CN108423650B - Preparation method of lithium ion battery anode material lithium iron phosphate - Google Patents

Preparation method of lithium ion battery anode material lithium iron phosphate Download PDF

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CN108423650B
CN108423650B CN201810265006.XA CN201810265006A CN108423650B CN 108423650 B CN108423650 B CN 108423650B CN 201810265006 A CN201810265006 A CN 201810265006A CN 108423650 B CN108423650 B CN 108423650B
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lithium
source
iron phosphate
phosphate
plasma
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CN108423650A (en
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杨改
王波
秦显忠
蔡飞鹏
蒋波
高金华
陈花
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Energy Research Institute of Shandong Academy of Sciences
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

A preparation method of lithium iron phosphate as a positive material of a lithium ion battery comprises the following steps: weighing a lithium source, an iron source, a phosphorus source and a carbon source according to a proportion, ball-milling all the raw materials, fully mixing, drying, putting into a plasma rotary furnace, performing plasma treatment for 5-60min at the temperature of 300-600 ℃ in an inert atmosphere or a reducing atmosphere at the furnace pressure of 6-100Pa to obtain the lithium iron phosphate serving as the positive electrode material of the lithium ion battery. According to the method, the plasma rotary furnace is selected as the plasma processing device, the relevant process conditions are optimized, the particle size of the lithium iron phosphate is further reduced, the crystal structure of the prepared lithium iron phosphate anode material is good in development, and impurities in the crystal structure are few.

