WO2012022264A1 - 制造电化学活性材料的方法 - Google Patents

制造电化学活性材料的方法 Download PDF

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Publication number
WO2012022264A1
WO2012022264A1 PCT/CN2011/078568 CN2011078568W WO2012022264A1 WO 2012022264 A1 WO2012022264 A1 WO 2012022264A1 CN 2011078568 W CN2011078568 W CN 2011078568W WO 2012022264 A1 WO2012022264 A1 WO 2012022264A1
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lithium
ball mill
grinding cylinder
phosphate
grinding
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PCT/CN2011/078568
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English (en)
French (fr)
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董明
苏振华
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恒正科技（苏州）有限公司
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Publication of WO2012022264A1 publication Critical patent/WO2012022264A1/zh

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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
    • C01B25/45—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for producing an electrochemically active material, in particular to a method for preparing an electrochemically active material by cyclic continuous carbon-free reduction-low temperature synthesis.
  • An excellent lithium-ion battery should have at least the following advantages: high and stable operating voltage, high specific energy, high energy density, long cycle life, and no memory effect.
  • SONY company in 1990 The commercial lithium-ion battery introduced in the year basically meets the above conditions. Therefore, this lithium-ion battery can be rapidly promoted and become a mainstream product in the secondary battery market.
  • mobile phones, laptops and other portable electrical devices mostly use lithium-ion batteries as the power source, and the demand for it will continue to grow.
  • lithium-ion batteries may be used in electric vehicles and large-scale energy storage batteries, which has led to the accelerated development of theoretical and applied research of lithium-ion batteries.
  • the materials used in lithium ion batteries mainly include positive electrode materials (including active materials and conductive materials, etc.) , anode materials, current collectors and separators.
  • positive electrode materials including active materials and conductive materials, etc.
  • the positive active material used in commercial lithium-ion batteries is still LiCoO2.
  • such a positive electrode active material has excellent electrochemical properties.
  • cobalt resources are scarce, expensive, toxic, and poor in biological safety, and are not suitable for large-scale applications. Therefore, researchers have been working on new positive active materials such as lithium iron phosphate. (LiFePO4), lithium vanadium phosphate (Li3V2(PO4)3), and the like.
  • Lithium iron phosphate (LiFePO4), which has stable crystal structure, good safety, excellent cycle performance, no use of strategic resources, nickel and cobalt, low price, non-toxic and environmentally friendly materials, due to its stable crystal structure, overcharge and overcharge It has a strong ability to release and is recognized as the best positive electrode material for manufacturing high-safety, low-cost, long-life lithium batteries.
  • Lithium vanadium phosphate (Li3V2(PO4)3) is a high performance lithium ion battery cathode material.
  • Patent CN 101172597A proposes the use of iron powder as the iron source, but using ammonium dihydrogen phosphate synthesis, which also emits polluting gases.
  • patent CN101172599 It is proposed to reduce the precursor of iron oxide and phosphoric acid by carbon coating method, and synthesize lithium iron phosphate.
  • the pre-production process is complicated, the cost is high, and the carbon coating cannot achieve uniform stability, and the synthesis produces a large amount of carbon dioxide. Emissions into the atmosphere cause pollution.
  • Patent application CN101106194 on January, January 16 The invention discloses a preparation method of lithium vanadium phosphate cathode material for lithium ion battery, and the prepared lithium vanadium phosphate matrix is coated with carbon material in vitro, and the cathode material lithium vanadium phosphate is synthesized by using nanoparticle secondary molding liquid phase method, which simplifies. Operating procedures, but liquid phase synthesis results in poor batch stability and high production costs.
  • Lithium iron phosphate materials are currently produced by industrial processes using wet mixing and spray drying followed by high temperature synthesis. This process has complicated procedures in the early stage, high cost, unstable process control, large batch variation, uneven material mixing, incomplete sintering reaction, large amount of electric energy consumption, and low production efficiency. The invention thus proceeds.
  • the object of the present invention is to provide a method for producing an electrochemically active material, which has a short processing reaction time, low energy consumption, and excellent performance of the processed product.
