TW201504137A - Amorphised iron (iii) phosphate - Google Patents

Amorphised iron (iii) phosphate Download PDF

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TW201504137A
TW201504137A TW103112293A TW103112293A TW201504137A TW 201504137 A TW201504137 A TW 201504137A TW 103112293 A TW103112293 A TW 103112293A TW 103112293 A TW103112293 A TW 103112293A TW 201504137 A TW201504137 A TW 201504137A
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iron
iii
amorphous
phosphate
orthophosphate
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Gunnar Buehler
Kilian Schwarz
Christian Graf
Manola Stay
Michael Rapphahn
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Chem Fab Budenheim Kg
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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
    • 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
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

Abstract

A process for the production of an amorphous or amorphised iron(III)phosphate anhydrate or a carbon composite of amorphous or amorphised iron(III)phosphate anhydrate, characterised in that iron(III)orthophosphate of the general formula FePO4 * 2H2O or carbon composite of iron(III)orthophosphate of the general formula FePO4 * 2H2O, wherein at least 80% by weight of the iron(III)orthophosphate is present in accordance with powder X-ray diffraction analysis with CuK[alpha] radiation in the phosphosiderite (metastrengite II)-crystal structure, is dehydrated at a temperature in the region of between 140 and 250 DEG C to a residual water content of between 0 and 1% by weight, which includes both bound water of crystallisation and also free water, and to a water of crystallisation content ≤ 0.2 H2O.

Description

非晶形磷酸鐵(III) Amorphous iron phosphate (III)

本發明關於一種新穎之結構為非晶形或非晶形化的磷酸鐵(III)無水物及碳複合物，以及製造方法。該結構為非晶形或非晶形化的磷酸鐵無水物適於直接用作鋰離子蓄電池之陰極材料或用作化學或熱鋰化之磷酸鐵或其碳複合物的製造之初步階段。 The present invention relates to a novel iron oxide (III) anhydrate and carbon composite having an amorphous or amorphous structure, and a method of producing the same. The amorphous or amorphous ferric phosphate anhydrate is suitable for use as a cathode material for a lithium ion battery or as a preliminary stage for the manufacture of chemically or thermally lithiated iron phosphate or a carbon composite thereof.

本發明另外關於經鋰化之磷酸鐵及其碳複合物，以及從非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物製造該經鋰化之磷酸鐵及其碳複合物的方法。該產物尤其適於用作鋰離子蓄電池之陰極材料。 The present invention further relates to lithiated iron phosphate and carbon composites thereof, and the production of the lithiated iron phosphate and carbon composite thereof from amorphous or amorphous iron (III) phosphate anhydrate or carbon composite thereof Methods. This product is particularly suitable for use as a cathode material for lithium ion batteries.

可充電鋰離子蓄電池係廣泛使用之儲能工具，特別是在行動電子裝置中，由於Li離子蓄電池以高能量密度著稱且可供應高標稱電壓，因此在相當之電力的情況下，鋰離子蓄電池明顯比慣用蓄電池更小及更輕。已公認尖晶石(如LiCoO2、LiNiO2、LiNi1-xCOxO2及LiMnnO4)作為陰極材料。為了提高Li離子蓄電池的安全性，特別是與操 作中之熱過載相關的安全性，已發展LiFePO4作為陰極材料。該材料以良好電源、高電容率及在操作時之高熱安定性著稱。正磷酸鐵為製造用於鋰離子蓄電池之LiFePO4陰極材料的起始材料。 Rechargeable lithium-ion batteries are widely used energy storage tools, especially in mobile electronic devices. Li ion batteries are known for their high energy density and can supply high nominal voltages. Therefore, in the case of equivalent power, lithium ion batteries Significantly smaller and lighter than conventional batteries. Spinel (such as LiCoO 2 , LiNiO 2 , LiNi 1-x CO x O 2 and LiMn n O 4 ) has been recognized as a cathode material. In order to improve the safety of Li-ion batteries, particularly in connection with thermal overload in operation, LiFePO 4 has been developed as a cathode material. This material is known for its good power supply, high permittivity and high thermal stability during operation. Iron orthophosphate is the starting material for the manufacture of LiFePO 4 cathode materials for lithium ion batteries.

因涉及在操作(充電及放電)期間不想要的氧化還原反應之任何污染均會不利地影響蓄電池的電力，故Li離子蓄電池之陰極材料對於純度的要求高。可能的污染之性質及濃度實質上取決於用於製造該陰極材料的原料之品質及其製造方法本身。在非晶形之製造方法中，可能採用一些措施以在隨後減少雜質，然而此做法通常與製造成本增加有關。因此，需要使用儘可能純的起始材料或原料來製造該陰極材料。除了起始材料的純度之外，其結果及形態亦實質影響所製造的陰極材料之品質。 Since any contamination involving an unwanted redox reaction during operation (charging and discharging) adversely affects the power of the battery, the cathode material of the Li ion battery has high purity requirements. The nature and concentration of possible contamination is substantially dependent on the quality of the raw materials used to make the cathode material and the method of manufacture itself. In the amorphous manufacturing method, some measures may be employed to subsequently reduce impurities, but this is usually associated with an increase in manufacturing cost. Therefore, it is necessary to manufacture the cathode material using as pure a starting material or material as possible. In addition to the purity of the starting materials, the results and morphology also substantially affect the quality of the cathode material produced.

DE 10 2009 001 204 A1描述呈包括特定形態及純度之磷菱鐵礦晶體形式(磷菱鐵礦(metastrengite)II)的結晶正磷酸鐵(III)(FOP)之製造。由於該特定純度及新穎材料性質，正磷酸鐵(III)(FOP)特別適於作為製造用於Li離子蓄電池之磷酸鋰鐵(LiFePO4；LFP)的起始材料，例如根據US 2010/0065787 A1中所述之方法。 DE 10 2009 001 204 A1 describes the manufacture of crystalline iron orthophosphate (III) (FOP) in the form of a crystal form of pyrite (metastrengite II) comprising a specific morphology and purity. Due to this particular purity and novel material properties, iron (III) orthophosphate (FOP) is particularly suitable as a starting material for the manufacture of lithium iron phosphate (LiFePO 4 ; LFP) for Li ion batteries, for example according to US 2010/0065787 A1 The method described in the above.

純磷酸鋰鐵(LFP)具有不良導電性，因此只能有限程度地使用其純形式作為陰極材料。因此已發展各種不同途徑以改善磷酸鋰鐵的導電性。因此，例如US 6 855 273 B2、US 2010/0065787 A1及DE 10 2011 003 125描述在FOP或LFP上製造碳塗層以改善導電性。該等產物亦稱為 FOP或LFP之碳複合物，且於本文中分別縮寫為FOP/C及LFP/C。 Pure lithium iron phosphate (LFP) has poor electrical conductivity, so its pure form can only be used to a limited extent as a cathode material. Various different approaches have therefore been developed to improve the conductivity of lithium iron phosphate. Thus, for example, US 6 855 273 B2, US 2010/0065787 A1 and DE 10 2011 003 125 describe the production of carbon coatings on FOP or LFP to improve electrical conductivity. These products are also known as A carbon composite of FOP or LFP, and is abbreviated herein as FOP/C and LFP/C, respectively.

DE 10 2007 049 757、DE 10 2009 001 204及DE 10 2011 003 125描述通式FePO4×nH2O(其中n2.5)之結晶正磷酸鐵(III)水合物或其碳複合物的製造，其中根據粉末X射線繞射分析，該正磷酸鐵(III)存在該磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構中，由於該等特別製造方法及新穎材料性質之故，該結晶正磷酸鐵(III)水合物或其碳複合物非常適於作為使用已知方法(例如利用藉由熱煅燒之固態合成或利用熱液或熱溶劑(solvothermal)法)製造磷酸鋰鐵(LFP)的前驅物。 DE 10 2007 049 757, DE 10 2009 001 204 and DE 10 2011 003 125 describe the general formula FePO 4 ×nH 2 O (where n 2.5) Manufacture of crystalline iron (III) orthophosphate hydrate or a carbon composite thereof, wherein the iron ore (III) orthophosphate is present in the metadrengite according to powder X-ray diffraction analysis II) In the crystal structure, the crystalline iron(III) orthophosphate hydrate or its carbon composite is very suitable for use as a known method (for example, by thermal calcination) due to the special manufacturing methods and novel material properties. The precursor of lithium iron phosphate (LFP) is produced by solid state synthesis or by hydrothermal or solvothermal method.

近年來已確立用於製造LFP或LFP/C之藉由熱煅燒之固相合成。相較於熱液或熱溶劑法，藉由熱煅燒之固相合成在需要複雜度及費用遠遠較低的裝置技術方面且明顯較低成本。然而，因所牽涉的製程之故，必須使用在介於600與700℃範圍內之高溫，然後隨之而來的是顯著之粒子生長及煅燒材料燒結在一起，故藉由熱煅燒之固相合成中的粒度控制極困難。然而，此係LFP之生產中特別應予避免的，以保持短Li離子擴散路徑。 Solid phase synthesis by thermal calcination for the production of LFP or LFP/C has been established in recent years. Compared to hydrothermal or thermal solvent processes, solid phase synthesis by thermal calcination is significantly less costly in terms of device technology that requires less complexity and expense. However, due to the process involved, it is necessary to use a high temperature in the range of 600 and 700 ° C, followed by significant particle growth and sintering of the calcined material, so the solid phase by thermal calcination Particle size control in synthesis is extremely difficult. However, this is particularly desirable in the production of LFP to maintain a short Li ion diffusion path.

US 2009/0311597描述以不同過渡金屬或過渡金屬化合物摻雜LFP以製造具有可接受水準之導電性的陰極材料。在該情況下，摻雜劑可以混合晶體形式均勻分布在該材料中，或可以除了LFP之外的獨立結晶相存在。摻雜過渡金屬或摻雜鑭系元素元素涉及該等摻雜劑本身的高成 本，以及亦需要非常複雜且成本高昂的方法以獲致提高導電性的摻雜及分布。因此，根據US 2009/0311597之方法需要800℃之非常高煅燒溫度及至高達96小時的長煅燒時間，此在經濟上來說是嚴重缺點。 US 2009/0311597 describes the doping of LFP with different transition metals or transition metal compounds to produce a cathode material having an acceptable level of electrical conductivity. In this case, the dopant may be uniformly distributed in the material in a mixed crystal form, or may exist in a separate crystalline phase other than LFP. Doping transition metals or doped lanthanide elements involves the high formation of the dopants themselves This, and also requires very complex and costly methods to achieve doping and distribution that increase conductivity. Therefore, the method according to US 2009/0311597 requires a very high calcination temperature of 800 ° C and a long calcination time of up to 96 hours, which is a serious disadvantage in terms of economy.

Wang等人(Solid State Ionics,2007,178,843-947)描述一種熱液方法，其供應非晶形正磷酸鐵(III)二水合物，然後在醇介質中於高溫下藉由添加抗壞血酸及鋰鹽將該非晶形正磷酸鐵(III)二水合物鋰化。所得之材料為非晶形，因此無法更詳細表示特徵。該材料在具有5%之氫的恆定氬流下於600℃煅燒2小時之後，獲得LFP，該LFP於電化學半電池測試中提供至少與當前技術相當之結果。然而，Wang等人所述之方法具有以大技術規模實施時相反一缺點，因此無法商業化。 Wang et al. (Solid State Ionics, 2007, 178, 843-947) describe a hydrothermal process that supplies amorphous iron (III) orthophosphate dihydrate, which is then added to the alcohol at elevated temperatures by adding ascorbic acid and lithium salts. The amorphous iron (III) orthophosphate dihydrate is lithiated. The resulting material is amorphous and therefore cannot be characterized in more detail. The material was calcined at 600 ° C for 2 hours under a constant argon flow with 5% hydrogen to obtain LFP which provided at least comparable results to current technology in electrochemical half-cell testing. However, the method described by Wang et al. has the opposite disadvantage of being implemented on a large-scale scale and therefore cannot be commercialized.

原則上，熱液法因需要視目標溫度及所選擇之反應介質而定的高壓，故需要昂貴程序設計及高成本設備。相反之下，不使用壓力進行之簡單沉澱反應享有明確的優點。 In principle, the hydrothermal process requires expensive programming and high cost equipment due to the high pressure required depending on the target temperature and the selected reaction medium. Conversely, a simple precipitation reaction without pressure has a clear advantage.

根據Wang等人，非晶形正磷酸鐵(III)二水合物為公認可從便宜FeSO4×7H2O製造，但該方法需要只有添加鹼金屬才能獲致的pH控制。因此該產物必然含有鹼金屬及/或鹼土金屬陽離子及硫酸根離子之污染。Wang等人因此描述以此方式所製造之非晶形正磷酸鐵(III)二水合物必須重複清洗以將該等硫酸根離子及鹼金屬及/或鹼土金屬陽離子的污染去除至適當程度。 According to Wang et al., amorphous iron (III) orthophosphate dihydrate is generally known to be made from inexpensive FeSO 4 × 7H 2 O, but this method requires pH control that can only be achieved by the addition of an alkali metal. Therefore, the product necessarily contains contamination with alkali metal and/or alkaline earth metal cations and sulfate ions. Wang et al. therefore describe that the amorphous iron(III) orthophosphate dihydrate produced in this manner must be repeatedly washed to remove the contamination of the sulfate ions and alkali metal and/or alkaline earth metal cations to an appropriate extent.

Wang等人所述之正磷酸鐵(III)二脫水具有介於 100與200nm之粒度。該高粒子表面積因而為污染性陰離子及陽離子提供大吸附面積，因此清洗製程只有些微效率。其亦描述可添加呈硝酸鹽形式之其他摻雜劑，該種摻雜劑反而將與硝酸根離子有關的其他污染引入該材料。 The iron (III) orthophosphate dehydrated by Wang et al. Particle size of 100 and 200 nm. This high particle surface area thus provides a large adsorption area for contaminating anions and cations, so the cleaning process is only slightly inefficient. It also describes the addition of other dopants in the form of nitrates which in turn introduce other contaminants associated with nitrate ions into the material.

熟悉本技術之人士明白電化學電池中呈硫酸鹽及/或硝酸鹽形式的陰離子污染導致氧化還原反應，該氧化還原反應會對電池組分發揮腐蝕作用及與電解質及/或陽極及/或陰極材料產生不要的交互作用。 Those skilled in the art will recognize that anionic contamination in the form of sulfates and/or nitrates in electrochemical cells results in redox reactions which can corrode battery components and interact with electrolytes and/or anodes and/or cathodes. The material creates unwanted interactions.

Wang等人所述之關於非晶形正磷酸鐵(III)因添加抗壞血酸及乙酸鋰而進一步反應在醇介質中產生LFP導致在高溫下反應約5小時後形成非晶形LFP相，該相無法進一步藉由非晶形特徵表示特徵。在大技術規模實施此方法時，由於形成可燃及***性氣體，故醇之蒸汽混合物需要全面性的安全性概念以及設備技術方面需要高複雜度及高費用。此外，視所使用之個別醇種類而定，因所使用之起始材料在醇中具有0.01莫耳/升的低溶解性而使其濃度水準非常低，因此與所獲得之產物相較下，必須使用非常大量醇反應介質，故此方法在生態及經濟觀點來看亦不利。 Wang et al. described that the amorphous iron (III) orthophosphate is further reacted by the addition of ascorbic acid and lithium acetate to produce LFP in an alcohol medium, resulting in the formation of an amorphous LFP phase after reacting at a high temperature for about 5 hours, which phase cannot be further borrowed. Features are represented by amorphous features. When this method is implemented on a large-scale scale, the vapor mixture of alcohol requires a comprehensive safety concept and equipment technology requires high complexity and high cost due to the formation of flammable and explosive gases. Further, depending on the type of the individual alcohol to be used, since the starting material used has a low solubility of 0.01 mol/liter in the alcohol, the concentration level is very low, and thus, compared with the obtained product, A very large amount of alcohol reaction medium must be used, so this method is also disadvantageous from an ecological and economic point of view.

為了獲得結晶LFP產物，必須在氬或氮中5%氫之還原保護性氣氛中於600℃下有效進行至少2小時的煅燒。在該情況下，原粒子之尺寸及形態僅無形地改變，但該公告中所述之高溫不可避免地造成該等原粒子燒結。然而，由燒結效應所產生之擴散障壁對於鋰離子蓄電池中之材料的電化學品質具有負面效果。此外，在該陰極材料中產生 孔隙度，從而降低電池組之工作陰極中的活性材料之比例。此對於陰極之最大能量密度或在待施用的最大活性材料量具有負面效果。 In order to obtain a crystalline LFP product, it is necessary to carry out at least 2 hours of calcination at 600 ° C in a reducing protective atmosphere of 5% hydrogen in argon or nitrogen. In this case, the size and shape of the original particles change only invisibly, but the high temperatures described in the publication inevitably cause the primary particles to sinter. However, the diffusion barrier produced by the sintering effect has a negative effect on the electrochemical quality of the material in the lithium ion battery. In addition, produced in the cathode material Porosity, thereby reducing the proportion of active material in the working cathode of the battery. This has a negative effect on the maximum energy density of the cathode or on the maximum amount of active material to be applied.