Description

Preparation method of lithium ion battery anode material lithium iron phosphate
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a preparation method of a lithium ion battery anode material lithium iron phosphate.
Background
Lithium iron phosphate (LiFePO) of orthorhombic olivine structure4) Has the following advantages: the raw materials are cheap and the resources are very rich; the working voltage is moderate (3.4V); the platform has good characteristics, and the voltage is extremely stable (comparable to a voltage-stabilized power supply); the theoretical capacity is large (170 mAh/g); stable structure and excellent safety performance (O and P are firmly combined by a strong covalent bond, so that the material is difficult to decompose by oxygen evolution); the high-temperature performance and the cycle performance are good; the volume is reduced during charging, and the volume effect is good when the carbon cathode material is matched; the electrolyte has good compatibility with most electrolyte systems and good storage performance; is nontoxic and is a real green material. At present, the lithium iron phosphate material is mainly sintered by a high-temperature solid phase method, the temperature is 700-800 ℃, the time is about 10-20 hours, the synthesis consumes time and energy, and the electrochemical performance of the material is unstable, so that the phase change is increasedAdding to the production cost of the material. How to reduce the production cost while taking into account the stable electrical properties of the material is a problem that many researchers are studying at present.
CN101604747A discloses a preparation method of a lithium iron phosphate anode material, which is used for preparing the lithium iron phosphate anode material and comprises the steps of preparing materials, spraying the materials by using a plasma spraying technology, wherein the plasma spraying technology is completed by plasma spraying equipment, a spraying outlet of the plasma spraying equipment is connected with a closed spraying forming cavity, the length of the spraying forming cavity is 8-15 m, and inert gases are filled in an inner cavity of the plasma spraying equipment and the spraying forming cavity. The reaction raw materials can be directly melted, and the lithium iron phosphate anode material with high sphericity, uniform components and stable performance can be instantly prepared.
CN102064318A discloses a method for realizing carbon coating of lithium iron phosphate by radio frequency plasma enhanced chemical vapor deposition. The method comprises the steps of placing lithium iron phosphate in a reaction chamber, reacting for 15-60 min in reactive gas under radio frequency plasma, maintaining the total air pressure of the reaction chamber at 8-30 Pa, and the power output power of the radio frequency plasma at 40-100W, wherein the reactive gas is acetylene or mixed gas of hydrogen and methane with the volume ratio of 1: 1. The carbon-coated film produced by the method has uniform components and easily controlled thickness, and has the advantages of low temperature and short reaction time compared with the conventional chemical vapor deposition. Prepared carbon-coated LiFePO4The crystal structure of the material is well developed, XRD diffraction test results do not contain impure phases, and the carbon-coated LiFePO4The material has large specific capacity and excellent rate capability and cycle performance. The test of a button type simulated battery formed by the lithium metal shows that the first discharge capacity is 166.0 mAh.g at 0.5C and 1C respectively-1And 165mAh · g-1The capacity retention after 50 cycles was 99.5% and 99.3%, respectively.
Disclosure of Invention
The invention aims to provide a preparation method of lithium iron phosphate serving as a positive electrode material of a lithium ion battery, which has the advantages of simple process and low cost and is suitable for industrial production.
Plasma is often referred to as a fourth state of matter existence, in addition to the solid, liquid, and gas states. When voltage is applied between two electrodes of the reaction chamber, electrons emitted by the cathode are accelerated under the action of an electromagnetic field to obtain energy, and the energy and gas atoms or molecules in the reaction chamber are subjected to inelastic collision to decompose, excite or ionize the electrons to generate glow on one hand, and charged particles (electrons, ions, active groups, metastable atomic nucleus molecules and the like) are formed in the reaction chamber on the other hand.
A preparation method of lithium iron phosphate as a positive material of a lithium ion battery comprises the following steps: weighing a lithium source, an iron source, a phosphorus source and a carbon source according to a proportion, ball-milling all the raw materials, fully mixing, drying, putting into a plasma rotary furnace, carrying out plasma treatment for 5-60min at 300-600 ℃ and preferably 400-500 ℃ in an inert atmosphere or a reducing atmosphere at the furnace pressure of 6-100Pa, preferably 20-50Pa to obtain the lithium iron phosphate serving as the cathode material of the lithium ion battery.
The lithium source is one or more of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate and lithium oxalate; the iron source is one or more of ferric phosphate, ferric nitrate, ferric trichloride and ferric sulfate; the phosphorus source is one or more of phosphoric acid, iron phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate and trisodium phosphate, the dosage of the lithium source, the dosage of the iron source and the dosage of the phosphorus source are respectively calculated by lithium, iron and phosphorus, and the molar ratio is (1-1.2) to 1: 1; the carbon source is selected from one or more of citric acid, ethylene glycol, sucrose and glucose, and the dosage of the carbon source is 0.1-20 wt% of that of the lithium iron phosphate; the inert and reducing atmosphere is one or more of nitrogen, argon, hydrogen, methane, acetylene and toluene, and the flow rate is 0.1-10 sccm.
The ball milling speed is 300-800rpm, the ball milling time is 0.5-2h, the drying temperature is 80-100 ℃, and the drying time is 2-10 h.
The selected plasma source is a radio frequency plasma source, the frequency is 1-50MHz, the power is 1-300W, and the rotating speed of the rotary furnace is 0.1-5 rpm.
The particle size of the lithium iron phosphate is 0.01-10 microns, and preferably 0.01-0.1 micron.
The invention has the beneficial effects that: the lithium iron phosphate cathode material of the lithium ion battery with good electrochemical performance is obtained at a lower temperature and in a shorter time by adopting a low-temperature plasma chemical vapor deposition process, so that the effects of reducing energy consumption and saving cost are achieved; the plasma rotary furnace is selected as the plasma processing device, so that the relevant process conditions are optimized, and the particle size of the lithium iron phosphate is further reduced. The heating time of the lithium iron phosphate is reduced, the particles are heated more uniformly, the crystal structure of the lithium iron phosphate anode material prepared by the method is good, and impurities in the crystal structure are few. The button cell assembled by taking the lithium iron phosphate material as the anode and the lithium sheet as the cathode has excellent high-rate charge-discharge and low-temperature discharge performance. The initial discharge specific capacities of 2.5-4.2V, 0.1C and 10C at room temperature can respectively reach 150mAh/g and 120mAh/g, and the capacity retention rates after 500 cycles are respectively 95.6% and 94.5%.
Detailed Description
Example 1
Weighing 30.2g of iron phosphate, 7.48g of lithium carbonate, 7g of sucrose and 20ml of deionized water, placing the materials in a ball milling tank, carrying out ball milling at the rotating speed of 600rpm for 1h, taking out the materials, drying the materials at the temperature of 80 ℃ for 2h, transferring the dried powder into a plasma enhanced chemical vapor deposition rotary furnace, wherein the rotating speed of the rotary furnace is 3rpm, vacuumizing the rotary furnace to 60Pa, introducing argon into the rotary furnace, controlling the flow rate to be 5sccm, heating the rotary furnace to 400 ℃, starting a plasma power supply, setting the power to be 200W, naturally cooling the power to room temperature after reacting for 30min, continuously introducing air to the pressure in the rotary furnace to be atmospheric pressure, taking out a lithium iron phosphate material, wherein the average particle size of the lithium iron. The lithium iron phosphate material is used as an anode, a lithium sheet is used as a cathode to assemble a battery, and the first discharge specific capacities of the battery at room temperature under the multiplying power of 0.1C and 10C are respectively 152mAh/g and 120 mAh/g.
Example 2
The same parts of this embodiment as embodiment 1 will not be described again, but the differences are: ferrous oxalate is selected as an iron source, hydrogen-argon mixed gas is selected as an atmosphere, the flow rate is 3sccm, the temperature of the rotary furnace is raised to 500 ℃, and the power of a plasma source is set to 300W. The average particle size of the lithium iron phosphate material particles is measured to be 0.04 mu m, the micro-nano lithium iron phosphate material is used as an anode, a lithium sheet is used as a cathode to assemble the battery, and the first discharge specific capacities at room temperature under the multiplying power of 0.1C and 10C are respectively 149mAh/g and 118 mAh/g.
Comparative example 1
Weighing 30.2g of iron phosphate, 7.48g of lithium carbonate, 7g of sucrose and 20ml of deionized water, placing the materials into a ball milling tank, carrying out ball milling at the rotating speed of 600rpm for 1h, taking out the materials, drying the materials at the temperature of 80 ℃ for 2h, transferring the dried powder into direct current arc plasma jet equipment, setting the length of a forming cavity to be 10m, starting a plasma power supply, setting the power to be 200W, naturally cooling the materials to the room temperature after reacting for 30min, continuously ventilating the reaction furnace until the pressure is atmospheric pressure, taking out the lithium iron phosphate material, wherein the average particle size of the lithium iron phosphate material is 7 microns. The lithium iron phosphate material is used as an anode, a lithium sheet is used as a cathode to assemble a battery, and the first discharge specific capacities of the battery at room temperature under the multiplying power of 0.1C and 10C are respectively 122mAh/g and 110 mAh/g.