  • the carbon-free synthesis process can be used to improve the purity of the material, reduce the emission of carbon dioxide, and contribute to environmental protection.
  • a method of making an electrochemically active material characterized in that the method comprises the steps of:
  • the iron salt, lithium salt or phosphorus salt compound is iron element: lithium element: phosphorus element molar ratio is 1 : 1 : 1
  • the proportion is pulverized and mixed in a vibrating ball mill, and the cycle is operated as above;
  • the mixture is transferred to a ball mill rotary furnace and fired in an inert atmosphere.
  • the iron salt is selected from one or more of the following compounds: ferrous phosphate, triiron tetroxide, ferric oxide, ferrous oxide, iron hydroxide, ferrous oxalate;
  • the lithium salt is selected from the group consisting of One or more of the following compounds: lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, dihydrogen phosphate, lithium phosphate;
  • the phosphorus salt is selected from one or more of the following compounds: ferrous phosphate, Dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, phosphorus pentoxide.
  • the vibrating ball mill comprises a grinding cylinder, wherein the grinding cylinder is provided with a ball grinding medium, and both ends of the grinding cylinder are provided with a feeding port and a discharging port, and the grinding cylinder discharging port is connected through a circulating feeding pipe
  • the feeding inlet of the grinding cylinder is provided with a base supporting the grinding cylinder at a lower end of the grinding cylinder, and a damping spring is arranged between the base and the grinding cylinder.
  • the grinding cylinder is one or more vibrating barrels with a ball grinding medium, and an exciter driven by a driving motor is disposed outside the vibrating barrel body, and after the vibrator is activated, the grinding medium in the grinding barrel resonates the grinding material.
  • the ball milling medium is one of metal, ceramic or a combination thereof; the ball milling medium is one of a column shape, a sphere shape, a rod shape or a combination thereof, and the size is a single size or a combination of a plurality of sizes.
  • the inert atmosphere in step (2) of the method is selected from the group consisting of argon, nitrogen, and helium.
  • the firing step is synthesized by a high temperature solid phase method, and the heating temperature and time are passed through the PID.
  • the controller is controlled separately, the calcination temperature is controlled at 20 0 °C to 900 °C, and the calcination time is 1 h to 6 h.
  • the invention adopts vibration
  • the moving ball mill circulates, mixes and dries the material.
  • the vibrating ball mill comprises one or more vibrating barrels with ball milling medium, and the outside of the barrel has heating means to realize circulation, mixing and drying of the materials.
  • the material is pulverized and mixed by the ball milling medium, so that the material particles are continuously pulverized and thoroughly mixed, thereby making the material synthesis fast and complete, and the finished product has good consistency.
  • the material is mainly a mixture of a ferrous salt, a lithium salt and a phosphate, and the molar ratio of the ferrous salt, the lithium salt and the phosphate is 1 : 1 : 1
  • the electrochemically active material is lithium iron phosphate. Different from the general treatment of lithium iron phosphate with ferric salt, the ferrous salt is carbon-free synthesis, no need to add carbon for redox reaction, no large amount of carbon dioxide is generated, which is not environmentally friendly, and the finished lithium iron phosphate contains Low carbon content, high purity and better performance.
  • the firing process passes PID (proportion - integral -
  • the differential controller is controlled separately, and the low temperature synthesis zone and the high temperature synthesis zone can be set to effectively control the material reaction time and temperature.
  • the bin connected to the discharge system has a cold water cooling system for cooling the processed active material.
  • the discharge port of the furnace tube can also be provided with a returning system, and the materials that need to be processed are returned to the ball mill heating zone for cycle processing.
  • the ball milling medium is one or more of metal and ceramic; the shape of the ball milling medium is spherical or cylindrical; the ball milling medium is of a single size or a plurality of sizes, that is, the ball milling medium is of the same size, or
  • the ball milling media is a mixture of ball milling media of various sizes. The material, shape and size of the ball mill media can be selected as needed to meet the crushing needs of the material.
