成磷酸铁前驱体。(3) After 20 hours of reaction, the slurry that came out almost kept the color of the molten metal, and the slurry was filtered, and almost no filter residue was obtained, that is, almost no precursor of iron phosphate was synthesized.
结果对比：Comparative Results:
将实施例1-4和对比例1-2制备的磷酸铁进行对比，得到如表3所示的结果：The ferric phosphates prepared by Example 1-4 and Comparative Example 1-2 were compared to obtain the results shown in Table 3:
表3table 3
Figure PCTCN2021142593-appb-000002
Figure PCTCN2021142593-appb-000002
从表3可得，通过本发明实施例1-4的方法制备得到粒度大，比表面积小，TD(振实密度)大的二水磷酸铁。其中实施例1-2制备的二水磷酸铁的比表面积低于对比例1和市售的磷酸铁，后续煅烧的能耗较低，粒度较对比例1和市售磷酸铁大，还有振实密度远高于对比例1-2。对比例1的反应温度太低，需要加碱促进沉淀，添加碱液沉淀会 影响制得的一次粒子堆积效果，一次粒子堆积不一样，就会影响二水磷酸铁的比表面积和压实密度。对比例1还有钠盐废水产生，还需要处理钠盐废水。对比例2的的反应温度太低，无法生成沉淀。As can be seen from Table 3, ferric phosphate dihydrate with large particle size, small specific surface area and large TD (tapped density) was prepared by the method of Examples 1-4 of the present invention. Wherein the specific surface area of the ferric phosphate dihydrate prepared in Example 1-2 is lower than that of Comparative Example 1 and commercially available ferric phosphate, the energy consumption of subsequent calcination is lower, the particle size is larger than that of Comparative Example 1 and commercially available ferric phosphate, and vibration The solid density is much higher than that of Comparative Examples 1-2. The reaction temperature of comparative example 1 is too low, need to add alkali to promote precipitation, adding alkali liquor precipitation can affect the primary particle stacking effect obtained, the primary particle stacking is not the same, will affect the specific surface area and compaction density of iron phosphate dihydrate. In Comparative Example 1, sodium salt wastewater is also generated, and the sodium salt wastewater needs to be treated. The reaction temperature of Comparative Example 2 was too low to form a precipitate.
图1为本发明实施例1的二水磷酸铁的SEM图；从图1可以看出实施例制备得到了球形度良好的球形颗粒磷酸铁，图2为本发明实施例1的二水磷酸铁的XRD图；从图2的XRD图谱可以看出实施例1制备所得为纯相二水磷酸铁。图3为本发明对比例1的二水磷酸铁的SEM图；从图3可以看出对比例1为细小一次粒子团聚而成的磷酸铁，因此对比例1的磷酸铁的比表面积大。Fig. 1 is the SEM image of the iron phosphate dihydrate of Example 1 of the present invention; it can be seen from Fig. 1 that the embodiment has prepared spherical particle iron phosphate with good sphericity, and Fig. 2 is the iron phosphate dihydrate of Example 1 of the present invention XRD pattern; from the XRD pattern in Figure 2, it can be seen that the preparation obtained in Example 1 is pure-phase iron phosphate dihydrate. 3 is the SEM image of the iron phosphate dihydrate of Comparative Example 1 of the present invention; it can be seen from FIG. 3 that Comparative Example 1 is an iron phosphate formed by agglomeration of fine primary particles, so the specific surface area of the iron phosphate of Comparative Example 1 is large.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种磷酸铁前驱体，其特征在于，所述磷酸铁前驱体的微观形貌呈球状且粒径D50为10-20μm，比表面积为1-3m 2/g，振实密度为1-1.5g/cm 3。 An iron phosphate precursor, characterized in that the microscopic morphology of the iron phosphate precursor is spherical, the particle size D50 is 10-20 μm, the specific surface area is 1-3 m 2 /g, and the tap density is 1-1.5 g /cm 3 .
