CN101640268A - Preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery - Google Patents
Preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery Download PDFInfo
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 title claims abstract description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 7
- 239000010406 cathode material Substances 0.000 title abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 16
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940116007 ferrous phosphate Drugs 0.000 claims description 7
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 7
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 7
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000004225 ferrous lactate Substances 0.000 claims description 2
- 235000013925 ferrous lactate Nutrition 0.000 claims description 2
- 229940037907 ferrous lactate Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- AULKGSAUVLLZLC-UHFFFAOYSA-H dilithium iron(2+) diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] AULKGSAUVLLZLC-UHFFFAOYSA-H 0.000 claims 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 25
- 239000002245 particle Substances 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
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Abstract
本发明公开了一种锂离子电池正极材料磷酸铁锂前驱体磷酸铁的制备方法。是按亚铁离子和磷酸根离子的化学计量比为0.8－1.2∶1，将浓度为0.05－2mol/L的亚铁离子水溶液和磷酸根水溶液以400－1000mL/h的速度同时加入反应器中，在反应温度为50－90℃、搅拌速度为400－1200rpm条件下，反应0.2－2h；再加入化学计量过量的双氧水，反应0.2－2h，再经陈化2－8h、过滤和洗涤、干燥；得到带两个结晶水的磷酸铁粉末。所得磷酸铁的总铁含量(Fe)为29.5－30.5％，P为16.0－16.9％，粒径为0.1－1μm，D50为1－5μm。本发明操作过程简便、设备简单、易于控制、能耗低，粒径分布均匀、细小，反应活性高，适用于制备锂离子电池正极材料磷酸铁锂。The invention discloses a preparation method of lithium iron phosphate precursor iron phosphate, which is a cathode material of a lithium ion battery. The stoichiometric ratio of ferrous ions and phosphate ions is 0.8-1.2:1, and the ferrous ion aqueous solution and phosphate aqueous solution with a concentration of 0.05-2mol/L are simultaneously added to the reactor at a rate of 400-1000mL/h , at a reaction temperature of 50-90°C and a stirring speed of 400-1200rpm, react for 0.2-2h; then add a stoichiometric excess of hydrogen peroxide, react for 0.2-2h, then age for 2-8h, filter, wash, and dry ; Obtain iron phosphate powder with two crystal waters. The obtained ferric phosphate has a total iron content (Fe) of 29.5-30.5 percent, a P of 16.0-16.9 percent, a particle size of 0.1-1 μm, and a D 50 of 1-5 μm. The invention has the advantages of simple operation process, simple equipment, easy control, low energy consumption, uniform and small particle size distribution, high reactivity, and is suitable for preparing lithium iron phosphate, a cathode material of lithium ion batteries.
Description
技术领域 technical field
本发明涉及一种锂离子电池正极材料磷酸铁锂前驱体磷酸铁的制备方法。The invention relates to a preparation method of iron phosphate, a lithium iron phosphate precursor, which is a cathode material of a lithium ion battery.