  • the processing is as follows: the materials are thoroughly mixed and continuously added to the ball mill rotary furnace through the feed system under the protection of an inert gas (preferably nitrogen), and the temperature is controlled at 200 to 900 during the low temperature synthesis. Degree, heat for 1 to 6 hours, then cool.
  • an inert gas preferably nitrogen
  • the material is pulverized, mixed and reacted by a vibrating ball mill, so that the materials are fully mixed, which is beneficial to the material to fully react and synthesize, the morphology and structure of the composite material, the particle size distribution, and the vibration. Excellent in solid density, specific surface area and electrochemical performance.
  • the invention can select the environment-friendly material for the carbon-free processing of lithium iron phosphate to meet the environmental protection needs; and at the same time, improve the purity of lithium iron phosphate.
  • the invention can effectively control the synthesis speed, temperature and time of the materials in the furnace body, so that the product can exhibit good electrochemical stability, high charge and discharge capacity and excellent rate performance. .
  • the invention has short reaction time, effectively reduces energy consumption and reduces product cost.
  • FIG. 1 is a schematic structural view of a vibratory ball mill according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural view of a ball mill rotary kiln according to an embodiment of the present invention
  • FIG. 3 is a graph showing electrochemical charge and discharge curves of the obtained material according to a specific embodiment of the present invention.
  • a vibrating ball mill is used to pulverize, mix, and circulate the material
  • the vibrating ball mill includes a grinding cylinder 1 , and the grinding cylinder 1
  • There is a ball milling medium 2 and two ends of the grinding cylinder are provided with a feeding port 11 and a discharging port 12, and the grinding cylinder discharging port 12 is connected to the grinding cylinder feeding port 11 through a circulating feeding pipe, and the lower end of the grinding cylinder Set support cylinder
  • a base of 1 is provided with a damping spring 3 between the base and the grinding cylinder 1 .
  • the structure of the ball mill rotary kiln 4 is as shown in Fig. 2, including the feeding system, the discharging system and the furnace tube.
  • At least one ball mill heating zone 43 having a ball milling medium 2 is disposed in the furnace tube 42 of the ball mill rotary kiln 4.
  • the baffle shape is the same as that of the furnace body, and is fixed to the furnace tube 42.
  • Ball milling media 2 It is spherical or cylindrical.
  • the ball milling medium 2 is one or more of a metal and a ceramic.
  • the ball mill media 2 can be of a uniform size or a plurality of sizes.
  • the material is continuously entered into the ball mill rotary furnace under nitrogen protection conditions, and the temperature is controlled by 200 to 400 degrees during the low temperature synthesis process.
  • the temperature in the high temperature zone is controlled at 400 to 800 degrees, and the rotation speed is 1 to 4 hours, 1 revolution per minute, and then cooled at room temperature.
  • the product is prepared by powdering, testing and packaging to obtain lithium iron phosphate.
  • conductive carbon black and binder are added to form a pole piece, and a metal lithium plate is selected for the electrochemical test.
  • the tap density of the material prepared in this embodiment is greater than 1.3. g/cm 3
  • the electrode material has an electrochemical discharge capacity of more than 150 mAh/g, as shown in FIG.
  • Iron oxide and dihydrogen phosphate and lithium carbonate or lithium hydroxide molar ratio 1 : 1 : 1 After mixing in a vibrating ball mill, and then adding conductive carbon black, the material is continuously entered into the ball mill rotary furnace under nitrogen protection conditions. During the low temperature synthesis process, the temperature is controlled by 200 to 400 degrees, and the temperature is kept 1 to 4 Hours, when the temperature in the high temperature zone is controlled at 400 to 800 degrees, the temperature is kept at 1 to 4 hours. Every minute, then cool at room temperature.
  • the product is prepared by powdering, testing and packaging to obtain lithium iron phosphate.
  • a conductive agent and a binder are added to prepare a pole piece, and a metal lithium piece is selected for the test electrode.
  • the tap density of the material prepared in this embodiment is greater than 1.2 g/cm 3
  • the electrochemical material discharge capacity of the electrode material is greater than 150 mAh/g.