其他文獻(Masquellier等人，Journal of The Electrochemical Society,149(8)A1037-A1044,2002；Hong等人，J Mater.Chem.2002,12,1870-1874；Prosini等人，Journal of The Electrochemical Society,149(3)A297-A301,2002)描述非晶形FePO4×nH2O(n=0至4)可藉由電化學鋰化作用而直接用作電化學電池中的陰極材料。所研究之磷酸鐵材料係市售或藉由從0.025莫耳/升Fe(NH4)2(SO4)2×6H2O及0.025莫耳/升NH4H2PO4以及作為氧化劑之過氧化氫的等莫耳水溶液沉澱所製造者。該等產物某種程度地接受熱程序以設定所需之水合水含量。 Other literature (Masquellier et al, Journal of The Electrochemical Society, 149 (8) A1037-A1044, 2002; Hong et al, J Mater. Chem. 2002, 12, 1870-1874; Prosini et al, Journal of The Electrochemical Society, 149(3) A297-A301, 2002) Description Amorphous FePO 4 ×nH 2 O (n = 0 to 4) can be directly used as a cathode material in an electrochemical cell by electrochemical lithiation. The iron phosphate material studied is commercially available or by oxidizing from 0.025 mol/L Fe(NH 4 ) 2 (SO 4 ) 2 ×6H 2 O and 0.025 mol/L NH 4 H 2 PO 4 A manufacturer of hydrogen peroxide such as a molar aqueous solution. The products are subjected to a thermal program to some extent to set the desired hydration water content.

亦可在無無先前鋰化作用下直接使用不同水合物階段之正磷酸鐵(III)作為電化學電池中的陰極材料。Masquellier等人及Hong等人之上述論文係從不同水合物階段的市售非晶形磷酸鐵(III)著手進行。與水合的標稱水含量相關之資訊依作者實驗判斷而各異。在一實例中，判斷以3.6H2O之水合水含量代替FePO4×4 H2O之標稱水合水含量，而在另一實例中，發現以1.6H2O之水合水含量代替FePO4×2H2O。Prosini等人測定磷酸鐵(III)所產生之水合水含量為1.5 H2O。因此，很明顯地，無法藉由製程而精確設定該等產物中之結晶水含量。此外，製程造 成來自原料之不想要的硫酸鹽污染。此外，所使用之原料的水溶液之濃度非常低，此現在使得在該程序中需要極大量的水。所獲得之產物亦非常細微，有鑑於大量流體相，對於過濾技術要求相當高，此外亦必須洗出硫酸鹽陰離子。 Iron (III) orthophosphate, which is a different hydrate stage, can also be used as a cathode material in an electrochemical cell without prior lithiation. The above papers by Masquellier et al. and Hong et al. were carried out starting from commercially available amorphous iron (III) phosphates of different hydrate stages. Information relating to the nominal water content of the hydration varies according to the author's experimental judgment. In one example, it is judged that the nominal hydrated water content of FePO 4 ×4 H 2 O is replaced by the hydrated water content of 3.6H 2 O, and in another example, it is found that the content of hydrated water of 1.6H 2 O is substituted for FePO 4 . ×2H 2 O. Prosini et al. determined that the hydrated water content of iron (III) phosphate was 1.5 H 2 O. Therefore, it is apparent that the crystal water content in the products cannot be accurately set by the process. In addition, the process causes unwanted sulfate contamination from the feedstock. Furthermore, the concentration of the aqueous solution of the raw materials used is very low, which now requires a very large amount of water in the process. The product obtained is also very fine, in view of the large number of fluid phases, the filtration technology is quite demanding, and in addition, the sulfate anions must be washed out.

上述論文中已顯示在與無水物相較下，含水合水之非晶形磷酸鐵(III)最初具有較佳電化學效率。Hong等人報告指出在大部分情況下含水合水之陰極甚至未能承受20次充電及放電循環。無水物展現明顯較佳之循環性(cyclability)。Prosini等人亦能證實無水物之較佳循環性。 It has been shown in the above paper that the amorphous iron (III) phosphate containing water initially has a preferred electrochemical efficiency compared to the anhydrate. Hong et al. reported that in most cases the cathode of water-containing water did not even withstand 20 charge and discharge cycles. Anhydrate exhibits significantly better cyclability. Prosini et al. also demonstrated the better circulation of anhydrate.

因此，本發明目的係提供一種磷酸鐵，其比當前技術有所改良且可容易而便宜地取得，可藉由電化學或化學鋰化作用轉化成用於鋰離子蓄電池之陰極材料，或藉由在低溫下熱後處理並短時間煅燒時間數次而成為具有比當前技術改良之性質的磷酸鋰鐵。 Accordingly, it is an object of the present invention to provide an iron phosphate which is improved over the prior art and which can be easily and inexpensively obtained, which can be converted into a cathode material for a lithium ion secondary battery by electrochemical or chemical lithiation, or by The post-heat treatment at a low temperature and a short-time calcination time are several times to become lithium iron phosphate having properties improved by the prior art.

圖1顯示根據當前技術所製造之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)二水合物(FePO4×2H2O)之電子顯微鏡影像(倍率為33570倍)， 圖2顯示如圖1所示的根據當前技術所製造之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)二水合物(FePO4×2H2O)之X射線繞射圖，圖3顯示藉由將如圖1所示之正磷酸鐵(III)二水合物(FePO4×2H2O)加熱至200℃所製造的非晶形正磷酸鐵(III)無水物之X射線繞射圖，圖4顯示根據當前技術所製造之具有紅磷鐵礦晶體結構的正磷酸鐵(III)二水合物(FePO4×2H2O)的X射線繞射圖及根據PDF卡33-0667和26-1080之峰列表(下圖)，圖5顯示如圖4所示之正磷酸鐵(III)二水合物(FePO4×2H2O)於加熱至200℃後的X射線繞射圖，圖6顯示根據DE 10 2011 003 125所製造之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構且具有板形原粒子形態的正磷酸鐵(III)二水合物(FePO4×2H2O)-碳複合物(FOP/C)之黏聚物的電子顯微鏡影像(上圖倍率為3730倍，下圖倍率為2130倍)，圖7顯示藉由將圖6所示之FOP/C產物加熱至200℃所製造的非晶形正磷酸鐵(III)無水物-碳複合物(FOP/C)之電子顯微鏡影像(上圖倍率為1350倍，下圖倍率為6270倍)，圖8顯示根據本發明藉由將圖7所示之正磷酸鐵(III)無水物-碳複合物(FOP/C)分散於水中，添加LiOH、乙酸及抗壞血酸，以及在110℃乾燥所製造的非晶 形正磷酸鋰鐵(III)-碳複合物(LFP/C)之電子顯微鏡影像(倍率為25260倍)，圖9顯示根據本發明藉由將圖7所示之正磷酸鐵(III)無水物-碳複合物(FOP/C)分散於水中，添加LiOH、乙酸及抗壞血酸，以及在200℃乾燥所製造的非晶形正磷酸鋰鐵(III)-碳複合物(LFP/C)之電子顯微鏡影像(倍率為11380倍)，圖10顯示從經鋰化之正磷酸鐵(III)-碳複合物的製造方法之不同階段獲得的材料之X射線繞射圖，其中：繞射圖1)顯示沉澱、脫水及在100℃下乾燥之具有磷菱鐵礦晶體結構的正磷酸鐵(III)-碳複合物(FOP/C)，繞射圖2)顯示本發明藉由將繞射圖1)之物質加熱至200℃所製造的非晶形Fe(III)PO4無水物-碳複合物，繞射圖3)顯示根據本發明在繞射圖2)之物質分散於水中及添加LiOH、乙酸及抗壞血酸之後，以及在110℃乾燥之後(如圖8所示)所製造的非晶形Fe(III)PO4無水物-碳複合物，繞射圖4)顯示根據本發明在繞射圖3)之物質於200℃下進一步乾燥之後(如圖9所示)所製造的Fe(III)PO4無水物-碳複合物，以及繞射圖5)顯示本發明藉由將繞射圖3)之物質在550℃煅燒之後所製造的經鋰化之Fe(III)PO4無水物-碳複合物， 圖11顯示根據本發明於N2氣氛中在550℃下煅燒所製造的正磷酸鋰鐵(III)(LFP)之電子顯微鏡影像(倍率為27080倍)，圖12顯示根據本發明於700℃煅燒所製造之正磷酸鋰鐵(III)(LFP)的電子顯微鏡影像(倍率為5840倍)，圖13顯示根據本發明在500℃於N2/H2氣氛煅燒中所製造之正磷酸鋰鐵(III)(LFP)的X射線繞射圖(上圖)，及根據PDF卡83-2092之峰列表(下圖)，圖14顯示根據本發明在550℃於N2氣氛煅燒中所製造之正磷酸鋰鐵(III)-碳複合物(LFP/C)的X射線繞射圖，及根據PDF卡40-1499及12-0212之峰列表(下圖)，圖15顯示根據本發明在700℃於N2氣氛煅燒中所製造之正磷酸鋰鐵(III)-碳複合物(LFP/C)的X射線繞射圖，及根據PDF卡81-1173及08-0415之峰列表(下圖)，圖16顯示根據對照實例於乙醇中在550℃於N2/H2氣氛中煅燒所製造之正磷酸鋰鐵(III)(LFP)的X射線繞射圖，及根據PDF卡81-1173及08-0415之峰列表(下圖)，以及圖17顯示根據對照實例於乙醇中在550℃於N2氣氛中煅燒所製造之正磷酸鋰鐵(III)無水物(LFP)的X射線繞射圖，及根據PDF卡40-1499及76-1762之峰列表 (下圖)。 1 shows an electron microscope image of iron (III) orthophosphate dihydrate (FePO 4 × 2H 2 O) having a crystal structure of a phosphate iron ore (metastrengite II) manufactured according to the prior art (magnification) Fig. 2 shows iron(III) orthophosphate dihydrate (FePO 4 ) having a crystal structure of a phosphate iron ore (metastrengite II) according to the prior art as shown in Fig. 1. X-ray diffraction pattern of ×2H 2 O), and Figure 3 shows an amorphous shape produced by heating iron (III) orthophosphate dihydrate (FePO 4 × 2H 2 O) as shown in Fig. 1 to 200 ° C X-ray diffraction pattern of iron (III) orthophosphate anhydrate, and FIG. 4 shows iron(III) orthophosphate dihydrate (FePO 4 × 2H 2 O) having a red pyrite crystal structure according to the prior art. X-ray diffraction pattern and peak list according to PDF cards 33-0667 and 26-1080 (below), Figure 5 shows iron(III) orthophosphate dihydrate (FePO 4 × 2H 2 O) as shown in Figure 4. X-ray diffraction pattern after heating to 200 ° C, FIG. 6 shows a crystal structure having a phosphorus siderite (metastrengite II) manufactured according to DE 10 2011 003 125 and having the shape of a plate-shaped original particle Iron (III) phosphate dihydrate (FePO 4 × 2H 2 O) - sticky prepolymer electron microscope image of the carbon composite (FOP / C) of (3730-fold magnification of the FIG., 2130 times magnification of the FIG.), FIG. 7 shows an electron microscope image of an amorphous iron(III) anhydrate-carbon complex (FOP/C) produced by heating the FOP/C product shown in Fig. 6 to 200 ° C (the upper magnification is 1350). The magnification of the lower image is 6270 times. FIG. 8 shows the addition of LiOH, acetic acid and the like by dispersing the iron(III) orthophosphate-carbon complex (FOP/C) shown in FIG. 7 in water according to the present invention. Ascorbic acid, and an electron microscopic image of an amorphous lithium iron (III)-carbonate orthophosphate (LFP/C) produced by drying at 110 ° C (25260 times magnification), Figure 9 shows Figure 7 in accordance with the present invention. The iron(III) anhydrate-carbon complex (FOP/C) shown is dispersed in water, added with LiOH, acetic acid and ascorbic acid, and amorphous lithium iron orthophosphate (III)-carbon produced by drying at 200 ° C Electron microscopic image of the composite (LFP/C) (11380 times magnification), Figure 10 shows the different stages of the method of manufacturing the lithiated iron(III) orthophosphate-carbon composite. X-ray diffraction pattern of the material, wherein: diffraction pattern 1) shows precipitation, dehydration and drying of iron (III)-carbon complex (FOP/C) having a crystal structure of phosphate iron ore at 100 ° C, Diffraction Figure 2) shows the amorphous Fe(III)PO 4 anhydrate-carbon composite produced by heating the material of Figure 1) to 200 ° C, and the diffraction pattern 3) is shown in accordance with the present invention. An amorphous Fe(III)PO 4 anhydrate-carbon composite produced by diffracting the material of Figure 2) after dispersing it in water and adding LiOH, acetic acid and ascorbic acid, and after drying at 110 ° C (as shown in Figure 8), Diffraction Figure 4) shows the Fe(III)PO 4 anhydrate-carbon composite produced by diffracting the material of Figure 3) after further drying at 200 ° C (as shown in Figure 9), and diffraction Figure 5) shows the lithiated Fe(III)PO 4 anhydrate-carbon composite produced by the present invention after calcining the material of Figure 3) at 550 ° C, Figure 11 shows the N2 atmosphere according to the present invention. An electron microscope image (magnification: 27080 times) of lithium iron orthophosphate (LFP) produced by calcination at 550 ° C, and FIG. 12 shows the positive production by calcination at 700 ° C according to the present invention. Electron microscopic image of lithium iron (III) (LFP) (magnification: 5840 times), and Figure 13 shows lithium iron orthophosphate (III) (LFP) produced by calcination at 500 ° C in N 2 /H 2 atmosphere according to the present invention. X-ray diffraction pattern (top), and according to the peak list of PDF cards 83-2092 (bottom), Figure 14 shows lithium iron orthophosphate (III) produced by calcination at 550 ° C in N2 atmosphere according to the present invention - X-ray diffraction pattern of carbon composite (LFP/C), and according to the peak list of PDF cards 40-1499 and 12-0212 (lower figure), Figure 15 shows the manufacture according to the invention in 700 ° C calcination in N2 atmosphere X-ray diffraction pattern of lithium iron orthophosphate (III)-carbon composite (LFP/C), and according to the peak list of PDF cards 81-1173 and 08-0415 (bottom), Figure 16 shows according to the comparative example X-ray diffraction pattern of lithium iron orthophosphate (III) (LFP) produced by calcination in ethanol at 550 ° C in N 2 /H 2 atmosphere, and the peak list according to PDF cards 81-1173 and 08-0415 (below) And FIG. 17 shows an X-ray diffraction pattern of lithium iron (III) orthophosphate (LFP) produced by calcination in ethanol at 550 ° C according to a comparative example, and according to PDF cards 40-1499 and 76 -1762 peak list (below).

發明說明 Description of the invention

本發明關於一種用於製造非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物的方法，其特徵在於通式FePO4×2H2O之正磷酸鐵(III)或通式FePO4×2H2O之正磷酸鐵(III)的碳複合物(其中根據使用CuKα輻射之粉末X射線繞射分析，磷菱鐵礦(phosphosiderite)(磷菱鐵礦(metastrengite)II)晶體結構中存在至少80重量%的該正磷酸鐵(III))係在介於140與250℃之範圍內的溫度下脫水至殘餘水含量介於0與1重量%之間(包括結晶之結合水以及自由水二者)，以及至結晶水含量0.2H2O。 The invention relates to a process for producing an amorphous or amorphous iron(III) phosphate anhydrate or an amorphous or amorphous iron(III) phosphate anhydrate carbon composite characterized by the general formula FePO 4 ×2H 2 O iron complex of iron (III) or iron (III) orthophosphate of the general formula FePO 4 × 2H 2 O (wherein according to powder X-ray diffraction analysis using CuKα radiation, phosphorus siderite ( Phosphosiderite) (at least 80% by weight of the iron(III) orthophosphate) in the crystal structure of the phosphosiderite II is dehydrated to a residual water content at a temperature in the range of 140 and 250 °C. Between 0 and 1% by weight (both crystalline water and free water), and to the water content of crystal water 0.2H 2 O.

根據使用CuKα輻射之粉末X射線繞射分析，在脫水操作之前，該磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構中較佳地存在至少90重量%，特佳係至少95重量%，又更佳係至少99重量%之該磷酸鐵(III)。 According to powder X-ray diffraction analysis using CuKα radiation, preferably at least 90% by weight, particularly preferably at least 95% by weight, of the pyrite (metastrengite II) crystal structure prior to the dehydration operation More preferably, at least 99% by weight of the iron (III) phosphate.

本發明另外關於非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物，其係或可根據本發明所述之方法製造。 The invention further relates to an amorphous or amorphous iron(III) phosphate anhydrate or a carbonaceous composite of an amorphous or amorphous iron(III) phosphate anhydrate, which may or may be made according to the process of the invention .

在本發明一實施態樣中，該非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物在基於CuKα輻射的粉末X射線繞射圖中 於2θ度為15.9±0.5、20.0±0.5、20.95±0.5、22.4±0.5及28.85±0.5處具有峰。 In an embodiment of the invention, the amorphous or amorphous iron(III) phosphate anhydrate or the amorphous or amorphous iron(III) phosphate anhydrate carbon composite is in powder X-ray based on CuKα radiation. Diffraction pattern There are peaks at 2θ degrees of 15.9±0.5, 20.0±0.5, 20.95±0.5, 22.4±0.5, and 28.85±0.5.