背景技术 Background technique
磷酸铁由于其价格便宜，对环境无污染，作为锂电池正极材料很有优势，Prosini等通过共沉淀法，得到无定形FePO4·1.5H2O；Hong等研究了无定形FePO4的合成条件。Croce等通过湿化学法，制得六方晶型的FePO4。FePO4·2H2O是粉红色单斜结晶，可用作食品和饲料添加剂，尤其适用于锂离子电池正极材料磷酸铁锂的制备。目前工业上磷酸铁的制备方法是由铁酸盐和磷酸盐高温反应合成，存在工艺流程复杂，生产条件苛刻，产品成分难控制等问题。中国专利200810049265.5公开了一种用于锂电池正极材料正磷酸铁的制备方法，由七水硫酸亚铁，磷酸，双氧水或氯酸钠，氢氧化钠或碳酸钠及水为原料制备，所得正磷酸铁的粒径为1-2μm，比表面积比较大，为48-55.5m2/g，会使以磷酸铁为前驱体制得的磷酸铁锂容量相对减少。本发明通过调整铁源和磷源，以降低成本、优化材料和保护环境为目的，控制过程各个条件，在不用调节pH值前提下得到粒径适中、特别适合制备磷酸铁锂的带两个结晶水的磷酸铁。Because of its low price and no pollution to the environment, iron phosphate has great advantages as a cathode material for lithium batteries. Prosini et al. obtained amorphous FePO 4 1.5H 2 O through co-precipitation method; Hong et al. studied the synthesis conditions of amorphous FePO 4 . Croce et al. prepared hexagonal FePO 4 by wet chemical method. FePO 4 ·2H 2 O is a pink monoclinic crystal, which can be used as a food and feed additive, especially for the preparation of lithium iron phosphate, a cathode material for lithium ion batteries. At present, the industrial iron phosphate preparation method is synthesized by high-temperature reaction of ferrite and phosphate, which has problems such as complicated process flow, harsh production conditions, and difficult control of product components. Chinese patent 200810049265.5 discloses a method for preparing ferric orthophosphate used as a positive electrode material for lithium batteries. It is prepared from ferrous sulfate heptahydrate, phosphoric acid, hydrogen peroxide or sodium chlorate, sodium hydroxide or sodium carbonate and water as raw materials, and the obtained orthophosphoric acid The particle size of iron is 1-2μm, and the specific surface area is relatively large, 48-55.5m 2 /g, which will relatively reduce the capacity of lithium iron phosphate prepared with iron phosphate as the precursor. The present invention adjusts the iron source and the phosphorus source, aims at reducing costs, optimizing materials and protecting the environment, controls various conditions in the process, and obtains two crystals with moderate particle size and is especially suitable for preparing lithium iron phosphate without adjusting the pH value. iron phosphate in water.
发明内容 Contents of the invention
本发明的目的在于提供一种锂离子电池正极材料磷酸铁锂前驱体磷酸铁的制备方法，以得到带两个结晶水的磷酸铁，操作过程简便、设备简单、易于控制、能耗低，得到的材料粒径分布均匀、细小，反应活性高，适用于制备锂离子电池材料磷酸铁锂。The object of the present invention is to provide a kind of preparation method of lithium iron phosphate precursor ferric phosphate of anode material lithium iron phosphate, to obtain iron phosphate with two crystal waters, the operation process is simple, the equipment is simple, easy to control, low energy consumption, obtain The particle size distribution of the material is uniform, fine, and the reaction activity is high, which is suitable for the preparation of lithium iron phosphate, a lithium ion battery material.
本发明的技术方案包括以下步骤：Technical scheme of the present invention comprises the following steps:
(1)磷酸亚铁的制备：按亚铁离子和磷酸根离子的化学计量比为0.8-1.2∶1，将浓度为0.05-2mol/L的亚铁离子水溶液和磷酸根水溶液以400-1000mL/h的速度同时加入反应器中，在反应温度为50-90℃、搅拌速度为400-1200rpm条件下，反应0.2-2h；(1) Preparation of ferrous phosphate: the stoichiometric ratio of ferrous ions and phosphate ions is 0.8-1.2: 1, and the ferrous ion aqueous solution and phosphate aqueous solution with a concentration of 0.05-2mol/L are mixed with 400-1000mL/ Add the speed of h into the reactor at the same time, and react for 0.2-2h under the condition of reaction temperature of 50-90°C and stirring speed of 400-1200rpm;
(2)磷酸铁的制备：在上述反应器中加入化学计量过量的双氧水，至大量白色沉淀产生，继续反应0.2-2h，再经陈化2-8h后，反复过滤和洗涤，分离得到磷酸铁；(2) Preparation of ferric phosphate: add stoichiometrically excess hydrogen peroxide to the above reactor until a large amount of white precipitates are produced, continue to react for 0.2-2h, and after aging for 2-8h, repeatedly filter and wash to obtain ferric phosphate ;
(3)放入鼓风干燥箱中在温度60-140℃干燥5-20h，得到干燥的FePO4·2H2O粉末。(3) Put it into a blast drying oven and dry at a temperature of 60-140° C. for 5-20 hours to obtain dry FePO 4 ·2H 2 O powder.