  • Will iron oxide and lithium phosphate molar ratio 1 : 1 After mixing in a vibrating ball mill, and then adding conductive carbon black, the material is continuously entered into the ball mill rotary furnace under nitrogen protection conditions. During the low temperature synthesis process, the temperature is controlled by 200 to 400 degrees, and the temperature is kept 1 to 4 Hours, when the temperature in the high temperature zone is controlled at 400 to 800 degrees, the temperature is kept at 1 to 4 hours. Every minute, then cool at room temperature.
  • the product is prepared by powdering, testing and packaging to obtain lithium iron phosphate.
  • a conductive agent and a binder are added to prepare a pole piece, and a metal lithium piece is selected for the test electrode.
  • the tap density of the material prepared in this embodiment is greater than 1.2 g/cm 3
  • the electrochemical material discharge capacity of the electrode material is greater than 150 mAh/g.
  • the ferrous iron ferrous phosphate used in the first embodiment is used as a reaction raw material, and does not need to add conductive carbon black when the reaction is carried out in a ball mill rotary kiln, and the process does not generate a large amount of carbon dioxide, is more environmentally friendly, and has high product purity; It can be seen that the tap density of the material prepared in the first embodiment is larger than that of the specific examples 2 and 3.
  • the processing time of the invention is short, the energy consumption is small, and the processed product has excellent performance, and at the same time
  • the use of carbon-free processing technology improves the purity of the material and reduces the emission of carbon dioxide, which is conducive to environmental protection.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Description

制造电化学活性材料的方法
技术领域