藉由本發明方法可避免本文所述之當前技術的缺點。該方法中所使用之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的結晶正磷酸鐵(III)或正磷酸鐵(III)之碳複合物已可以大技術規模獲得。該等材料可藉由DE 10 2007 049 757、DE 10 2009 001 204及DE 10 2011 003 125中所述之簡單方法的特別便宜及環保方式製造。 The disadvantages of the prior art described herein can be avoided by the method of the present invention. The carbon complex of crystalline iron orthophosphate (III) or iron orthophosphate (III) having a crystal structure of a phosphate ore (metastrengite II) used in the method can be obtained on a large scale. These materials can be produced in a particularly inexpensive and environmentally friendly manner by the simple method described in DE 10 2007 049 757, DE 10 2009 001 204 and DE 10 2011 003 125.

令人意外地發現，根據本發明所使用之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的結晶前驅物可藉由簡單加熱至介於140與250℃之範圍內的溫度下脫水至殘餘水含量介於0與1重量%之間(包括結晶之結合水以及自由水二者)。殘餘水含量為至多0.5重量%尤佳。特別是在是為二水合物之磷菱鐵礦中結合的結晶水實質上完全去除。在此簡單脫水操作中，該磷菱鐵礦完全或幾乎完全失去其原有結晶特徵，產生非晶形或非晶形化的磷酸鐵(III)。 Surprisingly, it has been found that the crystalline precursor having the crystal structure of the phosphate iron ore (metastrengite II) used in accordance with the present invention can be simply heated to a temperature in the range of 140 and 250 ° C. Dewatering to a residual water content between 0 and 1% by weight (including both crystalline combined water and free water). It is especially preferred that the residual water content is at most 0.5% by weight. In particular, the crystal water bound in the phosphate siderite which is a dihydrate is substantially completely removed. In this simple dehydration operation, the phosphate siderite completely or almost completely loses its original crystalline character, producing amorphous or amorphous iron (III) phosphate.

關於本發明之「非晶形化的」磷酸鐵(III)無水物一詞表示於粉末X射線繞射分析中不再展現尖銳峰(其為主要是結晶材料之特徵)，但至多展現相對低且分布廣之峰(對熟悉本技術之人士而言，此顯示該材料主要為非晶形)的磷酸鐵(III)無水物。根據本發明非晶形化的正磷酸鐵(III)無水物之此粉末X射線繞射圖的實例係示於 圖3，而根據本發明非晶形化的正磷酸鐵(III)無水物碳複合物係示於圖10，光譜2。完全非晶形材料在粉末X射線繞射圖中不展現任何峰，如本發明產物在進行化學鋰化之後所觀察到之情況(見圖10，繞射圖3，但無石墨所造成的反射)。 The term "amorphous" iron (III) phosphate anhydrate as used in the present invention means that in powder X-ray diffraction analysis no longer exhibits sharp peaks (which are predominantly characteristic of crystalline materials), but at most exhibits relatively low and An iron (III) phosphate anhydrate that is widely distributed (for those skilled in the art, this material is predominantly amorphous). An example of such a powder X-ray diffraction pattern of an amorphous iron (III) orthophosphate anhydrate according to the present invention is shown in Figure 3, while the amorphous iron(III) orthophosphate carbon complex according to the present invention is shown in Figure 10, spectrum 2. The completely amorphous material does not exhibit any peaks in the powder X-ray diffraction pattern, as observed by the product of the invention after chemical lithiation (see Figure 10, diffraction pattern 3, but no reflection by graphite) .

該結晶起始材料磷菱鐵礦在粉末X射線繞射圖中在基於CuKα輻射於2θ度為13.68±0.05、18.18±0.05、24.75+0.05、32.25±0.05、32.35±0.05、34.94±0.05、35.22±0.05、42.80±0.05及45.16±0.05處具有峰之粉末X射線繞射圖中展現特徵反射。在本發明之非晶形化的磷酸鐵(III)無水物之粉末圖中無法辨識該等為磷菱鐵礦之特徵的反射。基於CuKα輻射，只有一些非常不明顯且極廣的反射發生在2θ度為15.9±0.5、20.0±0.5、20.95±0.5、22.4±0.5及28.85±0.5處。由於極端之反射寬度及低強度，無法將已知結構明確歸類於僅微弱可識別反射。該X射線繞射圖中之非晶形化的產物仍可偵測到反射的原因之一可為些微比例之紅磷鐵礦，該紅磷鐵礦留在本發明產物中且因其低強度及輕微的結晶標記性而無法在起始材料之粉末繞射圖中偵測到(見圖10光譜1及2)。因此，本發明係指「非晶形化的磷酸鐵(III)無水物」。 The crystallization starting material of the metallite is in the powder X-ray diffraction pattern at the 2θ degree of 13.68±0.05, 18.18±0.05, 24.75+0.05, 32.25±0.05, 32.35±0.05, 34.94±0.05, 35.22 based on CuKα radiation. Characteristic reflections were exhibited in powder X-ray diffraction patterns with peaks at ±0.05, 42.80±0.05 and 45.16±0.05. These reflections, which are characteristic of the pyrite, are not recognized in the powder map of the amorphous iron(III) phosphate anhydrate of the present invention. Based on CuKα radiation, only some very inconspicuous and extremely broad reflections occur at 2θ degrees of 15.9±0.5, 20.0±0.5, 20.95±0.5, 22.4±0.5, and 28.85±0.5. Due to the extreme reflection width and low intensity, known structures cannot be clearly classified as weakly identifiable reflections. One of the reasons why the amorphous product in the X-ray diffraction pattern can still detect reflection may be a slight proportion of red iron phosphate, which remains in the product of the invention due to its low strength and Slightly crystalline and not detectable in the powder diffraction pattern of the starting material (see spectra 1 and 2 of Figure 10). Therefore, the present invention means "amorphous iron (III) phosphate anhydrate".

從所使用之前驅物製造本發明非晶形化的磷酸鐵(III)無水物係令人意外的，原因係作者們根據文獻(Reale等人，Chem.Mater.2003，15，第5051-5058頁)描述之研究製造的磷菱鐵礦係在140℃之溫度下轉化 成FePO4的無水單斜同素異形體，作者們將其稱為FePO4 II相，且其晶體結構係明確歸類。作者們另外描述所得之Fe-O-P結構單元相對於原始磷菱鐵礦幾乎保持不受影響，但晶胞體積縮小約27%。該相在高達550℃之溫度仍保持安定，從550℃起開始形成與α-石英惹似的FePO4相。 The manufacture of the amorphous iron(III) phosphate anhydrate of the present invention from the precursors used is surprising, for the reasons of the authors according to the literature (Reale et al., Chem. Mater. 2003, 15, pp. 5051-5058). The described pyriterite produced by the study was converted to an anhydrous monoclinic allotrope of FePO 4 at a temperature of 140 ° C, which the authors refer to as the FePO 4 II phase, and whose crystal structure is clearly classified. The authors additionally describe that the resulting Fe-OP structural unit remains almost unaffected relative to the original pyrite, but the unit cell volume is reduced by approximately 27%. The phase remains stable at temperatures up to 550 ° C, and begins to form a FePO 4 phase that is similar to α-quartz from 550 ° C.

根據本發明所使用之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)(其可根據DE 10 2007 049 757、DE 10 2009 001 204及DE 10 2011 003 125之方法製造)因而在熱脫水表現及相形成方面與Reale等人所研究的材料明顯不同。根據本發明所使用之磷菱鐵礦的原粒子之形態(見圖6)在脫水操作中不改變(見圖7)。 Iron(III) orthophosphate having a crystal structure of a phosphate iron ore (metastrengite II) according to the invention, which can be used according to DE 10 2007 049 757, DE 10 2009 001 204 and DE 10 2011 003 The method of 125) is thus significantly different from the materials studied by Reale et al. in terms of thermal dehydration performance and phase formation. The morphology of the primary particles of the phosphate siderite used in accordance with the present invention (see Figure 6) does not change during the dehydration operation (see Figure 7).

本發明之非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物之實質優點係可經由結晶磷菱鐵礦之初步階段明確且完整地表示關於該非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物的化學計量之特徵。此非如此處之文獻中所述的無法表示在任一刻所界定之化合物特徵的非晶形FePO4水合物之情況。可存在形成不想要的次相所造成之化學計量偏差，例如不同結晶水含量，該結晶水含量係描述於文獻中且在經進一步處理及後來用作陰極材料時對於該陰極材料的電力具有負面影響。 The substantial advantage of the amorphous or amorphous iron (III) phosphate anhydrate of the present invention or its carbon composite is that the amorphous or amorphous phosphoric acid can be clearly and completely expressed via the preliminary stage of crystalline phosphonite. The stoichiometric characteristics of iron (III) anhydrate or its carbon complex. This is not the case for the amorphous FePO 4 hydrate which does not represent the characteristics of the compound defined at any one time as described in the literature herein. There may be stoichiometric deviations caused by the formation of unwanted secondary phases, such as different crystallized water contents, which are described in the literature and which have a negative effect on the electrical power of the cathode material when further processed and later used as a cathode material. influences.

本發明之另一優點係本發明之非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物及其起始化合物可以大技 術規模便宜且兼顧生態地製造。 Another advantage of the present invention is that the amorphous or amorphous iron (III) phosphate anhydrate of the present invention or a carbon composite thereof and a starting compound thereof can be The scale of the operation is cheap and ecologically.

本發明之另一優點係當本發明之非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物的碳含量相對低時仍保留其導電性。不需要以碳隨後塗覆該非晶形化的材料。 Another advantage of the present invention is that the carbon composite of the amorphous or amorphous iron (III) phosphate anhydrate of the present invention retains its conductivity when it has a relatively low carbon content. It is not necessary to subsequently coat the amorphized material with carbon.

本發明之非晶形化的磷酸鐵(III)無水物或其碳複合物亦已可藉由選擇較高乾燥溫度而在製造期間無任何問題地獲得，且可直接引入本文所述用以製造LFP及LFP/C之製程。迄今僅已知呈結晶形式的碳複合物。 The amorphous iron(III) phosphate anhydrate of the present invention or a carbon composite thereof can also be obtained without any problem during the manufacturing process by selecting a higher drying temperature, and can be directly incorporated into the production of LFP as described herein. And the process of LFP/C. To date only carbon composites in crystalline form have been known.

本發明之非晶形或非晶形化的磷酸鐵(III)無水物之另一優點係該材料可經化學或電化學鋰化。反之，已知之結晶材料僅能熱鋰化，該熱鋰化需要高溫且涉及如不想要的結晶生長及原粒子燒結等已知問題。 Another advantage of the amorphous or amorphous iron (III) phosphate anhydrate of the present invention is that the material can be chemically or electrochemically lithiated. Conversely, known crystalline materials are only capable of thermal lithiation, which requires high temperatures and involves known problems such as unwanted crystal growth and sintering of the original particles.

已進行研究以發現本發明之非晶形或非晶形化的磷酸鐵(III)無水物是否可藉由電化學鋰化而直接用於半電池作為相對於鋰陽極或使用含鋰電解質之陰極材料。在該情況下，最初材料部分上未公認發現特殊活性，但該材料可無任何問題地經電化學鋰化及脫鋰。在該情況下，本發明之非晶形或非晶形化的磷酸鐵(III)無水物展現隨著循環次數增加而提高的電容率。 Studies have been conducted to find out whether the amorphous or amorphous iron(III) phosphate anhydrate of the present invention can be directly used in a half cell as a cathode material with respect to a lithium anode or a lithium-containing electrolyte by electrochemical lithiation. In this case, it is not recognized that a special activity is found on the initial material portion, but the material can be electrochemically lithiated and delithiated without any problem. In this case, the amorphous or amorphous iron(III) phosphate anhydrate of the present invention exhibits an increased permittivity as the number of cycles increases.

本發明之非晶形或非晶形化的磷酸鐵(III)無水物在鋰化操作中相較於結晶材料的優點據推測係基於該等材料的結構差異。在鋰化步驟中，鐵(III)係轉化成鐵(II)，且鋰離子沉降以使該結構中之腔中的電荷均衡。本發明之非晶形或非晶形化的材料為介穩的，且據推測已 具有鋰離子可相對容易移入之所需的腔。在結晶材料之情況下，該等所需之腔最初不存在或被結晶水佔據。熱重建只在高溫下發生，藉由該熱重建產生供鋰離子沉降所需的腔。此係本發明之新穎非晶形或非晶形化的磷酸鐵(III)無水物可進行根據先前技術之對應結晶材料無法實施的直接電化學或化學鋰化之推測原因。該結晶材料只能熱鋰化。 The advantages of the amorphous or amorphous iron (III) phosphate anhydrate of the present invention over the crystalline material in the lithiation operation are presumably based on structural differences of the materials. In the lithiation step, iron (III) is converted to iron (II) and lithium ions are settled to equalize the charge in the cavity in the structure. The amorphous or amorphous material of the present invention is metastable and is presumably It has the required cavity for lithium ions to move relatively easily. In the case of crystalline materials, such desired cavities are initially absent or occupied by crystallized water. Thermal reconstruction occurs only at high temperatures, and this thermal reconstruction produces a cavity for the deposition of lithium ions. The novel amorphous or amorphous iron(III) phosphate anhydrate of the present invention can be speculated for direct electrochemical or chemical lithiation that cannot be performed according to the corresponding crystalline materials of the prior art. The crystalline material can only be thermally lithiated.

當關於本發明提及殘留水含量時，此包括結晶之組合水以及自由水或自由水分或殘留水分。相較之下，結晶水含量只表示表示結晶之結合水。根據本發明，以判定在800℃下加熱10分鐘之該材料的燒失來確定殘留水含量。該熱處理之前及之後的重量差表示燒失，因此為本發明之殘留水含量。 When reference is made to the residual water content of the present invention, this includes combined water of crystallization as well as free water or free or residual moisture. In contrast, the water content of crystallization represents only the bound water which represents crystallization. According to the present invention, the residual water content is determined by determining the loss of ignition of the material heated at 800 ° C for 10 minutes. The difference in weight before and after the heat treatment indicates loss of ignition, and thus is the residual water content of the present invention.

如所述，本發明之新穎非晶形或非晶形化的磷酸鐵(III)無水物可直接用作鋰離子蓄電池之陰極材料。然而，或者該材料亦可經化學鋰化，然後可直接用作陰極材料，或其可在藉由煅燒轉化成結晶材料之後用作陰極材料。 As described, the novel amorphous or amorphous iron(III) phosphate anhydrate of the present invention can be directly used as a cathode material for a lithium ion secondary battery. However, either the material may be chemically lithiated and then used directly as a cathode material, or it may be used as a cathode material after being converted into a crystalline material by calcination.

因此，本發明另外提供一種用於製造經化學鋰化之正磷酸鐵或正磷酸鐵碳複合物的方法，其中a)通式FePO4×2H2O之正磷酸鐵(III)或通式FePO4×2H2O之正磷酸鐵(III)的碳複合物(其中根據使用CuKα輻射之粉末X射線繞射分析，磷菱鐵礦(phosphosiderite)(磷菱鐵礦(metastrengite)II)晶體 結構中存在至少80重量%的該正磷酸鐵(III))係介於在140與250℃之範圍內的溫度下脫水至殘餘水含量介於0與1重量%之間(包括結晶之結合水以及自由水二者)，以及至結晶水含量0.2H2O，b)將該脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物分散在水或水性溶劑中，且於該分散液中添加介於0.8與1.2莫耳當量之鋰鹽，或該脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物係分散在含有介於0.8與1.2莫耳當量之呈溶解形式的鋰鹽之水或水性溶劑中，其中莫耳當量係關於該分散液中之鐵(III)及該鋰鹽中之鋰(I)離子的莫耳量，c)該水性分散液係與介於0.9與1.2電子當量之還原酮反應，其中還原酮之電子當量意指用以將該分散液中之鐵(III)還原成鐵(II)所需的還原酮之量，及d)所獲得之反應產物係在介於100與300℃範圍內之溫度及/或在低於大氣壓力之減壓下予以乾燥。 Accordingly, the present invention further provides a process for producing a chemically lithiated iron orthophosphate or iron orthophosphate complex, wherein a) iron (III) orthophosphate of the formula FePO 4 × 2H 2 O or a general formula FePO 4 × 2H 2 O carbon complex of iron (III) orthophosphate (in which the powder X-ray diffraction analysis using CuKα radiation, in the crystal structure of phosphosiderite (metastrengite II) There is at least 80% by weight of the iron (III) orthophosphate) dehydrated at a temperature in the range of 140 and 250 ° C to a residual water content of between 0 and 1% by weight (including crystalline bound water and free Both water) and to the water content of crystal water 0.2H 2 O, b) dispersing the dehydrated iron complex of iron (III) or the iron (III) phosphate in water or an aqueous solvent, and adding 0.8 and 1.2 molar equivalents to the dispersion a lithium salt, or the dehydrated iron complex of the iron (III) phosphate or the iron (III) phosphate, is dispersed in water or an aqueous solvent containing a lithium salt in a dissolved form of between 0.8 and 1.2 moles, Wherein the molar equivalent is about the amount of iron (III) in the dispersion and the amount of lithium (I) ions in the lithium salt, c) the aqueous dispersion reacts with a reducing ketone of between 0.9 and 1.2 electron equivalents Wherein the electron equivalent of the reduced ketone means the amount of reducing ketone required to reduce iron (III) in the dispersion to iron (II), and d) the reaction product obtained is between 100 and 300 Dry at temperatures in the range of °C and/or under reduced pressure below atmospheric pressure.