  2. 根据权利要求1中所述的磷酸铁前驱体，其特征在于，所述磷酸铁前驱体主要由以下原料制得：铁源和磷源；所述铁源中铁元素和磷源中磷元素的摩尔比为(0.95～1.02):1；所述磷酸铁前驱体带两个结晶水；所述磷源为磷酸、亚磷酸、次磷酸钠、磷酸二氢铵或磷酸铵中的至少一种；所述铁源为铁粉、铁皮、氯化亚铁、氯化铁、硫酸亚铁、硝酸铁或醋酸亚铁中的一种。The iron phosphate precursor according to claim 1, wherein the iron phosphate precursor is mainly prepared from the following raw materials: iron source and phosphorus source; moles of iron in the iron source and phosphorus in the phosphorus source The ratio is (0.95～1.02): 1; the iron phosphate precursor has two crystal waters; the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate; The iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate.
  3. 权利要求1-2任一项所述的磷酸铁前驱体的制备方法，其特征在于，包括以下步骤：The preparation method of the iron phosphate precursor described in any one of claim 1-2, is characterized in that, comprises the following steps:
    S1、将铁源和磷源混合，调节pH为-1～2.5，得到金属液；S1. Mix the iron source and the phosphorus source, and adjust the pH to -1 to 2.5 to obtain molten metal;
    S2、将所述金属液搅拌，升温，反应，得到磷酸铁浆料；S2, the molten metal is stirred, heated, and reacted to obtain iron phosphate slurry;
    S3、将所述磷酸铁浆料过滤，得到磷酸铁沉淀；S3, the ferric phosphate slurry is filtered to obtain ferric phosphate precipitation;
    S4、取所述磷酸铁沉淀洗涤，烘干，得到二水磷酸铁。S4, get described ferric phosphate precipitation washing, oven dry, obtain ferric phosphate dihydrate.
  4. 根据权利要求3所述的制备方法，其特征在于，步骤S1中，所述磷源为磷酸、亚磷酸、次磷酸钠、磷酸二氢铵或磷酸铵中的至少一种。The preparation method according to claim 3, wherein in step S1, the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate or ammonium phosphate.
  5. 根据权利要求3所述的制备方法，其特征在于，步骤S1中，所述铁源为铁粉、铁皮、氯化亚铁、氯化铁、硫酸亚铁、硝酸铁或醋酸亚铁中的一种。The preparation method according to claim 3, wherein in step S1, the iron source is one of iron powder, iron sheet, ferrous chloride, ferric chloride, ferrous sulfate, ferric nitrate or ferrous acetate kind.
  6. 根据权利要求3所述的制备方法，其特征在于，当所述铁源为铁粉、铁皮、氯化亚铁、硫酸亚铁或醋酸亚铁中的一种时，所述铁源和磷源混合后还需添加氧化剂；所述氧化剂为双氧水、过氧化钠、过硫酸铵中的至少一种。The preparation method according to claim 3, wherein when the iron source is one of iron powder, iron sheet, ferrous chloride, ferrous sulfate or ferrous acetate, the iron source and the phosphorus source After mixing, an oxidant needs to be added; the oxidant is at least one of hydrogen peroxide, sodium peroxide and ammonium persulfate.
  7. 根据权利要求3中所述的制备方法，其特征在于，步骤S1中，所述金属液的铁元素和磷元素的摩尔比为(0.95～1.02)：1；步骤S1中，所述调节pH为-1～2.5所使用的物质为硫酸。The preparation method according to claim 3, wherein in step S1, the molar ratio of iron element and phosphorus element in the molten metal is (0.95-1.02):1; in step S1, the pH adjustment is as follows: The substance used in -1 to 2.5 is sulfuric acid.
  8. 根据权利要求3所述的制备方法，其特征在于，步骤S2中，所述搅拌的速度为300-500r/min。The preparation method according to claim 3, characterized in that, in step S2, the stirring speed is 300-500 r/min.
  9. 根据权利要求3所述的制备方法，其特征在于，步骤S2中，所述升温的温度为 70-100℃；步骤S4中，所述烘干的温度为60-110℃。The preparation method according to claim 3, characterized in that, in step S2, the temperature for heating is 70-100°C; in step S4, the temperature for drying is 60-110°C.
  10. 权利要求1-2任一项所述的磷酸铁前驱体在制备锂离子电池中的应用。Application of the iron phosphate precursor according to any one of claims 1-2 in the preparation of lithium ion batteries.
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