本发明涉及一种制造电化学活性材料的方法，特别是设计一种循环连续式无碳还原-低温合成制备电化学活性材料的方法。
背景技术
优秀的锂离子电池至少应具有以下优点：高而稳定的工作电压、高的比能量、高的能量密度、长的循环寿命以及无记忆效应等。 SONY 公司于 1990 年推出的商品化锂离子电池，基本满足上述条件，因此，这种锂离子电池得以迅速推广，成为二次电池市场上的主流产品。目前移动电话、笔记本电脑和其它一些便携式电气设备大多使用锂离子电池作为电源，而且对它的需求还将持续增长．将来，电动汽车和大型储能电池都可能使用锂离子电池，这使锂离子电池的理论和应用研究进入加速发展的阶段。
锂离子电池中使用的材料主要包括正极材料 ( 含活性物质和导电物质等 ) 、负极材料、集流体和隔膜等。目前，商品化的锂离子电池中使用的正极活性物质仍然是以 LiCoO2 为主，这种正极活性物质具有优异的电化学性能。然而，钴资源稀少、昂贵、有毒、生物学安全性差，不适合大规模的应用。因此，研究人员一直致力于研究新的正极活性物质，如磷酸亚铁锂 (LiFePO4) 、磷酸钒锂（ Li3V2(PO4)3 ）等。
磷酸亚铁锂(LiFePO4)，它具有稳定的晶体结构，安全性好，循环性能特别好，不使用战略资源镍钴、价格低、材料无毒环保，由于其晶体结构稳定，耐过充和过放的能力强，被公认为制造高安全、低成本、长寿命的锂电池的最佳正极材料。磷酸钒锂（Li3V2(PO4)3）是一种高性能锂离子电池正极材料。它具有较高放电平台；较高的充放电容量，理论容量为197mAh/g，相比于其他锂离子电池正极材料， 具有较大能量密度，良好的安全性能，并且价格低廉，被认为是未来最有前途的锂离子电池正极材料之一。
专利 CN 101172597A 提出了采用铁粉作为铁源，但采用磷酸二氢铵合成，其也排放污染气体。专利 CN101172599 提出采用碳包覆的方法还原氧化铁与磷酸组成的前驱体，合成磷酸亚铁锂，但是此制备技术前期工艺较为复杂，成本较高，且碳包覆无法达到均一稳定，合成产生大量二氧化碳，排放至大气中造成污染。
专利申请 CN101106194 于 2008 月 1 月 16 日公开了一种锂离子电池正极材料磷酸钒锂的制备方法，制备的磷酸钒锂基体，基体外包覆有碳材料，利用纳米颗粒二次成型液相法合成正极材料磷酸钒锂，简化了操作程序，但液相合成造成批次稳定性差，生产成本较高。
磷酸亚铁锂材料目前工业化生产采用的是湿法混合和喷雾干燥的方法，随后进行高温合成。此工艺，前期工序繁琐，成本较高，过程控制不稳定，造成批次性差异大，物料混合不均匀导致烧结反应不完全，消耗大量电能，生产效率低等问题。本发明由此而来。
发明内容
本发明目的是提供一种电化学活性材料的制造方法，加工 反应时间短，能源耗费少，加工出的产品 性能优良 ，同时可 采用无碳合成工艺，提高了材料的纯度，减少了二氧化碳的排出，有利于环保。
为了解决现有技术中的烧结反应不完全，消耗大量电能，生产效率低等问题，本发明提供的技术方案是：
一种制造电化学活性材料的方法，其特征在于所述方法包括以下步骤：
（ 1 ）将铁盐、锂盐或磷盐化合物按铁元素：锂元素：磷元素摩尔比为 1 ： 1 ： 1 的比例在振动球磨机中粉碎、混合，循环如上操作；
（ 2 ）在步骤（ 1 ）混匀工序之后，转入球磨回转炉中在惰性气氛下烧成。
优选的，所述方法步骤（ 1 ）中所述铁盐选自一种或两种以上的以下化合物：磷酸亚铁、四氧化三铁、三氧化二铁、氧化亚铁、氢氧化铁、草酸亚铁；所述锂盐选自一种或两种以上的以下化合物：碳酸锂、氢氧化锂、磷酸二氢锂、磷酸氢二锂、磷酸锂；所述磷盐选自一种或两种以上的以下化合物：磷酸亚铁、磷酸二氢氨、磷酸氢二氨、磷酸二氢锂、五氧化二磷。
优选的，所述振动球磨机包括磨筒，所述磨筒内设有球磨介质，所述磨筒两端设置有进料口和出料口，所述磨筒出料口通过循环送料管连接所述磨筒进料口，磨筒下端设置支撑磨筒的机座，所述机座与磨筒间设置减震弹簧。
优选的，所述磨筒为一个或多个具有球磨介质的振动桶体，振动桶体外侧设置驱动电机驱动的激振器，所述激振器启动后使磨筒内研磨介质共振研磨物料。
优选的，所述球磨介质为金属、陶瓷中的一种或其组合；所述球磨介质为柱形、球形、棒形的一种或其组合，大小尺寸为单一尺寸或多种尺寸的组合。
优选的，所述方法步骤（ 2 ）中惰性气氛选自选自氩气、氮气、氦气的一种。
优选的，所述方法中所述烧成工序采用高温固相法合成，加热温度和时间通过 PID 控制器单独控制，煅烧温度控制在 20 0 ℃～900℃，煅烧时间1h～6h。