所述亚铁离子水溶液是七水硫酸亚铁，硝酸亚铁，氯化亚铁，醋酸亚铁、乳酸亚铁或草酸亚铁水溶液中的一种。The ferrous ion aqueous solution is one of ferrous sulfate heptahydrate, ferrous nitrate, ferrous chloride, ferrous acetate, ferrous lactate or ferrous oxalate aqueous solution.
所述磷酸根水溶液为磷酸一氢铵或磷酸二氢铵或磷酸水溶液中的一种。The phosphate aqueous solution is one of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate or phosphoric acid aqueous solution.
所述双氧水的浓度为30％。The concentration of the hydrogen peroxide is 30%.
本发明所得磷酸铁的总铁含量(Fe)为29.5-30.5％，P为16.0-16.9％，粒径为0.1-1μm，D50为1-5μm。本发明操作简便、设备简单、易于控制、能耗低，得到的材料粒径分布均匀、细小，反应活性高，尤其适用于制备锂离子电池材料磷酸铁锂。The iron phosphate obtained by the invention has a total iron content (Fe) of 29.5-30.5%, a P of 16.0-16.9%, a particle size of 0.1-1 μm, and a D 50 of 1-5 μm. The invention has the advantages of simple operation, simple equipment, easy control, low energy consumption, uniform and small particle size distribution of the obtained material, and high reactivity, and is especially suitable for preparing lithium iron phosphate as a lithium ion battery material.
附图说明 Description of drawings
图1为实施例1得到的磷酸铁的SEM图谱；Fig. 1 is the SEM collection of illustrative plates of the ferric phosphate that embodiment 1 obtains;
图2为实施例1得到的磷酸铁的DSC-TGA图谱。Fig. 2 is the DSC-TGA collection of patterns of the ferric phosphate that embodiment 1 obtains.
具体实施方式 Detailed ways
实施例1：Example 1:
(1)称取七水硫酸亚铁55.604g，称取磷酸二氢铵23.004g，分别将其溶于0.2L的去离子水中，搅拌使之溶解；将硫酸亚铁溶液和磷酸二氢铵溶液同时以800mL/h的速度加入到反应器中，并开启搅拌仪进行强烈的搅拌，控制反应温度为80℃，在搅拌速度为800r/min条件下，反应时间为0.5h，得到灰色磷酸亚铁的悬浮液；(1) Weigh 55.604g of ferrous sulfate heptahydrate, weigh 23.004g of ammonium dihydrogen phosphate, dissolve it in 0.2L deionized water respectively, stir to dissolve it; mix ferrous sulfate solution and ammonium dihydrogen phosphate solution At the same time, it was added to the reactor at a speed of 800mL/h, and the stirrer was turned on for strong stirring. The reaction temperature was controlled at 80°C, and the reaction time was 0.5h under the condition of a stirring speed of 800r/min, and gray ferrous phosphate was obtained. suspension;
(2)取双氧水11.4mL加入到上述悬浮液中，马上有大量白色沉淀产生，继续反应0.5h，再经陈化6h后，反复过滤和洗涤，得到沉淀物磷酸铁，颜色为白色。所得磷酸铁的总铁含量(Fe)为29.8％，P为16.5％，粒径为300nm左右，D50＝2.5μm。(2) Take 11.4 mL of hydrogen peroxide and add it to the above suspension, a large amount of white precipitates will appear immediately, continue to react for 0.5 h, and after aging for 6 h, filter and wash repeatedly to obtain the precipitate iron phosphate, which is white in color. The total iron content (Fe) of the obtained ferric phosphate is 29.8%, P is 16.5%, the particle size is about 300nm, and D 50 =2.5μm.
(3)按已有技术将第2步分离的磷酸铁，放入鼓风干燥箱于120℃干燥12h；得到干燥的FePO4·2H2O粉末。(3) Put the iron phosphate separated in the second step into a blast drying oven at 120° C. for 12 hours according to the prior art; obtain dry FePO 4 ·2H 2 O powder.