Claims (3)

1. A preparation method of lithium iron phosphate as a positive material of a lithium ion battery comprises the following steps: weighing a lithium source, an iron source, a phosphorus source and a carbon source according to a proportion, ball-milling all the raw materials, fully mixing, drying, putting into a plasma rotary furnace, and carrying out plasma treatment for 5-60min in an inert atmosphere or a reducing atmosphere to obtain a lithium ion battery anode material lithium iron phosphate; the particle size of the lithium iron phosphate is 0.01-0.1 micrometer; the selected plasma source is a radio frequency plasma source, the frequency is 1-50MHz, the power is 1-300W, and the rotating speed of the plasma rotary furnace is 0.1-5 rpm; the pressure in the plasma rotary furnace is 20-50Pa, and the temperature is 400-500 ℃.
2. The production method according to claim 1, characterized in that the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate, and lithium oxalate; the iron source is one or more of ferric phosphate, ferric nitrate, ferric trichloride and ferric sulfate; the phosphorus source is one or more of phosphoric acid, iron phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate and trisodium phosphate, the dosage of the lithium source, the dosage of the iron source and the dosage of the phosphorus source are respectively calculated by lithium, iron and phosphorus, and the molar ratio is (1-1.2) to 1: 1; the carbon source is selected from one or more of citric acid, ethylene glycol, sucrose and glucose, and the dosage of the carbon source is 0.1-20 wt% of that of the lithium iron phosphate; the inert or reducing atmosphere is one or more of nitrogen, argon, hydrogen, methane, acetylene and toluene, and the flow rate is 0.1-10 sccm.
3. The preparation method according to claim 1, wherein the ball milling rotation speed is 300-800rpm, the ball milling time is 0.5-2h, the drying temperature is 80-100 ℃, and the drying time is 2-10 h.
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CN103794788A (en) * 2014-02-21 2014-05-14 合肥国轩高科动力能源股份公司 Surface carbon coating method of lithium iron phosphate positive electrode material
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KR101129368B1 (en) * 2009-03-31 2012-03-26 미쓰이 긴조꾸 고교 가부시키가이샤 Positive electrode active material for lithium battery
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Publication number Priority date Publication date Assignee Title
CN101237039A (en) * 2008-01-08 2008-08-06 上海大学 Method for synthesizing LiFePO4/C material based on chemical gas phase sediment auxiliary solid phase method
CN102148368A (en) * 2011-02-24 2011-08-10 宁波工程学院 Preparation method of lithium ion battery anode composite material and special device thereof
CN102745663A (en) * 2012-07-09 2012-10-24 四川九驰能源科技股份有限公司 Method for preparing lithium iron phosphate material
CN103794788A (en) * 2014-02-21 2014-05-14 合肥国轩高科动力能源股份公司 Surface carbon coating method of lithium iron phosphate positive electrode material
CN107221666A (en) * 2017-06-28 2017-09-29 深圳市贝特瑞纳米科技有限公司 Combination electrode material of Heteroatom doping graphene coated and preparation method thereof
CN107845807A (en) * 2017-10-31 2018-03-27 山东省科学院能源研究所 A kind of preparation method of Manganese Based Cathode Materials for Lithium Ion Batteries

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