本发明采用振 动球磨机对物料进行循环、混和、干燥，所述振动球磨机包括一个或多个具有球磨介质的振动桶体，桶体外侧具有加热装置，实现物料的循环、混和、干燥。通过球磨介质对物料进行粉碎和混合，使得物料颗粒不断被粉碎、混合彻底均匀，进而使得物料合成快速、完全，成品一致性好。
进一步的，所述物料主要为亚铁盐、锂盐和磷酸盐的混合物，所述亚铁盐、锂盐和磷酸盐的摩尔比为 1 ： 1 ： 1 ，所述电化学活性材料为磷酸亚铁锂。与一般采用三价铁盐加工磷酸亚铁锂不同，采用亚铁盐为无碳合成，无需再加入碳进行氧化还原反应，不会产生大量二氧化碳而不利于环保，同时成品的磷酸亚铁锂含碳量少，纯度高，性能更加优良。
进一步的，所述烧成工序通过 PID （比例 - 积分 - 微分）控制器单独控制，可以设置低温合成区和高温合成区，有效控制物料反应时间、温度。与出料系统连接的接料仓具有冷水冷却系统，用来对加工好的活性材料进行冷却。炉管的出料口还可以设置回料系统，将还需要加工的物料回送到球磨加热区间，循环加工。
进一步的，所述球磨介质为金属、陶瓷中的一种或多种；球磨介质的形状为球形或圆柱形；所述球磨介质为单一尺寸或多个尺寸，即球磨介质为同一尺寸规格，或球磨介质为多种尺寸规格的球磨介质混合而成。球磨介质的材质、形状和大小可以根据需要选取，以满足物料的粉碎需要。
进一步的，加工过程如下：将物料充分混合，并在惰性气体（优选的是氮气）保护条件下通过进料系统连续加入球磨回转炉内，低温合成过程中，温度控制在 200 ～ 900 度，保温 1 ～ 6 小时，随后冷却。
相对于现有技术中的方案，本发明的优点是：
1 、本发明在进行电化学活性材料的加工时，通过振动球磨机对物料进行边粉碎、边混合、边反应，使得物料混合充分，利于材料充分反应合成，合成材料的形貌结构、粒度分布、振实密度、比表面积和电化学性能优良。
2 ．本发明可以选用环境友好物料进行磷酸亚铁锂的无碳加工，满足环保需要；同时提高了磷酸亚铁锂的纯度。
3 ．本发明相比现有静态烧结和动态烧结，其能有效控制炉体中的物料的合成速度、温度、时间，使得产品能表现出具有良好的电化学稳定性，充放电容量高、倍率性能优良。
4 ．本发明反应时间短，有效降低能耗，降低产品成本。
附图说明
下面结合附图及实施例对本发明作进一步描述：
图 1 为本发明具体实施例振动球磨机的结构示意图；
图 2 为本发明具体实施例球磨回转炉的结构示意图；
图 3 为本发明具体实施例一所得材料电化学充放电曲线图。
其中：1为磨筒；2为球磨介质，3为减震弹簧，4为球磨回转炉；42炉管；43球磨加热区间；45常规加热区间；47挡板；48进料系统；49出料系统。
具体实施方式
以下结合具体实施例对上述方案做进一步说明。应理解，这些实施例是用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以根据具体厂家的条件做进一步调整，未注明的实施条件通常为常规实验中的条件。
实施例 1 磷酸亚铁锂的制备
该实施例中采用振动球磨机进行物料的粉碎、混合、循环，振动球磨机包括磨筒 1 ，所述磨筒 1 内设有球磨介质 2 ，所述磨筒两端设置有进料口 11 和出料口 12 ，所述磨筒出料口 12 通过循环送料管连接所述磨筒进料口 11 ，磨筒下端设置支撑磨筒 1 的机座，所述机座与磨筒 1 间设置减震弹簧 3 。
然后采用球磨回转炉合成，球磨回转炉 4 的结构如图 2 所示，包括进料系统、出料系统和炉管 42 ，所述球磨回转炉 4 的炉管 42 内设有至少一个具有球磨介质 2 的球磨加热区间 43 。炉管 42 内部分布的一个常规加热区间 45 和两个球磨加热区间 43 。每个区间的加热温度和时间采用 PID 单独控制。在每个球磨加热区间两侧有挡板 47 ，中间有球磨介质 2 ，挡板形状和炉体截面相同，固定在炉管 42 内支架上，挡板 47 直径小于炉管管径，挡板上分布着筛孔，炉体和挡板 47 之间的空隙以及筛孔的孔径小于球磨介质 2 的最小直径。球磨介质 2 为球形或圆柱形。球磨介质 2 为金属、陶瓷中的一种或多种。球磨介质 2 可以是均一尺寸，也可以是多个尺寸。