实施例2：Example 2:
(1)称取七水硫酸亚铁55.604g，称取磷酸二氢铵23.004g，分别将其溶于2L的去离子水中，搅拌使之溶解；将硫酸亚铁溶液和磷酸二氢铵溶液同时以600mL/h的速度加入到反应器中，并开启搅拌仪进行强烈的搅拌，控制反应温度为60℃，在搅拌速度为1000r/min条件下，反应时间为1h，得到浅灰色磷酸亚铁的悬浮液；(1) Weigh 55.604g of ferrous sulfate heptahydrate, weigh 23.004g of ammonium dihydrogen phosphate, dissolve it in 2L of deionized water respectively, and stir to dissolve it; mix ferrous sulfate solution and ammonium dihydrogen phosphate solution simultaneously Add it into the reactor at a speed of 600mL/h, and turn on the stirrer for strong stirring, control the reaction temperature at 60°C, and under the condition of a stirring speed of 1000r/min, the reaction time is 1h to obtain light gray ferrous phosphate suspension;
(2)取双氧水15.6mL加入到上述悬浮液中，马上有大量白色沉淀产生，继续反应1h，再经陈化8h后，反复过滤和洗涤，得到沉淀物磷酸铁，颜色为浅黄色。所得磷酸铁的总铁含量(Fe)为31.8％，P为17.2％，粒径为100nm左右，D50＝1.8μm。(2) Take 15.6 mL of hydrogen peroxide and add it to the above suspension, a large amount of white precipitates will appear immediately, continue to react for 1 hour, and after aging for 8 hours, filter and wash repeatedly to obtain precipitated ferric phosphate, which is light yellow in color. The total iron content (Fe) of the obtained ferric phosphate is 31.8%, P is 17.2%, the particle size is about 100nm, and D 50 =1.8μm.
(3)按已有技术将第2步分离的磷酸铁放入鼓风干燥箱于140℃干燥14h；得到干燥的FePO4·2H2O粉末。(3) Put the iron phosphate separated in the second step into a blast drying oven at 140° C. for 14 hours according to the prior art; obtain dry FePO 4 ·2H 2 O powder.
实施例3：Example 3:
(1)称取七水硫酸亚铁55.604g，称取磷酸二氢铵23.004g，分别将其溶于0.1L的去离子水中，搅拌使之溶解；将硫酸亚铁溶液和磷酸二氢铵溶液同时以1000mL/h的速度加入到反应器中，并开启搅拌仪进行搅拌，控制反应温度为90℃，在搅拌速度为600r/min条件下，反应时间为0.3h，得到浅灰色磷酸亚铁的悬浮液；(1) Weigh 55.604g of ferrous sulfate heptahydrate, weigh 23.004g of ammonium dihydrogen phosphate, dissolve it in 0.1L deionized water respectively, stir to dissolve it; mix ferrous sulfate solution and ammonium dihydrogen phosphate solution At the same time, it was added to the reactor at a speed of 1000mL/h, and the stirrer was turned on for stirring, and the reaction temperature was controlled to be 90°C. Under the condition of a stirring speed of 600r/min, the reaction time was 0.3h, and light gray ferrous phosphate was obtained. suspension;
(2)取双氧水11.4mL加入到上述悬浮液中，马上有大量白色沉淀产生，继续反应0.3h，再经陈化4h后，反复过滤和洗涤，得到沉淀物磷酸铁，颜色为白色。所得磷酸铁的总铁含量(Fe)为25.2％，P为13.7％，粒径为1μm左右，D50＝4.3μm。(2) Take 11.4mL of hydrogen peroxide and add it to the above suspension, a large amount of white precipitates will appear immediately, continue to react for 0.3h, and after aging for 4h, filter and wash repeatedly to obtain precipitate iron phosphate, which is white in color. The total iron content (Fe) of the obtained ferric phosphate is 25.2%, P is 13.7%, the particle size is about 1 μm, and D 50 =4.3 μm.
(3)按已有技术将第2步分离的磷酸铁，放入鼓风干燥箱于80℃干燥10h；得到干燥的FePO4·2H2O粉末。(3) Put the iron phosphate separated in the second step into a blast drying oven at 80° C. for 10 h according to the prior art; obtain dry FePO 4 ·2H 2 O powder.