根據粉末X射線繞射分析，在脫水步驟之前，該磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構中較佳地存在至少90重量%，特佳係至少95重量%，又更佳係至少99重量%之該磷酸鐵(III)。 According to the powder X-ray diffraction analysis, preferably at least 90% by weight, particularly preferably at least 95% by weight, in the crystal structure of the phosphorus siderite (metastrengite II) before the dehydration step, Preferably at least 99% by weight of the iron (III) phosphate.

由於其特別性質，可從藉由脫水所獲得的本發明之非晶形化的磷酸鐵(III)無水物製造細微水性分散液，其中在作為基質的水中簡單攪拌固態材料即完足夠，不需添加添加劑。將認可熟悉本技術之人士已知各種技術(諸如使 用濕式碾磨機、Ultraturrax、超音波等)以及添加表面活性物質對於分散液形成的速度及品質有正面影響。然而，當使用表面活性物質時，應注意的是未引入隨後會對電池組應用造成負面影響的離子污染。該分散液之固體濃度較佳係在介於40與60重量%範圍內。 Due to its special properties, a fine aqueous dispersion can be produced from the amorphous iron(III) phosphate of the present invention obtained by dehydration, wherein simply stirring the solid material in the water as a substrate is sufficient, and no need to add additive. Various techniques known to those skilled in the art will be recognized (such as The use of wet mills, Ultraturrax, ultrasonic waves, etc., and the addition of surface active materials have a positive effect on the speed and quality of dispersion formation. However, when using surface active materials, it should be noted that ionic contamination that subsequently adversely affects the battery pack application is not introduced. The solids concentration of the dispersion is preferably in the range of 40 and 60% by weight.

於本發明方法之步驟c)中，使用一或多種還原酮將鐵(III)還原成鐵(II)。還原酮係C=C雙鍵的兩個碳原子攜有兩個羥基(「烯二醇」)且另外具有直接位在該相鄰碳原子之羰基的有機化合物。該等烯二醇之雙鍵係藉由與該羰基共軛而安定化；因此，在互變異構平衡(「酮-烯醇互變異構機制」)中，主要存在烯二醇形式而非酮形式。作為插烯物(vinylogue)羧酸，還原酮涉及酸反應。彼等具有強還原效果。 In step c) of the process of the invention, iron (III) is reduced to iron (II) using one or more reducing ketones. The two carbon atoms of the ketone-based C=C double bond carry two hydroxyl groups ("olefinic diols") and additionally have organic compounds directly adjacent to the carbonyl groups of the adjacent carbon atoms. The double bonds of the olefinic diols are stabilized by conjugated with the carbonyl group; therefore, in the tautomeric equilibrium ("keto-enol tautomerism mechanism"), the olefinic diol form is predominantly present rather than a ketone form. As a vinylogue carboxylic acid, the reducing ketone involves an acid reaction. They have a strong reduction effect.

在這方面，還原酮之電子當量表示還原一莫耳鐵(III)所需之還原酮的量。若一莫耳還原酮例如提供兩個用於還原操作之原子(例如抗壞血酸)，則還原一莫耳鐵(III)之一電子當量對應於半莫耳還原酮。 In this regard, the electron equivalent of the reduced ketone represents the amount of reducing ketone required to reduce one mole of iron (III). If a molar reducing ketone, for example, provides two atoms for the reduction operation (e.g., ascorbic acid), then one of the electron equivalents of one mole of iron (III) is reduced to correspond to the half molar reducing ketone.

在將Fe(III)還原成Fe(II)中，在磷酸鐵(III)無水物之情況下，該混合物之色彩立刻從白-偏黃色變成黑色，而在磷酸鐵(III)無水物之碳複合物的情況下係從灰色變成黑色。同時，該有機還原劑而非替其氧化分解程序中之中間物發生氧化。 In the reduction of Fe(III) to Fe(II), in the case of an iron (III) phosphate anhydrate, the color of the mixture immediately changes from white to yellow to black, while in the iron of iron (III) anhydrate In the case of a composite, it turns from gray to black. At the same time, the organic reducing agent is not oxidized by the intermediate in its oxidative decomposition process.

先前分散的本發明之非晶形化的磷酸鐵(III)無水物於該還原操作中依原粒子基礎再次分成更小單元，其尤其 係由所獲得之固體比例無法藉由一般過濾方法或藉由超速離心予以分離或沉積來顯示。 The previously dispersed amorphous form of iron (III) phosphate of the present invention is again subdivided into smaller units in the reduction operation based on the original particle basis, which is especially The ratio of solids obtained can not be shown by conventional filtration methods or by ultracentrifugation separation or deposition.

為此，藉由在高溫下及/或在減壓下移除水來乾燥整體混合物。在該情況下，於乾燥操作期間永久混合(permanent mixing)有利於不產生該混合物之可能溶解成分的濃度梯度以及確保該經乾燥混合物之最高可能均勻度水準。 To this end, the overall mixture is dried by removing water at elevated temperatures and/or under reduced pressure. In this case, permanent mixing during the drying operation is advantageous in not producing a concentration gradient of the possible dissolved components of the mixture and ensuring the highest possible level of uniformity of the dried mixture.

圖8及9顯示在分散於水中及添加LiOH、乙酸及抗壞血酸，以及在110℃乾燥(圖8)及在200℃(圖9)乾燥之後的根據本發明經鋰化之非晶形Fe(III)PO4無水物碳複合物。 Figures 8 and 9 show the lithiated amorphous Fe(III) according to the present invention after dispersion in water and addition of LiOH, acetic acid and ascorbic acid, and drying at 110 ° C (Figure 8) and drying at 200 ° C (Figure 9). PO4 anhydrate carbon composite.

在該方面，有趣的是，相較於本發明在200℃乾燥之非晶形化的及非經鋰化之磷酸鐵(III)無水物碳複合物(圖10，繞射圖2)，在110℃乾燥的經鋰化之產物的X射線繞射圖顯示完全平坦曲線(圖10，繞射圖3)。然而，若該經鋰化之產物係在200℃乾燥，則已有不同忽視比例之結晶LFP/C(圖10，光譜4)。此明確顯示該分散之固體中發生Fe3+還原成Fe2+，其中藉由結合來自該分散液之先前溶解的Li+進行電荷均衡。 In this respect, it is interesting to compare the amorphous and non-lithiated iron(III) phosphate anhydrate carbon composite dried at 200 ° C in accordance with the present invention (Fig. 10, diffraction pattern 2), at 110 The X-ray diffraction pattern of the dried lithiated product at °C shows a perfectly flat curve (Fig. 10, diffraction pattern 3). However, if the lithiated product is dried at 200 ° C, there are different neglected ratios of crystalline LFP/C (Figure 10, Spectrum 4). This clearly shows that Fe 3+ is reduced to Fe 2+ in the dispersed solid, wherein charge equalization is carried out by combining previously dissolved Li + from the dispersion.

該混合物之乾燥可在標準大氣及/或保護或氣氛及/或在減壓下選擇性進行。在該方面，通常該混合器的徹底混合較佳係於乾燥操作期間例如在桶式乾燥機中進行，以抵消因一些組分在液相中的溶解性造成的混合物分離程序。以該方法可確保所有組分在該混合物中的均勻分布。因而 可完全抑制因隨意的後續煅燒操作期間該等組分之不均勻分布事件中的濃度梯度而形成次相。根據本發明所製造之經煅燒LFP/C的X射線繞射圖只展現LFP之反射及在LFP實例中不會發生的額外碳反射。 Drying of the mixture can be carried out selectively in a standard atmosphere and/or protection or atmosphere and/or under reduced pressure. In this respect, it is generally preferred that the thorough mixing of the mixer be carried out during a drying operation, such as in a barrel dryer, to counteract the mixture separation procedure due to the solubility of some components in the liquid phase. This method ensures an even distribution of all components in the mixture. thus The formation of a secondary phase can be completely inhibited by concentration gradients in the event of non-uniform distribution of such components during random subsequent calcination operations. The X-ray diffraction pattern of the calcined LFP/C produced in accordance with the present invention exhibits only the reflection of LFP and additional carbon reflection that would not occur in the LFP example.

在標準大氣下之乾燥、較佳使用循環空氣乾燥、於約100℃之較高溫度、介於100與200℃的產物溫度為佳，此涉及先前藉由還原酮所還原之鐵(II)的部分表面氧化。在另一方面，由於氧化分解產物及該還原酮之中間物在該等溫度下為揮發性，以該方法可移除藉由還原酮引入之有機成分部分。若該程序係在真空或比大氣壓力降低之壓力下進行，實質上可防止氧化且亦可在較低溫度下移除有機成分。該程序較佳用於製造具有介於約2與4重量%之範圍的低碳含量之LFP/C。 Drying under standard atmosphere, preferably using circulating air drying, at a higher temperature of about 100 ° C, product temperature between 100 and 200 ° C, which relates to iron (II) previously reduced by reducing ketone Partial surface oxidation. On the other hand, since the oxidative decomposition product and the intermediate of the reduced ketone are volatile at the temperatures, the organic component portion introduced by the reducing ketone can be removed by this method. If the procedure is carried out under vacuum or at a pressure lower than atmospheric pressure, it substantially prevents oxidation and also removes organic components at lower temperatures. This procedure is preferably used to produce LFP/C having a low carbon content ranging from about 2 to 4 weight percent.

於保護性氣氛(例如氮)或在真空下，在介於60與350℃乾燥僅部分去除該等有機成分。因此，在於保護性氣氛下煅燒且在真空下於60℃事先乾燥之樣本中分析到約12重量%之碳含量。 The organic components are only partially removed by drying at 60 and 350 ° C under a protective atmosphere (e.g., nitrogen) or under vacuum. Thus, a carbon content of about 12% by weight was analyzed in a sample which was calcined under a protective atmosphere and previously dried under vacuum at 60 °C.

由於本發明之非晶形化的磷酸鐵(III)無水物可能電化學鋰化及直接用作陰極材料，以及由於分別藉由從煅燒本發明之非晶形化的磷酸鐵(III)無水物所製得之LFP及LFP/C的良好效率，很明顯的結論係經化學鋰化之磷酸鐵(III)可直接用作電化學電池中的陰極材料。使用該文獻中所使用之非晶形磷酸鐵(III)水合物的變體之優點係介於1與1.05莫耳當量鋰陽離子已存在該化合物中，因 此不必經由電解質或經由陽極(通常為金屬鋰箔)提供鋰化必要的鋰。優於藉由煅燒所產生之LFP及/或LFP/C的優點正好可免除煅燒操作。 Since the amorphous iron(III) phosphate anhydrate of the present invention may be electrochemically lithiated and used directly as a cathode material, and as a result of calcination of the amorphous form of iron (III) phosphate of the present invention, respectively. With the good efficiency of LFP and LFP/C, it is obvious that the chemically lithiated iron (III) phosphate can be directly used as a cathode material in electrochemical cells. The advantage of using a variant of the amorphous iron(III) phosphate hydrate used in this document is that between 1 and 1.05 moles of lithium cation are already present in the compound, This does not have to provide the lithium necessary for lithiation via the electrolyte or via the anode (usually a metallic lithium foil). The advantage of LFP and/or LFP/C produced by calcination is just as good as the calcination operation.

在本發明一實施態樣中，本發明之經乾燥的經鋰化之磷酸鐵(III)無水物或其碳複合物係在介於400與800℃範圍內的溫度下煅燒達一介於1與24小時之期間。 In an embodiment of the present invention, the dried lithiated iron(III) phosphate anhydrate of the present invention or a carbon composite thereof is calcined at a temperature ranging from 400 to 800 ° C to a ratio of 1 and During the 24-hour period.

較佳地，該經乾燥產物之煅燒係在介於450與700℃，較佳係介於500與650℃範圍內之溫度進行達介於1與12小時，較佳係介於2與6小時之期間。 Preferably, the calcined product is calcined at a temperature between 450 and 700 ° C, preferably between 500 and 650 ° C for between 1 and 12 hours, preferably between 2 and 6 hours. During the period.

過高之煅燒溫度具有晶體生長及燒結發生程度提高的缺點。過低之煅燒溫度具有非結晶區可能留在產物中及/或有機成分可能留在產物中的程度提高的缺點。有機成分可具有電絕緣效果。 Excessive calcination temperatures have the disadvantage of increasing crystal growth and increasing the degree of sintering. Too low a calcination temperature has the disadvantage that the amorphous region may remain in the product and/or the organic component may remain in the product. The organic component can have an electrical insulating effect.

為了進一步減少藉由煅燒所製造之LFP或LFP/C中的碳含量，可在煅燒操作中設定氧分壓。在該情況下，氧分壓可設為使得Fe2+成為Fe3+之部分氧化係由混合物中之有機組分補償。熟悉本技術之人士已知呈例如烴、碳水化合物、聚合物等或形式或石墨或其他碳改質物之有機添加劑確保在煅燒操作中Fe3+有效率還原成Fe2+。 In order to further reduce the carbon content in the LFP or LFP/C produced by calcination, the oxygen partial pressure can be set in the calcination operation. In this case, the oxygen partial pressure may be set such that the partial oxidation of Fe 2+ to Fe 3+ is compensated by the organic component in the mixture. Known to those skilled in the art of organic form, for example a hydrocarbon, carbohydrate, polymer, or other forms of carbon or graphite or other additives to ensure modified product of the calcining operation in a reducing Fe 3+ to efficiently Fe 2+.

煅燒溫度及滯留時間亦可經選擇以引發純LFP相形成。測試已顯示可在550℃之溫度下獲得純LFP相(見圖4)。亦已發現，煅燒只可能在氮氣氛中進行，亦即，不必使用形成氣體防止氧化及次相形成(見圖13)。X射線繞射圖中明確顯示具有高強度半高寬度之明顯反射，此 指示小粒子。與之相較，於700℃煅燒之反射明顯較尖銳(見圖15)。 The calcination temperature and residence time can also be selected to initiate the formation of a pure LFP phase. The test has been shown to be available at A pure LFP phase was obtained at a temperature of 550 ° C (see Figure 4). It has also been found that calcination can only be carried out in a nitrogen atmosphere, i.e., it is not necessary to use a forming gas to prevent oxidation and secondary phase formation (see Figure 13). The X-ray diffraction pattern clearly shows a significant reflection with a high intensity half-height width, which indicates small particles. In contrast, the reflection at 700 ° C is significantly sharper (see Figure 15).

所得之LFP及其碳複合物LFP/C可具有>80m2/g之比表面積。在較介於600與800℃範圍內之較高煅燒溫度下，因引入之原粒子燒結而導致發生粒子生長。視煅燒期間個別選擇之溫度及混合物的滯留時間而定，可設定目標粒度分布及形態。在該情況下，LFP或LFP/C之比表面積亦縮小，且可以特別針對目標之方式予以影響。 The resulting LFP and its carbon composite LFP/C may have a specific surface area of >80 m 2 /g. At higher calcination temperatures in the range of between 600 and 800 ° C, particle growth occurs due to sintering of the introduced primary particles. The target particle size distribution and morphology can be set depending on the temperature selected individually during the calcination and the residence time of the mixture. In this case, the specific surface area of LFP or LFP/C is also reduced, and it can be influenced particularly in the manner of the target.

由於奈米等級材料之短擴散路徑之故，在不超過550℃煅燒之LFP樣本在快速放電率下呈現良好效率。超過50%該可在C/10下儲存之能量可以20C之放電率(在3分鐘內放電)取用。1C之充電電流意指容量指定為例如2Ah之電池係以2A之充電電流充電1小時，然後含有2Ah之能量。以C/10充電意指該電池係以對應於其容量之充電電流的十分之一充電，然而，其亦持續10倍時間，即，10小時。一般使用該慣用作法能比較電池而不考慮真實容量。以C/10充電在負載測試中很常見，因此造成特別小心且完整的充電。20C之放電率意指放電在1/20小時(即，在3分鐘內)期間發生。具有小比表面積(即較大粒子)之LFP及LFP/C在此種高放電率下無法電化學反應。所有所製造之活性材料均呈現超過30次以0.5C/0.5C充電/放電程序的良好循環性。 Due to the short diffusion path of nanoscale materials, LFP samples calcined at no more than 550 °C exhibited good efficiencies at fast discharge rates. More than 50% of the energy that can be stored at C/10 can be taken at a discharge rate of 20C (discharged within 3 minutes). The charging current of 1C means that the battery whose capacity is specified as, for example, 2 Ah is charged with a charging current of 2 A for 1 hour, and then contains 2 Ah of energy. Charging at C/10 means that the battery is charged at one tenth of the charging current corresponding to its capacity, however, it also lasts 10 times, i.e., 10 hours. This customary method is generally used to compare batteries without considering the true capacity. Charging at C/10 is common in load testing, resulting in a particularly careful and complete charging. A discharge rate of 20C means that the discharge occurs during 1/20 hours (i.e., within 3 minutes). LFP and LFP/C having a small specific surface area (i.e., larger particles) cannot electrochemically react at such a high discharge rate. All of the active materials produced exhibited more than 30 cycles of good cycling with a 0.5 C/0.5 C charge/discharge procedure.