将磷酸亚铁和碳酸锂或氢氧化锂按摩尔比1：1在振动球磨机充分混合后，在氮气保护条件下将物料连续进入球磨回转炉中，低温合成过程中，温度控制200～400度，保温1～4小时，高温区控制温度在400～800度时，保温1～4小时回转速度1周转/每分钟，随后室温冷却。经制粉、测试、包装得到产品磷酸亚铁锂。电化学测试过程，添加导电碳黑，粘结剂，制成极片，电化学测试对电极选用金属锂片。本实施例制备出的材料振实密度大于1.3 g/cm 3 ,电极物质电化学放电克容量大于150mAh/g，如图3所示。
实施例 2 磷酸亚铁锂的制备
振动球磨机和球磨回转炉如实施例 1 所述。
将氧化铁和磷酸二氢氨和碳酸锂或氢氧化锂按摩尔比 1 ： 1 ： 1 在振动球磨机充分混合，随后添加导电碳黑混合后，在氮气保护条件下将物料连续进入球磨回转炉，低温合成过程中，温度控制 200 ～ 400 度，保温 1 ～ 4 小时，高温区控制温度在 400 ～ 800 度时，保温 1 ～ 4 小时回转速度 1 周转 / 每分钟，随后室温冷却。经制粉、测试、包装得到产品磷酸亚铁锂。电化学测试过程中，添加导电剂，粘结剂，制作极片，测试对电极选用金属锂片。本实施例制备出的材料振实密度大于 1.2 g/cm 3 , 电极物质电化学放电克容量大于 150mAh/g 。
实施例 3 磷酸亚铁锂的制备
振动球磨机和球磨回转炉如实施例 1 所述。
将铁的氧化物和磷酸锂按摩尔比 1 ： 1 在振动球磨机充分混合，随后添加导电碳黑混合后，在氮气保护条件下将物料连续进入球磨回转炉，低温合成过程中，温度控制 200 ～ 400 度，保温 1 ～ 4 小时，高温区控制温度在 400 ～ 800 度时，保温 1 ～ 4 小时回转速度 1 周转 / 每分钟，随后室温冷却。经制粉、测试、包装得到产品磷酸亚铁锂。电化学测试过程中，添加导电剂，粘结剂，制作极片，测试对电极选用金属锂片。本实施例制备出的材料振实密度大于 1.2 g/cm 3 , 电极物质电化学放电克容量大于 150mAh/g 。
可以看出，具体实施例一采用的二价铁的磷酸亚铁作为反应原料，在球磨回转炉中反应时，无需添加导电碳黑，加工过程不产生大量二氧化碳，更加环保，同时产品纯度高；可以看出具体实施例一制备出材料的振实密度要较具体实施例二和三大。
本发明加工 反应时间短，能源耗费少，加工出的产品 性能优良 ，同时可 采用无碳加工工艺，提高了材料的纯度，减少了二氧化碳的排出，有利于环保。
上述实例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人是能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。

Claims (7)

1 ．一种制造电化学活性材料的方法，其特征在于所述方法包括以下步骤：
（ 1 ）将铁盐、锂盐或磷盐化合物按铁元素：锂元素：磷元素摩尔比为 1 ： 1 ： 1 的比例在振动球磨机中粉碎、混合，循环如上操作；
（ 2 ）在步骤（ 1 ）混匀工序之后，转入球磨回转炉中在惰性气氛下烧成。
2 、根据权利要求 1 所述的方法，其特征在于所述方法步骤（ 1 ）中所述铁盐选自一种或两种以上的以下化合物：磷酸亚铁、四氧化三铁、三氧化二铁、氧化亚铁、氢氧化铁、草酸亚铁；所述锂盐选自一种或两种以上的以下化合物：碳酸锂、氢氧化锂、磷酸二氢锂、磷酸氢二锂、磷酸锂；所述磷盐选自一种或两种以上的以下化合物：磷酸亚铁、磷酸二氢氨、磷酸氢二氨、磷酸二氢锂、五氧化二磷。
3 、根据权利要求 1 所述的方法，其特征在于所述振动球磨机包括磨筒（ 1 ），所述磨筒（ 1 ）内设有球磨介质（ 2 ），所述磨筒两端设置有进料口（ 11 ）和出料口（ 12 ），所述磨筒出料口（ 12 ）通过循环送料管连接所述磨筒进料口（ 11 ），磨筒下端设置支撑磨筒（ 1 ）的机座，所述机座与磨筒（ 1 ）间设置减震弹簧（ 3 ）。
4 、根据权利要求 3 所述的方法，其特征在于所述磨筒（ 1 ）为一个或多个具有球磨介质的振动桶体，振动桶体外侧设置驱动电机驱动的激振器，所述激振器启动后使磨筒内研磨介质共振研磨物料。
5 、根据权利要求 3 所述的方法，其特征在于所述球磨介质为金属、陶瓷中的一种或其组合；所述球磨介质为柱形、球形、棒形的一种或其组合，大小尺寸为单一尺寸或多种尺寸的组合。
6 、根据权利要求 1 所述的方法，其特征在于所述方法步骤（ 2 ）中惰性气氛选自选自氩气、氮气、氦气的一种。