实施例4：Example 4:
(1)称取硝酸亚铁36g，称取磷酸一氢铵26.4g，分别将其溶于0.4L的去离子水中，搅拌使之溶解；将硝酸亚铁溶液和磷酸一氢铵溶液同时以800mL/h的速度加入到反应器中，并开启搅拌仪进行搅拌，控制反应温度为80℃，在搅拌速度为800r/min条件下，反应时间为1h，得到浅灰色磷酸亚铁的悬浮液；(1) Weigh 36g of ferrous nitrate and 26.4g of ammonium monohydrogen phosphate, respectively dissolve them in 0.4L deionized water, stir to dissolve them; Add it into the reactor at a speed of 1/h, and turn on the stirrer to stir, control the reaction temperature to 80°C, and under the condition of stirring speed of 800r/min, the reaction time is 1h, and a suspension of light gray ferrous phosphate is obtained;
(2)取双氧水11.4mL加入到上述悬浮液中，马上有大量白色沉淀产生，继续反应1h，再经陈化4h后，反复过滤和洗涤，得到沉淀物磷酸铁，颜色为白色。所得磷酸铁的总铁含量(Fe)为29.1％，P为15.9％，粒径为200nm左右，D50＝2.2μm。(2) Take 11.4 mL of hydrogen peroxide and add it to the above suspension, a large amount of white precipitates will appear immediately, continue to react for 1 hour, and after aging for 4 hours, filter and wash repeatedly to obtain precipitate iron phosphate, which is white in color. The total iron content (Fe) of the obtained ferric phosphate is 29.1%, P is 15.9%, the particle size is about 200nm, and D 50 =2.2μm.
(3)按已有技术将第2步分离的磷酸铁，放入鼓风干燥箱于140℃干燥10h；得到干燥的FePO4·2H2O粉末。(3) Put the iron phosphate separated in the second step into a blast drying oven at 140° C. for 10 h according to the prior art; obtain dry FePO 4 ·2H 2 O powder.
实施例5：Example 5:
(1)称取二水草酸亚铁36g，称取磷酸二氢铵23.004g，分别将其溶于150mL的去离子水中，搅拌使之溶解；将二水草酸亚铁溶液和磷酸二氢铵溶液同时以800mL/h的速度加入到反应器中，并开启搅拌仪进行搅拌，控制反应温度为80℃，在搅拌速度为800r/min条件下，反应时间为0.5h，得到浅灰色磷酸亚铁的悬浮液；(1) Weigh 36g of ferrous oxalate dihydrate and 23.004g of ammonium dihydrogen phosphate, respectively dissolve them in 150mL of deionized water, stir to dissolve them; mix ferrous oxalate dihydrate solution and ammonium dihydrogen phosphate solution At the same time, it was added to the reactor at a speed of 800mL/h, and the stirrer was turned on to stir, the reaction temperature was controlled to be 80°C, and the reaction time was 0.5h under the condition of a stirring speed of 800r/min, and the light gray ferrous phosphate was obtained. suspension;
(2)取双氧水11.4mL加入到上述悬浮液中，马上有大量白色沉淀产生，继续反应0.5h，再经陈化6h后，反复过滤和洗涤，得到沉淀物磷酸铁，颜色为白色。所得磷酸铁的总铁含量(Fe)为30.6％，P为17.1％，粒径为500nm左右，D50＝3.2μm。(2) Take 11.4 mL of hydrogen peroxide and add it to the above suspension, a large amount of white precipitates will appear immediately, continue to react for 0.5 h, and after aging for 6 h, filter and wash repeatedly to obtain the precipitate iron phosphate, which is white in color. The total iron content (Fe) of the obtained ferric phosphate is 30.6%, P is 17.1%, the particle size is about 500nm, and D 50 =3.2μm.
(3)按已有技术将第2步分离的磷酸铁，放入鼓风干燥箱于120℃干燥14h，得到干燥的FePO4·2H2O粉末。(3) Put the iron phosphate separated in the second step into a blast drying oven at 120° C. for 14 hours according to the prior art to obtain dry FePO 4 ·2H 2 O powder.
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