在本發明方法一更佳實施態樣中，在添加該鋰鹽之前及在添加該還原酮之前，該脫水磷酸鐵(III)或該磷酸鐵 (III)之脫水碳複合物的水性分散液之pH值係設定及/或緩衝至7.0，較佳為6.5，尤佳為6.0之值，其中較佳地使用有機羧酸及/或其酐及/或其鋰鹽，特佳地使用甲酸、乙酸、丙酸、正丁酸、戊酸及/或其酐及/或其鋰鹽來設定及/或緩衝該pH值。 In a preferred embodiment of the method of the present invention, the aqueous dispersion of the dehydrated iron (III) or the iron (III) iron dehydrated carbon complex is added before the addition of the lithium salt and before the addition of the reducing ketone. pH is set and / or buffered to 7.0, preferably 6.5, especially good for a value of 6.0, wherein an organic carboxylic acid and/or its anhydride and/or a lithium salt thereof are preferably used, and fortunately, formic acid, acetic acid, propionic acid, n-butyric acid, valeric acid and/or its anhydride and/or The lithium salt is used to set and/or buffer the pH.

若該水性分散液之pH值太高，則於添加鋰鹽期間，特別是可局部導致pH值>7之LiOH(即，該LiOH之滴入位置的局部緩衝作用)不適宜，此情況下，會形成氫氧化鐵或氧化鐵氫氧化物(iron oxide hydroxide)及/或氧化鐵水合物，其不會如所希望反應。 If the pH of the aqueous dispersion is too high, particularly during the addition of the lithium salt, LiOH which locally causes a pH of >7 (i.e., the local buffering effect of the drop position of the LiOH) is not suitable. Iron hydroxide or iron oxide hydroxide and/or iron oxide hydrate may be formed which does not react as desired.

在本發明一更佳實施態樣中，該鋰鹽在水性分散液中之用量介於0.9與1.1，特佳地使用介於1.0與1.05莫耳當量及/或該還原酮之用量介於該水性分散液的1.0與1.05電子當量。 In a further preferred embodiment of the invention, the lithium salt is present in the aqueous dispersion in an amount between 0.9 and 1.1, particularly preferably between 1.0 and 1.05 molar equivalents and/or the amount of the reducing ketone is between The aqueous dispersion was 1.0 and 1.05 electron equivalents.

若使用過於大量之鋰鹽，則在稍後煅燒反應中可能形成不想要的富鋰次相。若使用過於少量之鋰鹽，則在稍後煅燒反應中可能形成不想要的具有低鋰含量之次相。 If an excessively large amount of lithium salt is used, an undesired lithium-rich secondary phase may be formed in a later calcination reaction. If an excessively small amount of lithium salt is used, an undesirable secondary phase having a low lithium content may be formed in a later calcination reaction.

若使用過於大量之還原酮，存在過量還原酮負面地影響反應之其他過程的危險。此外，此係不必要的成本。若使用過於少量之還原酮，存在Fe3+之還原發生不完全，因此所結合的鋰離子非化學計量之量的風險。 If too much of the reducing ketone is used, there is a risk that excess reducing ketone negatively affects other processes of the reaction. In addition, this is an unnecessary cost. If too small a reducing ketone is used, there is a risk that the reduction of Fe 3+ is incomplete and therefore the amount of lithium ions incorporated is not stoichiometric.

在本發明一更佳實施態樣中，水性分散液中之鋰鹽係選自由以下所組成之群組：氫氧化鋰(LiOH)、碳酸鋰(Li2CO3)、乙酸鋰、甲酸鋰及其混合物。 In a further preferred embodiment of the present invention, the lithium salt in the aqueous dispersion is selected from the group consisting of lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium acetate, lithium formate, and Its mixture.

使用該等鋰鹽具有不會因鋰鹽而將麻煩的陰離子污染(例如硫酸鹽離子或硝酸鹽離子)引入最終產物的優點。諸如乙酸鹽之有機陰離子在後續煅燒程序中被氧化及/或排出。 The use of such lithium salts has the advantage of not introducing cumbersome anionic contamination (e.g., sulfate ions or nitrate ions) into the final product due to the lithium salt. Organic anions such as acetate are oxidized and/or vented in subsequent calcination procedures.

在本發明一更佳實施態樣中，還原酮係選自由以下所組成之群組：羥基丙二醛(tartronaldehyde)(羥基丙二醛(hydroxypropandial))、抗壞血酸、還原酸(2,3-二羥基-2-環戊烯酮)、乙醯基福滿(acetylformoin)及上述者之混合物，其中該還原酮較佳為抗壞血酸。 In a further preferred embodiment of the invention, the reducing ketone is selected from the group consisting of tartronaldehyde (hydroxypropandial), ascorbic acid, reducing acid (2,3-di) Hydroxy-2-cyclopentenone), acetylformoin, and mixtures thereof, wherein the reducing ketone is preferably ascorbic acid.

根據本發明之上述還原酮用以將鐵(III)還原成鐵(II)的用途優於其他已知還原劑的優點係該等還原酮特別是與醇相較下與作為反應基質之水相容以及具有高溶解性水準。 The use of the above-mentioned reduced ketone according to the present invention for reducing iron (III) to iron (II) is superior to other known reducing agents in that the reducing ketone is in particular compared with an alcohol and a water phase as a reaction substrate. Capacity and high solubility level.

在本發明一更佳實施態樣中，步驟d)中該反應產物之乾燥係以混合實施。乾燥製程期間永久混合防止發生該混合物之可能溶解成分的濃度梯度以及確保該經乾燥產物之高均勻度。 In a more preferred embodiment of the invention, the drying of the reaction product in step d) is carried out by mixing. Permanent mixing during the drying process prevents concentration gradients of possible dissolved components of the mixture and ensures high uniformity of the dried product.

在本發明一更佳實施態樣中，步驟a)中所獲得之脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物在基於CuKα輻射的粉末X射線繞射圖中於2θ度為15.9±0.5、20.0±0.5、20.95±0.5、22.4±0.5及28.85±0.5處具有峰。該非晶形化的產物具有本文所述之優點。 In a further preferred embodiment of the present invention, the dehydrated iron (III) phosphate obtained in step a) or the dehydrated carbon complex of iron (III) phosphate is in 2θ in a powder X-ray diffraction pattern based on CuKα radiation. The peaks have peaks at 15.9±0.5, 20.0±0.5, 20.95±0.5, 22.4±0.5, and 28.85±0.5. The amorphized product has the advantages described herein.

根據本發明之極特別有利的方式，本文所使用之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正 磷酸鐵(III)或正磷酸鐵(III)之碳複合物為或可根據DE 102007049757、DE 102009001204或DE 102011003125所製造之產物。因引用而希望DE 102007049757、DE 102009001204及DE 102011003125之內容包括在本說明的揭示中。 In a very particularly advantageous manner according to the invention, the crystal structure of the phosphorus siderite (metastrengite II) used herein is positive The carbon complex of iron (III) phosphate or iron (III) orthophosphate is a product which can be produced according to DE 102007049757, DE 102009001204 or DE 102011003125. The contents of DE 102007049757, DE 102009001204 and DE 102011003125 are hereby incorporated by reference.

根據DE 102007049757之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)包括以下衡量： Iron(III) orthophosphate having a crystal structure of a phosphate iron ore (metastrengite II) according to DE 102007049757 includes the following measures:

1.藉由其中選自氫氧化物、氧化物、氧化物-氫氧化物、氧化物水合物、碳酸鹽及氫氧化物碳酸鹽之鐵(II)、鐵(III)或混合鐵(II,III)化合物係與濃度在介於5%與50%範圍內之磷酸反應的方法製造通式FePO4×nH2O(n2.5)之正磷酸鐵(III)，可能存在的鐵(II)在該反應之後藉由添加氧化劑而轉化成鐵(III)，以及從該反應混合物分離出固態正磷酸鐵(III)。 1. Iron (II), iron (III) or mixed iron (II, selected from the group consisting of hydroxides, oxides, oxide-hydroxides, oxide hydrates, carbonates and hydroxide carbonates) III) a method for reacting a compound with phosphoric acid having a concentration in the range of 5% and 50% to produce a general formula FePO 4 ×nH 2 O(n 2.5) Iron (III) orthophosphate, possibly iron (II) is converted to iron (III) by addition of an oxidizing agent after the reaction, and solid iron (III) orthophosphate is separated from the reaction mixture.

2.較佳地，該鐵化合物與磷酸之反應係在介於50℃與180℃範圍內，較佳係在介於60℃與150℃範圍內，特佳係介於70℃與120℃範圍內之溫度進行。 2. Preferably, the reaction of the iron compound with phosphoric acid is in the range of 50 ° C and 180 ° C, preferably in the range of 60 ° C and 150 ° C, and particularly preferably in the range of 70 ° C and 120 ° C. The temperature inside is carried out.

3.更佳地，該鐵化合物與磷酸之反應係在充分混合下進行。 3. More preferably, the reaction of the iron compound with phosphoric acid is carried out with thorough mixing.

4.更佳地，該鐵化合物與磷酸之反應進行達介於0.5分鐘與120分鐘，較佳係介於1分鐘與60分鐘，特佳係介於2分鐘與30分鐘之期間。 4. More preferably, the reaction of the iron compound with phosphoric acid is carried out for between 0.5 minutes and 120 minutes, preferably between 1 minute and 60 minutes, and particularly preferably between 2 minutes and 30 minutes.

5.更佳地，該鐵化合物與磷酸之反應係在介於8% 與23%範圍內之濃度下進行。 5. More preferably, the reaction of the iron compound with phosphoric acid is between 8% It is carried out at a concentration within the range of 23%.

6.更佳地，可能存在之鐵(III)的氧化係藉由添加過氧化氫(H2O2)或藉由進料空氣、純氧或臭氧來進行。 6. More preferably, the oxidation of iron (III) which may be present is carried out by the addition of hydrogen peroxide (H 2 O 2 ) or by feed air, pure oxygen or ozone.

7.更佳地，磷酸鐵(III)係在高溫及/或在減壓下從該反應混合物分離之後予以乾燥。 7. More preferably, iron (III) phosphate is dried after separation from the reaction mixture at elevated temperature and/or under reduced pressure.

8.更佳地，>80重量%，較佳係>90重量%，特佳係>95重量%之該正磷酸鐵(III)係以磷菱鐵礦(metastrengite)II(磷菱鐵礦)晶體結構存在。 8. More preferably, > 80% by weight, preferably > 90% by weight, particularly preferably > 95% by weight of the iron (III) orthophosphate is based on metastennite II (phosphorite) The crystal structure exists.

9.更佳地，正磷酸鐵(III)的至少一個維度之平均原粒子粒度為<1μm，較佳為<500nm，特佳為<100nm。 9. More preferably, the average primary particle size of at least one dimension of iron(III) orthophosphate is <1 μm, preferably <500 nm, and particularly preferably <100 nm.

10.正磷酸鐵(III)之體密度為>600g/l，較佳為>800g/l，特佳為>1000g/l。 10. The body density of iron (III) orthophosphate is >600 g/l, preferably >800 g/l, particularly preferably >1000 g/l.

11.更佳地，正磷酸鐵(III)之鉀及鈉的含量各為<300ppm。 11. More preferably, the content of potassium and sodium of iron (III) orthophosphate is <300 ppm.

12.更佳地，正磷酸鐵(III)之硫含量為<300ppm。 12. More preferably, the iron (III) orthophosphate has a sulfur content of <300 ppm.

13.更佳地，正磷酸鐵(III)之硝酸鹽含量為<100ppm。 13. More preferably, the nitrate content of iron (III) orthophosphate is <100 ppm.

根據DE 102009001204之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)包括以下衡量： Iron(III) orthophosphate having a crystal structure of phosphodendrite (metastrengite II) according to DE 102009001204 includes the following measures:

1.藉由一種方法製造通式FePO4×nH2O(n2.5)之正磷酸鐵(III)，該方法中a)含Fe2+離子之水溶液係藉由選自氫氧化物、氧化物、氧化物-氫氧化物、氧化物水合物、碳酸鹽及氫氧化 物碳酸鹽之氧化性鐵(II)、鐵(III)或混合鐵(II,III)化合物與元素鐵一起引入含磷酸之水性介質，且溶解Fe2+離子並使Fe3+與元素Fe反應(在歸一反應中)以產生Fe2+的製程製造，b)從該磷酸Fe2+水溶液分離固體，c)氧化劑係添加至該磷酸Fe2+水溶液以氧化該溶液中之鐵(II)，及沉澱通式FePO4×nH2O之正磷酸鐵(III)。 1. A method for producing FePO 4 ×nH 2 O(n) by a method 2.5) Iron (III) orthophosphate, in which a) an aqueous solution containing Fe 2+ ions is selected from the group consisting of hydroxides, oxides, oxide-hydroxides, oxide hydrates, carbonates and hydrogen An oxidized iron (II), iron (III) or mixed iron (II, III) compound of an oxide carbonate is introduced into an aqueous medium containing phosphoric acid together with elemental iron, and dissolves Fe 2+ ions and makes Fe 3+ and element Fe The reaction (in the normalization reaction) is produced in a process for producing Fe 2+ , b) the solid is separated from the aqueous solution of Fe 2+ phosphate, and c) the oxidant is added to the aqueous solution of Fe 2+ phosphate to oxidize the iron in the solution (II) And precipitating iron (III) orthophosphate of the general formula FePO 4 × nH 2 O.

2.較佳地，沉澱試劑係添加至該磷酸水溶液以使固體沉澱出該溶液，及將之從該磷酸Fe2+水溶液分離出，及/或從該溶液溶解於該磷酸水溶液之金屬電解分離金屬。 2. Preferably, a precipitation reagent is added to the aqueous phosphoric acid solution to precipitate a solid from the solution, and is separated from the aqueous solution of Fe 2+ phosphate, and/or from the electrolytic separation of the solution in the aqueous solution of the phosphoric acid. metal.

3.更佳地，該氧化性鐵化合物之反應係在具有磷酸之水性介質中(步驟a)於介於15℃與90℃範圍內，較佳係介於20℃與75℃範圍內，特佳係25℃與65℃範圍內之溫度及/或在充分混合下與元素鐵一起進行。 3. More preferably, the reaction of the oxidizing iron compound is in an aqueous medium having phosphoric acid (step a) in the range of 15 ° C and 90 ° C, preferably in the range of 20 ° C and 75 ° C, Preferably, the reaction is carried out with elemental iron at a temperature in the range of 25 ° C and 65 ° C and/or with sufficient mixing.

4.更佳地，該氧化性鐵化合物之反應係在具有磷酸之水性介質中(步驟a)與元素鐵一起進行達介於1分鐘與120分鐘，較佳係介於5分鐘與60分鐘，特佳係介於20分鐘與40分鐘之期間。 4. More preferably, the reaction of the oxidizing iron compound is carried out in an aqueous medium having phosphoric acid (step a) with elemental iron for between 1 minute and 120 minutes, preferably between 5 minutes and 60 minutes. The special system is between 20 minutes and 40 minutes.

5.更佳地，該水性介質中之磷酸的濃度相對於該水溶液之重量計係介於5%與85%，較佳係介於10%與40%，特佳係介於15%與30%。 5. More preferably, the concentration of phosphoric acid in the aqueous medium is between 5% and 85%, preferably between 10% and 40%, and particularly preferably between 15% and 30%, based on the weight of the aqueous solution. %.

6.更佳地，添加用以氧化該溶液中之鐵(II)的氧化劑為過氧化氫(H2O2)之水溶液，較佳係濃度介於15 與50重量%，特佳係介於30與40重量%。 6. More preferably, an oxidizing agent for oxidizing iron (II) in the solution is added as an aqueous solution of hydrogen peroxide (H 2 O 2 ), preferably at a concentration of between 15 and 50% by weight. 30 and 40% by weight.

7.或者，添加用以氧化該溶液中之鐵(II)的氧化劑係選自空氣、純氧或臭氧之氣態介質，其係吹入該分散液中。 7. Alternatively, the oxidizing agent for oxidizing iron (II) in the solution is selected from a gaseous medium selected from the group consisting of air, pure oxygen or ozone, which is blown into the dispersion.

8.更佳地，正磷酸鐵(III)係在沉澱之後與該水溶液分離，且較佳係在高溫及/或減壓下分離操作之後乾燥。 8. More preferably, iron (III) orthophosphate is separated from the aqueous solution after precipitation, and is preferably dried after separation operation at elevated temperature and/or reduced pressure.

9.更佳地，正磷酸鐵(III)的至少一個維度之平均原粒子粒度為<1μm，較佳為<500nm，特佳為<300nm，又特佳為<100nm。 9. More preferably, the average primary particle size of at least one dimension of iron (III) orthophosphate is <1 μm, preferably <500 nm, particularly preferably <300 nm, and particularly preferably <100 nm.