7、根据权利要求1所述的方法，其特征在于所述方法中所述烧成工序采用高温固相法合成，加热温度和时间通过PID控制器单独控制，煅烧温度控制在200℃～900℃，煅烧时间1h～6h。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114887719A (zh) * 2022-04-12 2022-08-12 临沂大学 一种机械化学法制作纳米粉体的工艺方法
CN116177513A (zh) * 2022-12-08 2023-05-30 攀钢集团攀枝花钢铁研究院有限公司 两段式焙烧制备磷酸钒锂锂电正极材料的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101916860A (zh) * 2010-08-19 2010-12-15 恒正科技（苏州）有限公司 制造电化学活性材料的方法
CN102522526B (zh) * 2011-12-13 2013-11-20 济宁市无界科技有限公司 转炉式锂电池正极或负极材料的生产设备及工艺
CN108483061A (zh) * 2018-05-21 2018-09-04 埃肯有机硅（上海）有限公司 非防爆车间用低闪点增粘剂加料装置
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1348231A (zh) * 2000-10-05 2002-05-08 索尼株式会社 非水电解质电池和固体电解质电池
CN201006459Y (zh) * 2007-02-27 2008-01-16 徐慰南 多功能超细振动球磨机
US20090081549A1 (en) * 2007-06-18 2009-03-26 Ben-Jie Liaw Electrochemical Composition and Associated Technology
CN201407891Y (zh) * 2009-05-19 2010-02-17 恒正科技（苏州）有限公司 球磨回转炉
CN101671012A (zh) * 2009-10-13 2010-03-17 恒正科技（苏州）有限公司 电化学活性材料的制造方法
CN101916860A (zh) * 2010-08-19 2010-12-15 恒正科技（苏州）有限公司 制造电化学活性材料的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2311305Y (zh) * 1997-12-11 1999-03-24 徐锦华 超细粉碎机
CN100567142C (zh) * 2006-09-30 2009-12-09 中南大学 磷酸铁锂系复合氧化物的制备方法
CN100576608C (zh) * 2007-05-22 2009-12-30 龚思源 一种锂离子电池正极材料磷酸铁锂的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1348231A (zh) * 2000-10-05 2002-05-08 索尼株式会社 非水电解质电池和固体电解质电池
CN201006459Y (zh) * 2007-02-27 2008-01-16 徐慰南 多功能超细振动球磨机
US20090081549A1 (en) * 2007-06-18 2009-03-26 Ben-Jie Liaw Electrochemical Composition and Associated Technology
CN201407891Y (zh) * 2009-05-19 2010-02-17 恒正科技（苏州）有限公司 球磨回转炉
CN101671012A (zh) * 2009-10-13 2010-03-17 恒正科技（苏州）有限公司 电化学活性材料的制造方法
CN101916860A (zh) * 2010-08-19 2010-12-15 恒正科技（苏州）有限公司 制造电化学活性材料的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114887719A (zh) * 2022-04-12 2022-08-12 临沂大学 一种机械化学法制作纳米粉体的工艺方法
CN116177513A (zh) * 2022-12-08 2023-05-30 攀钢集团攀枝花钢铁研究院有限公司 两段式焙烧制备磷酸钒锂锂电正极材料的方法

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