10.更佳地，正磷酸鐵(III)之體密度為>400g/l，較佳為>700g/l，特佳為>1000g/l，及/或夯實密度>600g/l，較佳為>750g/l，又更佳為>1100g/l。 10. More preferably, the iron (III) orthophosphate has a bulk density of >400 g/l, preferably >700 g/l, particularly preferably >1000 g/l, and/or a tamping density of >600 g/l, preferably >750 g/l, more preferably >1100 g/l.

11.更佳地，正磷酸鐵(III)之鉀及鈉的含量各為<300ppm，較佳為<200ppm，特佳為<100ppm，及/或硫含量為<300ppm，較佳為<200ppm，特佳為<100ppm，及/或硝酸鹽含量為<300ppm，較佳為<200ppm，特佳為<100ppm，及/或金屬及排除鐵以外之過渡金屬含量各為<300ppm，較佳為<200ppm，特佳為<100ppm。 11. More preferably, the content of potassium and sodium of iron (III) orthophosphate is <300 ppm, preferably <200 ppm, particularly preferably <100 ppm, and/or the sulfur content is <300 ppm, preferably <200 ppm, Particularly preferably <100 ppm, and/or having a nitrate content of <300 ppm, preferably <200 ppm, particularly preferably <100 ppm, and/or a transition metal content other than metal and iron excluding <300 ppm, preferably <200 ppm , especially good <100ppm.

根據DE 102011003125之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)之碳複合物包括以下衡量： The carbon composite of iron(III) orthophosphate having the crystal structure of the phosphorus siderite (metastrengite II) according to DE 102011003125 comprises the following measures:

1.含有通式FePO4×nH2O(n2.5)之正磷酸鐵(III)的正磷酸鐵(III)-碳複合物的製造，其中碳源係 分散在含有Fe2+離子之磷酸水溶液中，且正磷酸鐵(III)-碳複合物(FOP/C)係藉由將氧化劑添加至該分散液而從該水溶液沉澱出，及從該水溶液分離。 1. Contains the general formula FePO 4 × nH 2 O(n 2.5) Manufacture of an iron (III) orthophosphate complex of iron (III) orthophosphate, wherein the carbon source is dispersed in an aqueous solution of phosphoric acid containing Fe 2+ ions, and the iron (III) orthophosphate complex (FOP/C) is precipitated from the aqueous solution by adding an oxidizing agent to the dispersion, and is separated from the aqueous solution.

2.較佳地，該含Fe2+離子之水溶液係藉由選自氫氧化物、氧化物、氧化物-氫氧化物、氧化物水合物、碳酸鹽及氫氧化物碳酸鹽之氧化性鐵(II)、鐵(III)或混合鐵(II,III)化合物與元素鐵一起引入含磷酸之水性介質，且溶解Fe2+離子並使Fe3+與元素Fe反應(在歸一反應中)以產生Fe2+的製程製造，然後從該磷酸Fe2+水溶液分離固體。 2. Preferably, the aqueous solution containing Fe 2+ ions is made of oxidized iron selected from the group consisting of hydroxides, oxides, oxide-hydroxides, oxide hydrates, carbonates and hydroxide carbonates. (II), iron (III) or mixed iron (II, III) compound is introduced into the aqueous medium containing phosphoric acid together with elemental iron, and Fe 2+ ions are dissolved and Fe 3+ is reacted with element Fe (in normalization reaction) It is produced in a process for producing Fe 2+ and then separating the solid from the aqueous solution of Fe 2+ phosphate.

3.更佳地，該碳源包括元素碳或只由元素碳組成，該元素碳較佳係選自石墨、膨脹石墨(expanded graphite)、煙灰(諸如碳黑或松煙)、奈米碳管(CNT)、富勒烯(fullerene)、石墨烯(graphene)、玻璃碳(glass carbon，玻璃狀碳)、碳纖維、活性碳或其混合物。 3. More preferably, the carbon source comprises or consists solely of elemental carbon, which is preferably selected from the group consisting of graphite, expanded graphite, soot (such as carbon black or loose smoke), carbon nanotubes. (CNT), fullerene, graphene, glass carbon, carbon fiber, activated carbon or a mixture thereof.

4.更佳地，除了元素碳之外，該碳源亦包括有機化合物，其中該等有機化合物較佳係選自烴、醇、醛、羧酸、表面活性劑、寡聚物、聚合物、碳水化合物或其混合物。 4. More preferably, in addition to elemental carbon, the carbon source also includes organic compounds, wherein the organic compounds are preferably selected from the group consisting of hydrocarbons, alcohols, aldehydes, carboxylic acids, surfactants, oligomers, polymers, Carbohydrate or a mixture thereof.

5.更佳地，該碳源於含磷酸Fe2+離子之水溶液中的分散液包括相對於該沉澱之FOP的重量計為介於1與10重量%之碳，較佳為介於1.5與5重量%之碳，特佳為介於1.8與4重量%之碳的量之碳源。 5. More preferably, the dispersion of the carbon source in the aqueous solution containing Fe 2+ ions comprises between 1 and 10% by weight of carbon, preferably between 1.5 and the weight of the precipitated FOP. 5% by weight of carbon, particularly preferably a carbon source in an amount of between 1.8 and 4% by weight of carbon.

6.更佳地，用以製造該分散液的含磷酸Fe2+離子之水溶液的Fe2+離子濃度係介於0.8與2.0mol/l，較佳為介於1.0與1.7mol/l，特佳為介於1.1與1.3mol/l，且pH在介於1.5與2.5，較佳為介於1.8與2.3，特佳為介於2.0與2.1範圍內。 6. More preferably, the Fe 2+ ion concentration of the aqueous solution containing phosphoric acid Fe 2+ ions for producing the dispersion is between 0.8 and 2.0 mol/l, preferably between 1.0 and 1.7 mol/l. Preferably, it is between 1.1 and 1.3 mol/l, and the pH is between 1.5 and 2.5, preferably between 1.8 and 2.3, and particularly preferably between 2.0 and 2.1.

7.更佳地，添加至該分散液之氧化劑為過氧化氫(H2O2)之水溶液，較佳係濃度介於15與50重量%，特佳係介於30與40重量%，或選自空氣、純氧或臭氧之氣態介質，其係吹入該分散液中。 7. More preferably, the oxidizing agent added to the dispersion is an aqueous solution of hydrogen peroxide (H 2 O 2 ), preferably at a concentration of 15 and 50% by weight, particularly preferably between 30 and 40% by weight, or A gaseous medium selected from the group consisting of air, pure oxygen or ozone, which is blown into the dispersion.

8.更佳地，該正磷酸鐵(III)-碳複合物於沉澱及從該水溶液分離之後係以水、水性及/或有機溶劑清洗一或多次，然後在高溫及/或減壓下乾燥，或製備成固體含量介於1與90重量%之水性分散液形式。 8. More preferably, the iron(III) orthophosphate complex is precipitated and separated from the aqueous solution by one or more times with water, aqueous and/or organic solvent, and then subjected to high temperature and/or reduced pressure. It is dried or prepared in the form of an aqueous dispersion having a solid content of between 1 and 90% by weight.

9.更佳地，該正磷酸鐵(III)-碳複合物的至少一個維度之平均原粒子粒度為<1μm，較佳為<500nm，特佳為<300nm，又特佳為<100nm。 9. More preferably, the average primary particle size of at least one dimension of the iron (III) orthophosphate complex is <1 μm, preferably <500 nm, particularly preferably <300 nm, and particularly preferably <100 nm.

10.更佳地，該正磷酸鐵(III)-碳複合物之體密度為>400g/l，較佳為>700g/l，特佳為>1000g/l，及/或夯實密度>600g/l，較佳為>750g/l，又更佳為>1100g/l。 10. More preferably, the iron (III) orthophosphate complex has a bulk density of >400 g/l, preferably >700 g/l, particularly preferably >1000 g/l, and/or a tamping density of >600 g/ l, preferably > 750 g/l, more preferably > 1100 g/l.

本發明另外包括如本文所述方式製造的經鋰化之磷酸鐵或經鋰化之至少-碳複合物。 The invention additionally includes lithiated iron phosphate or lithiated at least-carbon composites made as described herein.

最後，本發明亦包括根據本發明之非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物或是經鋰化之磷酸鐵或其碳複合物用於鋰離子蓄電池的陰極材料之用途。 Finally, the present invention also includes an amorphous or amorphous iron(III) phosphate anhydrate or a carbon composite thereof according to the present invention or a lithiated iron phosphate or a carbon composite thereof for use as a cathode material for a lithium ion secondary battery. Use.

本發明經鋰化之磷酸鐵或經鋰化之磷酸鐵-碳複合物作為鋰離子蓄電池的陰極材料之用途。 The use of the lithiated iron phosphate or the lithiated iron phosphate-carbon composite of the present invention as a cathode material for a lithium ion secondary battery.

實施例Example 實施例1-根據DE 10 2007 049 757製造正磷酸鐵(III)(FOP) Example 1 - Preparation of iron (III) orthophosphate (FOP) according to DE 10 2007 049 757

將2.4l之密度為1.121g/l的磷酸溶液加熱至92℃，然後與130g之Fe3O4(FarbuHuzhou Hauman Chem.Ind.Co Ltd)混合。攪動該反應混合物並在11分鐘後色彩朝灰色改變，此被視為反應結束的指標。然後在先前設定之溫度下，於6分鐘內逐滴添加35ml之35% H2O2溶液以將存在該反應混合物中的鐵(II)氧化成鐵(III)。以適用之Merck測試條檢查反應混合物中的鐵(II)含量。無法再偵測到任何鐵(II)時，立刻再攪動該粉紅-灰色批料15分鐘。該色彩朝粉紅色改變。濾除該產物並於150℃在大氣壓力下乾燥。 2.4 l of a phosphoric acid solution having a density of 1.121 g/l was heated to 92 ° C and then mixed with 130 g of Fe 3 O 4 (FarbuHuzhou Hauman Chem. Ind. Co Ltd). The reaction mixture was agitated and the color changed to gray after 11 minutes, which was regarded as an indicator of the end of the reaction. Then 35 ml of a 35% H 2 O 2 solution was added dropwise over 6 minutes at the previously set temperature to oxidize the iron (II) present in the reaction mixture to iron (III). The iron (II) content of the reaction mixture was checked using a suitable Merck test strip. When it is no longer possible to detect any iron (II), immediately stir the pink-gray batch for 15 minutes. The color changes towards pink. The product was filtered off and dried at 150 ° C under atmospheric pressure.

濕產率：370g Wet yield: 370g

乾產率：305g Dry yield: 305g

產率%：96.7 Yield%: 96.7

體密度：920g/l Bulk density: 920g/l

實施例2-根據DE 10 2007 049 757製造正磷酸鐵(III)(FOP) Example 2 - Preparation of iron (III) orthophosphate (FOP) according to DE 10 2007 049 757

在95℃下加熱1l之密度為1.133g/l的磷酸溶液加 熱，然後與92g之新沉澱的氫氧化鐵(固體含量為約63%)混合。在5分鐘後，色彩朝灰色改變。在先前設定之溫度下，於4分鐘內逐滴添加22ml之35% H2O2溶液。然後該反應混合物仍保持於100℃為時19分鐘直到色彩改變成粉紅色為止。濾除該產物並於150℃在大氣壓力下乾燥。 1 l of a phosphoric acid solution having a density of 1.133 g/l was heated at 95 ° C and then mixed with 92 g of freshly precipitated iron hydroxide (solid content of about 63%). After 5 minutes, the color changes towards gray. At the previously set temperature, 22 ml of a 35% H 2 O 2 solution was added dropwise over 4 minutes. The reaction mixture was then held at 100 ° C for 19 minutes until the color changed to pink. The product was filtered off and dried at 150 ° C under atmospheric pressure.

濕產率：214g Wet yield: 214g

乾產率：124g Dry yield: 124g

產率%：約93 Yield%: about 93

體密度：890g/l Bulk density: 890g/l

實施例3-根據DE 10 2007 049 757製造正磷酸鐵(III)(FOP) Example 3 - Preparation of iron (III) orthophosphate (FOP) according to DE 10 2007 049 757

在90℃下加熱2.7l之密度為1.09g/l的磷酸溶液加熱，然後與200g之新沉澱的氫氧化鐵碳酸鹽(固體含量為約48%)之濾餅逐部分混合。在添加期間，溫度上升至96℃。在5分鐘之後，色彩朝紅-灰色改變。之後，在4分鐘內添加20g之35% H2O2溶液。再次以適用之Merck測試條檢查鐵(II)含量。然後再攪動該批料15分鐘，過濾並於150℃在周圍氣氛下乾燥。 2.7 l of a phosphoric acid solution having a density of 1.09 g/l was heated at 90 ° C, and then mixed with 200 g of freshly precipitated iron hydroxide carbonate (solid content of about 48%) of the filter cake. During the addition, the temperature rose to 96 °C. After 5 minutes, the color changes towards red-grey. Thereafter, 20 g of a 35% H 2 O 2 solution was added over 4 minutes. The iron (II) content was again checked with the applicable Merck test strip. The batch was then agitated for a further 15 minutes, filtered and dried at 150 ° C under ambient atmosphere.

濕產率：193g Wet yield: 193g

乾產率：128g Dry yield: 128g

產率%：約96 Yield%: about 96

體密度：810g/l Bulk density: 810g/l

實施例4-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 4 - Preparation of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

在室溫(20℃)下提供稀釋磷酸(18重量%；密度=於20℃下為1.146g/ml)並與20g之氧化鐵(磁鐵礦；Fe3O4)混合。該混合物係使用分散棒以10,000rpm予以均質化。然後採用攪動將所得之懸浮液與7g之鐵粉末混合。 Diluted phosphoric acid (18% by weight; density = 1.146 g/ml at 20 ° C) was supplied at room temperature (20 ° C) and mixed with 20 g of iron oxide (magnetite; Fe 3 O 4 ). The mixture was homogenized using a dispersing bar at 10,000 rpm. The resulting suspension was then mixed with 7 g of iron powder using agitation.

發生放熱反應。溫度在20分鐘內從約20℃上升至約40℃。在該期間，該懸浮液的色彩定黑色朝綠-棕色改變，且起始材料溶解。藉由該懸浮液中之小泡泡可看出正發生氣體發展(H2)。所產生之氣體量係以氣泡計數器量化。在溶解程序結束之後，過濾該溶液以從該溶液分離出固體。然後將該溶液加熱至80℃並與約55ml之H2O2溶液(35重量%)混合以將該溶液中之Fe2+離子氧化成Fe3+離子。產生氧作為H2O2分解產物。藉由快速測試Fe2+離子(Merck測試條)，進行檢查以判定氧化反應是否完成。可能隨後計量添加H2O2。將現在變成粉紅色之溶液保持在約85℃，並使正磷酸鐵(III)沉澱。沉澱持續約30分鐘。最終產物為亮粉紅色，且在沉澱之後吸過玻璃料並以400ml的水清洗。該材料愈細微，該吸濾移除程序可持續對應較長時間。然後該產物係在乾燥櫥中於80℃乾燥3小時。產率為至少90%。最終產物為細微正磷酸鐵(III)。 An exothermic reaction occurs. The temperature rose from about 20 ° C to about 40 ° C in 20 minutes. During this time, the color of the suspension turned black to green-brown and the starting material dissolved. It is seen by the small bubbles in the suspension that gas evolution (H 2 ) is occurring. The amount of gas produced is quantified by a bubble counter. After the dissolution procedure is over, the solution is filtered to separate the solids from the solution. The solution was then heated to 80 ° C and mixed with about 55 ml of H 2 O 2 solution (35 wt%) to oxidize the Fe 2+ ions in the solution to Fe 3+ ions. Oxygen is produced as a decomposition product of H 2 O 2 . By quickly testing Fe 2+ ions (Merck test strips), a check is made to determine if the oxidation reaction is complete. It is possible to subsequently meter the addition of H 2 O 2 . The solution which is now pinked is kept at about 85 ° C and iron (III) orthophosphate is precipitated. The precipitation lasted for about 30 minutes. The final product was bright pink and the glass frit was sucked after precipitation and washed with 400 ml of water. The finer the material, the suction removal procedure can last for a longer period of time. The product was then dried in a drying cabinet at 80 ° C for 3 hours. The yield is at least 90%. The final product is fine iron (III) orthophosphate.

實施例5-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 5 - Preparation of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

如實施例4但提供稍微更高度濃縮之磷酸(25重量%；密度=於200℃下為1.208g/ml)，且在氧化反應之後於100℃下沉澱該正磷酸鐵(III)。產率超過90%。最終產物為比實施例1粗之正磷酸鐵(III)。 As in Example 4, a slightly more highly concentrated phosphoric acid (25% by weight; density = 1.208 g/ml at 200 ° C) was provided, and the iron (III) orthophosphate was precipitated at 100 ° C after the oxidation reaction. The yield is over 90%. The final product was iron (III) orthophosphate thicker than Example 1.

實施例6-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 6 - Production of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

將20g之Fe3O4提供於125g之H2O，並使用Ultraturrax以10,000rpm預處理30分鐘。然後在室溫下添加125g之75%磷酸、另外125g之H2O及7g之Fe。於該混合物中之該稀釋磷酸的密度於20℃下為1.146g/ml。發生些微產氣，此持續整個反應期間。在7分鐘內，溫度上升至42℃，且懸浮液之色彩朝棕色改變。在9分鐘後，發現溫度未進一步提高，因此在油浴(T=120℃)中加熱反應混合物。在70分鐘之後，形成稍微渾濁的綠色溶液。觀察到不再有進一步氣體發展。藉由過濾移除渾濁物，並在80℃下將該濾液與40ml之H2O2溶液(35重量%)混合。色彩從強烈紅色改變成亮粉紅色，該情況下，產生具有亮粉紅色之細微固體作為產物。產率為99.8%(71.7g)。 20 g of Fe 3 O 4 was supplied to 125 g of H 2 O, and pretreated at 10,000 rpm for 30 minutes using an Ultraturrax. Then 125 g of 75% phosphoric acid, an additional 125 g of H 2 O and 7 g of Fe were added at room temperature. The density of the diluted phosphoric acid in the mixture was 1.146 g/ml at 20 °C. Some micro gas production occurs, which lasts throughout the reaction period. Within 7 minutes, the temperature rose to 42 ° C and the color of the suspension changed towards brown. After 9 minutes, it was found that the temperature did not increase further, so the reaction mixture was heated in an oil bath (T = 120 ° C). After 70 minutes, a slightly cloudy green solution formed. No further gas development was observed. The haze was removed by filtration and the filtrate was mixed with 40 ml of H 2 O 2 solution (35 wt%) at 80 °C. The color changes from intense red to bright pink, in which case a fine pink with a bright pink color is produced as a product. The yield was 99.8% (71.7 g).

實施例7-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 7 - Production of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

在室溫下將20g之Fe3O4、7g之Fe、250g之H2O及125g之75%磷酸放置在一起。於該混合物中之該稀釋磷酸的密度於20℃下為1.146g/ml。發生些微產氣，此持續整個反應期間。在20分鐘內，溫度上升至38℃，且懸浮液之色彩朝棕色改變。在30分鐘後，發現溫度未進一步提高，因此在油浴(T=120℃)中加熱反應混合物。在90分鐘之後，形成稍微渾濁的綠色溶液。觀察到不再有進一步氣體發展。藉由過濾移除渾濁物，並在85℃下將該濾液與40ml之H2O2溶液(35重量%)混合。色彩從強烈紅色改變成亮粉紅色，該情況下，產生具有亮粉紅色之細微固體作為產物。產率為83.5%(60.0g)。 20 g of Fe 3 O 4 , 7 g of Fe, 250 g of H 2 O and 125 g of 75% phosphoric acid were placed together at room temperature. The density of the diluted phosphoric acid in the mixture was 1.146 g/ml at 20 °C. Some micro gas production occurs, which lasts throughout the reaction period. Within 20 minutes, the temperature rose to 38 ° C and the color of the suspension changed towards brown. After 30 minutes, it was found that the temperature did not increase further, so the reaction mixture was heated in an oil bath (T = 120 ° C). After 90 minutes, a slightly cloudy green solution formed. No further gas development was observed. The haze was removed by filtration and the filtrate was mixed with 40 ml of H 2 O 2 solution (35 wt%) at 85 °C. The color changes from intense red to bright pink, in which case a fine pink with a bright pink color is produced as a product. The yield was 83.5% (60.0 g).

實施例8-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 8 - Production of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

在室溫下將20g之Fe3O4、7g之Fe、250g之H2O及204g之75%磷酸放置在一起。於該混合物中之該稀釋磷酸的密度於20℃下為1.232g/ml。發生些微產氣，此持續整個反應期間。在10分鐘內，溫度上升至53℃，且懸浮液之色彩朝棕色改變。利用冰浴立刻進行冷卻至50℃。在50℃下又過40分鐘之後，形成稍微渾濁的綠色溶液。觀察到不再有進一步氣體發展。藉由過濾移除渾濁物，並在85℃下將該濾液與40ml之H2O2溶液(35重量 %)混合。色彩從強烈紅色改變成亮粉紅色，該情況下，產生具有亮粉紅色之粗固體作為產物。產率為85.8%(61.6g)。 20 g of Fe 3 O 4 , 7 g of Fe, 250 g of H 2 O and 204 g of 75% phosphoric acid were placed together at room temperature. The density of the diluted phosphoric acid in the mixture was 1.232 g/ml at 20 °C. Some micro gas production occurs, which lasts throughout the reaction period. Within 10 minutes, the temperature rose to 53 ° C and the color of the suspension changed towards brown. Immediately cooling to 50 ° C using an ice bath. After another 40 minutes at 50 ° C, a slightly cloudy green solution formed. No further gas development was observed. The haze was removed by filtration and the filtrate was mixed with 40 ml of H 2 O 2 solution (35 wt%) at 85 °C. The color changes from intense red to bright pink, in which case a coarse solid with a bright pink color is produced as a product. The yield was 85.8% (61.6 g).

實施例9-根據DE 10 2009 001 204製造正磷酸鐵(III)(FOP) Example 9 - Production of iron (III) orthophosphate (FOP) according to DE 10 2009 001 204

在50℃下將10g之Fe3O4、3.2g之Fe、211g之H2O及93g之75%磷酸放置在一起。於該混合物中之該稀釋磷酸的密度於20℃下為1.134g/ml。發生些微產氣，此持續整個反應期間。在50℃下157分鐘之後，形成稍微渾濁的綠色溶液。觀察到不再有進一步氣體發展。藉由過濾移除渾濁物，並在85℃下將該濾液與20ml之H2O2溶液(35重量%)混合。色彩從強烈紅色改變成亮粉紅色，該情況下，產生具有亮粉紅色之細微固體作為產物。產率為30.2g。 10 g of Fe 3 O 4 , 3.2 g of Fe, 211 g of H 2 O and 93 g of 75% phosphoric acid were placed together at 50 °C. The density of the diluted phosphoric acid in the mixture was 1.134 g/ml at 20 °C. Some micro gas production occurs, which lasts throughout the reaction period. After 157 minutes at 50 ° C, a slightly cloudy green solution formed. No further gas development was observed. The haze was removed by filtration and the filtrate was mixed with 20 ml of H 2 O 2 solution (35 wt%) at 85 °C. The color changes from intense red to bright pink, in which case a fine pink with a bright pink color is produced as a product. The yield was 30.2 g.

實施例10-根據DE 10 2009 001 204製造正磷酸鐵(IIl)(FOP) Example 10 - Production of iron (IIl) orthophosphate (FOP) according to DE 10 2009 001 204

在室溫下將10g之Fe3O4、11g之Fe、379g之H2O及168g之75%磷酸放置在一起。於該混合物中之該稀釋磷酸的密度於20℃下為1.134g/ml。發生些微產氣，此持續整個反應期間。在63℃下進行加熱並在120分鐘後產生具有非常輕微渾濁的綠色溶液。觀察到不再有進一步氣體發展。藉由過濾移除渾濁物，並在85℃下將該濾液與 30ml之H2O2溶液(35重量%)混合。色彩從強烈紅色改變成亮粉紅色，該情況下，產生具有亮粉紅色之細微固體作為產物。產率為58.0g。 10 g of Fe 3 O 4 , 11 g of Fe, 379 g of H 2 O and 168 g of 75% phosphoric acid were placed together at room temperature. The density of the diluted phosphoric acid in the mixture was 1.134 g/ml at 20 °C. Some micro gas production occurs, which lasts throughout the reaction period. Heating at 63 ° C and after 120 minutes produced a green solution with very slight turbidity. No further gas development was observed. The haze was removed by filtration and the filtrate was mixed with 30 ml of H 2 O 2 solution (35 wt%) at 85 °C. The color changes from intense red to bright pink, in which case a fine pink with a bright pink color is produced as a product. The yield was 58.0 g.

實施例11：根據DE 10 2011 003 125製造具有7.3%石墨之正磷酸鐵(III)-碳複合物(FOP/C) Example 11: Preparation of iron (III)-carbon complex (FOP/C) with 7.3% graphite according to DE 10 2011 003 125

將2540g(約2L)之Fe2+溶液提供於攪拌器容器中，並藉由裝配0.4-0.6mm之研磨球的攪拌器球磨機(LabStar，Netzsch)以循環模式泵送。然後將33.1g之石墨(UF2，得自Graphitwerk Kropfmühl KG)分4部分於5分鐘內加入。利用DLS測量(動態光散射器，Malvern Zetasizer)每30分鐘檢查該分散液的粒度分布及品質。3小時之後，無法偵測到相對於兩個先前測量的任何改變。結束該實驗並將該分散液收集在玻璃燒杯中。 A 2540 g (about 2 L) Fe 2+ solution was supplied to the agitator vessel and pumped in a circulating mode by a stirrer ball mill (LabStar, Netzsch) equipped with a 0.4-0.6 mm grinding ball. Then 33.1 g of graphite (UF2, available from Graphitwerk Kropfmühl KG) was added in 4 portions over 5 minutes. The particle size distribution and quality of the dispersion were examined every 30 minutes using DLS measurement (Dynamic Light Scatterer, Malvern Zetasizer). After 3 hours, no changes relative to the two previous measurements could be detected. The experiment was ended and the dispersion was collected in a glass beaker.

將1100g該分散液加熱至75℃，然後在攪拌下添加110ml之H2O2(於水中35%)以開始FOP的沉澱。在發生之氣體發展逐漸消退之後，於85℃再持續攪動15分鐘。混合物中之固體部分係藉由吸濾器分離，然後再懸浮兩次，每次各於1L之去離子水中進行，然後過濾之。在循環空氣乾燥櫥中於100℃下乾燥之後，獲得182g之灰色固體。產物之XRD分析展現磷菱鐵礦及石墨的特徵反射。 1100 g of this dispersion was heated to 75 ° C, and then 110 ml of H 2 O 2 (35% in water) was added with stirring to start precipitation of FOP. After the gas evolution that has occurred gradually subsides, stirring is continued for another 15 minutes at 85 °C. The solid portion of the mixture was separated by a suction filter and then resuspended twice, each time in 1 L of deionized water, and then filtered. After drying at 100 ° C in a circulating air drying cabinet, 182 g of a gray solid was obtained. XRD analysis of the product revealed characteristic reflection of the pyrite and graphite.

實施例12：製造具有7.3%膨脹石墨之正磷酸鐵(III)-碳 複合物(FOP/C) Example 12: Fabrication of iron(III) orthophosphate-carbon with 7.3% expanded graphite Composite (FOP/C)

將3367g(約2.6L)之Fe2+溶液提供於攪拌器容器中，並藉由裝配0.4-0.6mm之研磨球的攪拌器球磨機(LabStar，Netzsch)以循環模式泵送。然後將43.9g之膨脹石墨(SGL Carbon)分4部分於5分鐘內加入。2小時後將該分散液收集在玻璃燒杯中。 A 3367 g (about 2.6 L) Fe2 + solution was supplied to the agitator vessel and pumped in a circulating mode by a stirrer ball mill (LabStar, Netzsch) equipped with 0.4-0.6 mm grinding balls. Then 43.9 g of expanded graphite (SGL Carbon) was added in 4 portions over 5 minutes. The dispersion was collected in a glass beaker after 2 hours.

將1500g該分散液加熱至75℃，然後在攪拌下添加160ml之H2O2(於水中35%)以開始FOP的沉澱。在發生之氣體發展逐漸消退之後，於85℃再持續攪動15分鐘。混合物中之固體部分係藉由吸濾器分離，然後再懸浮兩次，每次係於1.5L之去離子水中進行，然後過濾之。在循環空氣乾燥櫥中於100℃下乾燥之後，獲得273g之灰色固體。產物之XRD分析展現磷菱鐵礦及石墨的特徵反射。 1500 g of this dispersion was heated to 75 ° C, then 160 ml of H 2 O 2 (35% in water) was added with stirring to start precipitation of FOP. After the gas evolution that has occurred gradually subsides, stirring is continued for another 15 minutes at 85 °C. The solid portion of the mixture was separated by a suction filter and then resuspended twice, each time in 1.5 L of deionized water, and then filtered. After drying at 100 ° C in a circulating air drying cabinet, 273 g of a gray solid was obtained. XRD analysis of the product revealed characteristic reflection of the pyrite and graphite.

實施例13：製造具有4%經預處理石墨之正磷酸鐵(III)-碳複合物(FOP/C) Example 13: Production of iron (III)-carbon complex (FOP/C) with 4% pretreated graphite

在球磨機中懸浮液之前，約30g之石墨(SGL Carbon)係在500ml之濃縮HNO3中於回流下加熱1小時30分鐘，直到沸騰為止。然後固體係藉由吸濾器分離，再懸浮兩次，每次各於1L之去離子水中進行，過濾並在100℃下於循環空氣乾燥櫥乾燥一夜。將13.2g之以該方法處理的石墨分部分於5分鐘內添加至1850g(約2L)之Fe2+溶液，同時藉由配備有0.4-0.6mm之研磨球的攪 拌器球磨機(LabStar，Netzsch)以循環模式泵送。2小時後將該分散液收集在玻璃燒杯中。 Before the suspension in the ball mill, about 30 g of graphite (SGL Carbon) was heated in 500 ml of concentrated HNO 3 under reflux for 1 hour and 30 minutes until boiling. The solids were then separated by suction filter, resuspended twice, each time in 1 L of deionized water, filtered and dried overnight at 100 ° C in a circulating air drying cabinet. 13.2 g of the graphite treated in this way was added to a 1850 g (about 2 L) Fe 2+ solution over 5 minutes while being agitator ball mill (LabStar, Netzsch) equipped with a 0.4-0.6 mm grinding ball. Pumped in a cyclic mode. The dispersion was collected in a glass beaker after 2 hours.

將800g該分散液加熱至75℃，然後在攪拌下添加110ml之H2O2(於水中35%)以開始FOP的沉澱。在發生之氣體發展逐漸消退之後，於85℃再持續攪動15分鐘。混合物中之固體部分係藉由吸濾器分離，然後再懸浮兩次，每次各於1L之去離子水中進行，然後過濾之。在循環空氣乾燥櫥中於100℃下乾燥之後，獲得133g之灰色固體。產物之XRD分析展現磷菱鐵礦及石墨的特徵反射。 800 g of this dispersion was heated to 75 ° C, and then 110 ml of H 2 O 2 (35% in water) was added with stirring to start precipitation of FOP. After the gas evolution that has occurred gradually subsides, stirring is continued for another 15 minutes at 85 °C. The solid portion of the mixture was separated by a suction filter and then resuspended twice, each time in 1 L of deionized water, and then filtered. After drying at 100 ° C in a circulating air drying cabinet, 133 g of a gray solid was obtained. XRD analysis of the product revealed characteristic reflection of the pyrite and graphite.

實施例14：製造具有2.3%之Ketjen Black的正磷酸鐵(III)-碳複合物(FOP/C) Example 14: Production of iron (III)-carbon complex (FOP/C) with 2.3% Ketjen Black

將23g之Ketjen Black® EC-300J(Akzo Nobel)在15分鐘內逐份添加至5600g(約4.5L)之Fe2+溶液。在該情況下，藉由裝配0.8-1.0mm之研磨球的攪拌器球磨機(LabStar，Netzsch)以循環模式泵送該溶液。3小時後將該分散液收集在玻璃燒杯中。 23 g of Ketjen Black ® EC-300J (Akzo Nobel) was added portionwise to a 5600 g (about 4.5 L) Fe 2+ solution over 15 minutes. In this case, the solution was pumped in a circulating mode by means of a stirrer ball mill (LabStar, Netzsch) equipped with 0.8-1.0 mm grinding balls. The dispersion was collected in a glass beaker after 3 hours.

將3.8g該分散液加熱至75℃，然後在攪拌下添加390ml之H2O2(於水中35%)以開始FOP的沉澱。在發生之氣體發展逐漸消退之後，於85℃再持續攪動15分鐘。混合物中之固體部分係藉由吸濾器分離，然後再懸浮兩次，每次係於1L之去離子水中進行，然後過濾之。在循環空氣乾燥櫥中於100℃下乾燥之後，獲得850g之淺 灰色固體。產物之XRD分析展現磷菱鐵礦及石墨的特徵反射。 3.8 g of this dispersion was heated to 75 ° C, then 390 ml of H 2 O 2 (35% in water) was added with stirring to start precipitation of FOP. After the gas evolution that has occurred gradually subsides, stirring is continued for another 15 minutes at 85 °C. The solid portion of the mixture was separated by a suction filter and then resuspended twice, each time in 1 L of deionized water, and then filtered. After drying at 100 ° C in a circulating air drying cabinet, 850 g of a light gray solid was obtained. XRD analysis of the product revealed characteristic reflection of the pyrite and graphite.

實施例15：製造非晶形或非晶形化的磷酸鐵(III)無水物 Example 15: Production of amorphous or amorphous iron (III) phosphate anhydrate

非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物之製造係根據實施例1至14在介於150℃與220℃於標準大氣、保護性氣氛下或真空中簡單熱處理具有磷菱鐵礦結構之正磷酸鐵(III)(FOP)或正磷酸鐵(III)-碳複合物(FOP/C)介於8與20小時來進行。 The amorphous or amorphous iron(III) phosphate anhydrate or its carbon composite is produced according to Examples 1 to 14 by simple heat treatment at 150 ° C and 220 ° C under standard atmosphere, protective atmosphere or vacuum. The iron orthophosphate iron (III) (FOP) or iron orthophosphate (III)-carbon complex (FOP/C) of the pyrite structure is carried out at 8 and 20 hours.

實施例16：製造經鋰化之磷酸鐵(III)無水物(LFP) Example 16: Production of lithiated iron (III) phosphate anhydrate (LFP)

將45.46g之LiOH×1H2O溶解於300ml之H2O，然後添加100ml之96%乙酸。將100g之抗壞血酸溶解於該溶液，然後根據實施例14添加156g之非晶形化的磷酸鐵(III)無水物。所得之分散液於60℃下攪動2小時，然後在真空爐中於60℃下乾燥14小時。該乾燥操作或者可在110℃或210℃下於循環空氣乾燥櫥中進行14小時。 45.46 g of LiOH x 1H 2 O was dissolved in 300 ml of H 2 O, and then 100 ml of 96% acetic acid was added. 100 g of ascorbic acid was dissolved in the solution, and then 156 g of the amorphous iron (III) phosphate anhydrate was added according to Example 14. The resulting dispersion was stirred at 60 ° C for 2 hours and then dried in a vacuum oven at 60 ° C for 14 hours. The drying operation can be carried out in a circulating air drying cabinet at 110 ° C or 210 ° C for 14 hours.

實施例17：煅燒經鋰化之磷酸鐵(III)無水物(LFP) Example 17: Calcination of lithiated iron (III) phosphate anhydrate (LFP)

在具有石英反應管之旋轉窯中於氮氣氛中在1.5小時內將根據實施例16所製造的經鋰化之磷酸鐵(III)無水物或其碳複合物加熱至550℃，然後在該溫度保持1小時。然後關掉該加熱，使該反應管冷卻至室溫。 The lithiated iron(III) phosphate anhydrate or its carbon composite produced according to Example 16 was heated to 550 ° C in a rotary kiln with a quartz reaction tube in a nitrogen atmosphere for 1.5 hours, and then at this temperature Hold for 1 hour. The heating was then turned off and the reaction tube was allowed to cool to room temperature.

或者，在具有石英反應管之旋轉窯中於氮氣氛中在1.5小時內將根據實施例16所製造的經鋰化之磷酸鐵(III)無水物或其碳複合物加熱至700℃，然後在該溫度保持1小時。然後關掉該加熱，使該反應管冷卻至室溫。 Alternatively, the lithiated iron(III) phosphate anhydrate or its carbon composite produced according to Example 16 is heated to 700 ° C in a nitrogen atmosphere at a rotary kiln having a quartz reaction tube for 1.5 hours, and then This temperature was maintained for 1 hour. The heating was then turned off and the reaction tube was allowed to cool to room temperature.

或者，在氮氣氛中於5體積%之氫流下在2小時內將根據實施例16所製造的經鋰化之磷酸鐵(III)無水物或其碳複合物加熱至700℃，然後在該溫度保持2小時。然後關掉該加熱，使該反應管冷卻至室溫。 Alternatively, the lithiated iron(III) phosphate anhydrate or its carbon composite produced according to Example 16 is heated to 700 ° C in a nitrogen atmosphere at a flow rate of 5 vol% under a nitrogen atmosphere, and then at this temperature. Keep it for 2 hours. The heating was then turned off and the reaction tube was allowed to cool to room temperature.

或者，在氮氣氛中於5體積%之氫流下在2小時內將根據實施例16所製造的經鋰化之磷酸鐵(III)無水物或其碳複合物加熱至300℃，然後在該溫度保持2小時，之後在2小時內加熱至600℃，然後在該溫度保持1小時。然後關掉該加熱，使該反應管冷卻至室溫。 Alternatively, the lithiated iron(III) phosphate anhydrate or its carbon composite produced according to Example 16 is heated to 300 ° C in a nitrogen atmosphere at a flow rate of 5 vol% under a nitrogen atmosphere, and then at this temperature It was kept for 2 hours, then heated to 600 ° C in 2 hours, and then kept at this temperature for 1 hour. The heating was then turned off and the reaction tube was allowed to cool to room temperature.

或者，在真空下於1.5小時內將根據實施例16所製造的經鋰化之磷酸鐵(III)無水物或其碳複合物加熱至350℃，然後在該溫度保持1小時。在***之冷卻阱中未觀察到凝結產物。然後以氮氣氛中5體積%之氫流置換該真空，且在1.5小時內將該材料加熱至700℃，且在該溫度下再保持1小時。然後關掉該加熱，使該反應管冷卻至室溫。 Alternatively, the lithiated iron(III) phosphate anhydrate or its carbon composite produced according to Example 16 was heated to 350 ° C under vacuum for 1.5 hours and then held at this temperature for 1 hour. No condensation product was observed in the inserted cooling trap. The vacuum was then replaced with a 5 vol% hydrogen stream in a nitrogen atmosphere and the material was heated to 700 ° C over 1.5 hours and held at this temperature for an additional hour. The heating was then turned off and the reaction tube was allowed to cool to room temperature.

對照實例：於作為流體介質之乙醇中化學鋰化 Comparative Example: Chemical Lithiation in Ethanol as a Fluid Medium

將24.48g之乙酸鋰二脫水溶解於2000ml之乙醇中。將21.13g之抗壞血酸亦溶解於該溶液，然後添加 30.16g之非晶形磷酸鐵(III)無水物。所得之分散液係在50℃下攪動3小時，然後過濾固體並以乙醇清洗之。乾燥係在室溫下進行數天。然後該材料係在a)氮氣氛或b)於氮氣氛中之5體積%的氫之下在1.5小時內加熱至550℃，且在該溫度保持2小時。二者樣本a)及b)均展現顯著比例之Fe2P2O7相(見圖15+16)。 24.48 g of lithium acetate was dehydrated and dissolved in 2000 ml of ethanol. 21.13 g of ascorbic acid was also dissolved in the solution, and then 30.16 g of amorphous iron (III) phosphate anhydrate was added. The resulting dispersion was stirred at 50 ° C for 3 hours, then the solid was filtered and washed with ethanol. The drying was carried out for several days at room temperature. The material was then heated to 550 ° C in 1.5 hours under a) nitrogen atmosphere or b) under 5 vol% hydrogen in a nitrogen atmosphere and maintained at this temperature for 2 hours. Both samples a) and b) exhibited a significant proportion of the Fe 2 P 2 O 7 phase (see Figure 15+16).

Claims (15)

一種用於製造非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物的方法，其特徵在於通式FePO4×2H2O之正磷酸鐵(III)或通式FePO4×2H2O之正磷酸鐵(III)的碳複合物(其中根據使用CuKα輻射之粉末X射線繞射分析，磷菱鐵礦(phosphosiderite)(磷菱鐵礦(metastrengite)II)晶體結構中存在至少80重量%的該正磷酸鐵(III))係在介於140與250℃之範圍內的溫度下脫水至殘餘水含量介於0與1重量%之間(包括結晶之結合水以及自由水二者)，以及至結晶水含量0.2H2O。 A method for producing an amorphous or amorphous iron(III) phosphate anhydrate or an amorphous or amorphous iron(III) phosphate anhydrate carbon composite characterized by the general formula FePO 4 × 2H 2 Carbon complex of iron orthophosphate (III) or iron (III) orthophosphate of the general formula FePO 4 × 2H 2 O (wherein based on powder X-ray diffraction analysis using CuKα radiation, phosphosiderite ( At least 80% by weight of the iron(III) orthophosphate in the crystal structure of the metasalgite II) is dehydrated to a residual water content of 0 and 1 at a temperature in the range of 140 and 250 °C. Between % by weight (both crystalline combined water and free water), and to crystalline water content 0.2H 2 O. 一種非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物，其係或可如申請專利範圍第1項所述方式製造。 An amorphous or amorphous iron (III) phosphate anhydrate or an amorphous or amorphous iron (III) phosphate anhydrate carbon composite, which may be manufactured as described in claim 1 . 如申請專利範圍第2項所述之非晶形或非晶形化的磷酸鐵(III)無水物或非晶形或非晶形化的磷酸鐵(III)無水物之碳複合物，其中在基於CuKα輻射的粉末X射線繞射圖中於2θ度為15.9±0.5、20.0±0.5、20.95±0.5、22.4±0.5及28.85±0.5處具有峰。 A carbon composite of amorphous or amorphous iron(III) phosphate anhydrate or amorphous or amorphous iron(III) phosphate anhydrate as described in claim 2, wherein CuKα radiation-based The powder X-ray diffraction pattern has peaks at 2θ degrees of 15.9±0.5, 20.0±0.5, 20.95±0.5, 22.4±0.5, and 28.85±0.5. 一種用於製造經鋰化的正磷酸鐵或經鋰化的正磷酸鐵碳複合物之方法，其特徵在於a)通式FePO4×2H2O之正磷酸鐵(III)或通式FePO4×2H2O之正磷酸鐵(III)的碳複合物(其中根據使用CuKα輻射之粉末X射線繞射分析，磷菱鐵礦 (phosphosiderite)(磷菱鐵礦(metastrengite)II)晶體結構中存在至少80重量%的該正磷酸鐵(III))係介於在140與250℃之範圍內的溫度下脫水至殘餘水含量介於0與1重量%之間(包括結晶之結合水以及自由水二者)，以及至結晶水含量0.2H2O，b)將該脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物分散在水或水性溶劑中，且於該分散液中添加介於0.8與1.2莫耳當量之鋰鹽，或該脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物係分散在含有介於0.8與1.2莫耳當量之呈溶解形式的鋰鹽之水或水性溶劑中，其中莫耳當量係關於該分散液中之鐵(III)及該鋰鹽中之鋰(I)離子的莫耳量，c)該水性分散液係與介於0.9與1.2電子當量之還原酮反應，其中還原酮之電子當量意指用以將該分散液中之鐵(III)還原成鐵(II)所需的還原酮之量，及d)所獲得之反應產物係在介於100與300℃範圍內之溫度及/或在低於大氣壓力之減壓下予以乾燥。 A method for producing lithiated iron orthophosphate or lithiated iron orthophosphate complex, characterized in that a) iron (III) orthophosphate of the formula FePO 4 × 2H 2 O or FePO 4 ×2H 2 O carbon complex of iron (III) orthophosphate (wherein according to powder X-ray diffraction analysis using CuKα radiation, there is a crystal structure of phosphosiderite (metastrengite II)) At least 80% by weight of the iron(III) orthophosphate) is dehydrated at a temperature in the range of from 140 to 250 ° C to a residual water content of between 0 and 1% by weight (including crystalline bound water and free water) Both) and to the water content of crystal water 0.2H 2 O, b) dispersing the dehydrated iron complex of iron (III) or the iron (III) phosphate in water or an aqueous solvent, and adding 0.8 and 1.2 molar equivalents to the dispersion a lithium salt, or the dehydrated iron complex of the iron (III) phosphate or the iron (III) phosphate, is dispersed in water or an aqueous solvent containing a lithium salt in a dissolved form of between 0.8 and 1.2 moles, Wherein the molar equivalent is about the amount of iron (III) in the dispersion and the amount of lithium (I) ions in the lithium salt, c) the aqueous dispersion reacts with a reducing ketone of between 0.9 and 1.2 electron equivalents Wherein the electron equivalent of the reduced ketone means the amount of reducing ketone required to reduce iron (III) in the dispersion to iron (II), and d) the reaction product obtained is between 100 and 300 Dry at temperatures in the range of °C and/or under reduced pressure below atmospheric pressure. 如申請專利範圍第4項所述之方法，其中該經乾燥之產物進一步在介於400與800℃範圍內之溫度下煅燒達一介於1與24小時之期間。 The method of claim 4, wherein the dried product is further calcined at a temperature in the range of 400 and 800 ° C for a period of between 1 and 24 hours. 如申請專利範圍第4及5項中之一項所述之方法，其中在添加該鋰鹽之前及在添加該還原酮之前，該脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物的水性分散液之pH值係設定及/或緩衝至7.0，較佳為6.5， 尤佳為6.0之值，其中較佳地使用有機羧酸及/或其酐及/或其鋰鹽，特佳地使用甲酸、乙酸、丙酸、正丁酸、戊酸及/或其酐及/或其鋰鹽來設定及/或緩衝該pH值。 The method of any one of claims 4 and 5, wherein the dehydrated iron (III) or the iron (III) iron is dehydrated before the addition of the lithium salt and before the addition of the reducing ketone. The pH of the aqueous dispersion of the composite is set and/or buffered to 7.0, preferably 6.5, especially good for a value of 6.0, wherein an organic carboxylic acid and/or its anhydride and/or a lithium salt thereof are preferably used, and fortunately, formic acid, acetic acid, propionic acid, n-butyric acid, valeric acid and/or its anhydride and/or The lithium salt is used to set and/or buffer the pH. 如申請專利範圍第4或5項所述之方法，其中該鋰鹽在水性分散液中之用量介於0.9與1.1，特佳地使用介於1.0與1.05莫耳當量及/或該還原酮之用量介於該水性分散液的1.0與1.05電子當量。 The method of claim 4, wherein the lithium salt is used in an aqueous dispersion in an amount of between 0.9 and 1.1, particularly preferably between 1.0 and 1.05 molar equivalents and/or the reducing ketone. The amount is between 1.0 and 1.05 electron equivalents of the aqueous dispersion. 如申請專利範圍第4或5項所述之方法，其中該水性分散液中之該鋰鹽係選自由以下所組成之群組：氫氧化鋰(LiOH)、碳酸鋰(Li2CO3)、乙酸鋰、甲酸鋰及其混合物。 The method of claim 4, wherein the lithium salt in the aqueous dispersion is selected from the group consisting of lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), Lithium acetate, lithium formate and mixtures thereof. 如申請專利範圍第4或5項所述之方法，其中該還原酮係選自由以下所組成之群組：羥基丙二醛(tartronaldehyde)(羥基丙二醛(hydroxypropandial))、抗壞血酸、還原酸(2,3-二羥基-2-環戊烯酮)、乙醯基福滿(acetylformoin)及上述者之混合物，其中該還原酮較佳為抗壞血酸。 The method of claim 4, wherein the reducing ketone is selected from the group consisting of tartronaldehyde (hydroxypropandial), ascorbic acid, and reducing acid ( 2,3-dihydroxy-2-cyclopentenone), acetylformoin, and mixtures thereof, wherein the reducing ketone is preferably ascorbic acid. 如申請專利範圍第4或5項所述之方法，其中步驟d)中該反應產物之乾燥係以混合實施。 The method of claim 4, wherein the drying of the reaction product in step d) is carried out by mixing. 如申請專利範圍第4或5項所述之方法，其中該經乾燥之產物之煅燒係在介於450與700℃，較佳係介於500與650℃範圍內之溫度進行達介於1與12小時，較佳係介於2與6小時之期間。 The method of claim 4, wherein the dried product is calcined at a temperature between 450 and 700 ° C, preferably between 500 and 650 ° C. 12 hours, preferably between 2 and 6 hours. 如申請專利範圍第4或5項所述之方法，其中步 驟a)中所獲得之脫水磷酸鐵(III)或該磷酸鐵(III)之脫水碳複合物在基於CuKα輻射的粉末X射線繞射圖中於2θ度為15.9±0.5、20.0±0.5、20.95±0.5、22.4±0.5及28.85±0.5處具有峰。 For example, the method described in claim 4 or 5, wherein the step The dehydrated iron complex of the dehydrated iron(III) phosphate or the iron(III) phosphate obtained in the step a) is 15.9±0.5, 20.0±0.5, 20.95 at the 2θ degree in the powder X-ray diffraction pattern based on CuKα radiation. There are peaks at ±0.5, 22.4±0.5 and 28.85±0.5. 如申請專利範圍第4或5項所述之方法，其中所使用之具有磷菱鐵礦(磷菱鐵礦(metastrengite)II)晶體結構的正磷酸鐵(III)或正磷酸鐵(III)之碳複合物為係根據或可根據DE 102007049757、DE 102009001204或DE 102011003125所製造的產物。 The method of claim 4, wherein the iron (III) orthophosphate (III) orthophosphate (III) having a crystal structure of a phosphate iron ore (metastrengite II) is used. The carbon composite is a product which is manufactured according to DE 102007049757, DE 102009001204 or DE 102011003125. 一種經鋰化的磷酸鐵或經鋰化的磷酸鐵碳複合物，其係如申請專利範圍第4項所述方式製造。 A lithiated iron phosphate or lithiated iron phosphate carbon composite produced in the manner described in claim 4 of the patent application. 一種如申請專利範圍第項2或3所述之非晶形或非晶形化的磷酸鐵(III)無水物或其碳複合物或如申請專利範圍第14項所述之經鋰化的磷酸鐵或其碳複合物的用途，其係用作鋰離子蓄電池(accumulator)之陰極材料。 An amorphous or amorphous iron (III) phosphate anhydrate or a carbon composite thereof according to claim 2 or 3, or a lithiated iron phosphate as described in claim 14 or The use of its carbon composite is used as a cathode material for a lithium ion accumulator.
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