CN101640267B - Preparation method of lithium iron phosphate as cathode material of lithium ion battery - Google Patents
Preparation method of lithium iron phosphate as cathode material of lithium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of lithium iron phosphate as a cathode material of a lithium ion battery, which comprises the following steps: uniformly mixing reaction liquid and pressurizing the reaction liquid; then enabling reaction raw materials to mix, carry out crystal nucleation and grow in a flowing process through an external heating heat pipe by utilizing the continuous flow of liquid in the heating pipe and the heating outside the heat pipe so as to continuously synthesize a lithium iron phosphate material; at the tail end of the reaction, cooling, filtering, washing and drying the liquid to obtain a finished lithium iron phosphate product. The invention can avoid large energy waste caused by repeated heating when a reaction kettle is utilized and is beneficial to energy saving and environment protection. When the liquid flows in the heating pipe, the materials are uniformly mixed and have smaller grain size, narrow grain size distribution and high purity; and because of continuous production, the performance of the materials is extremely stable, thus the invention is suitable for industrial mass production.
Description
Technical field
The present invention relates to the continuous preparation method of a kind of power lithium-ion battery with positive electrode, specifically, is a kind of flowing of water under high pressure hot liquid of utilizing, and prepares the method for ferrousphosphate lithium material continuously.
Background technology
LiFePO 4 (LiFePO
4) material be a new generation anode material for lithium-ion batteries, have aboundresources, cheap, safety and stability, discharge platform characteristic are good under extreme conditions such as super-charge super-discharge electricity, the cycle life advantages of higher, and become the outstanding candidate material of electrokinetic cell of generally acknowledging at present both at home and abroad.It is carried out a large amount of research both at home and abroad, particularly its synthesis technique, doping characteristic, carbon method for coating etc. have been carried out a large amount of research.The domestic patent that can retrieve is above 200 at present.In recent years, be that the industry such as electric automobile, electric tool, energy-storage battery of power is all developed faster with the lithium ion battery, also increasing to the demand of ferrousphosphate lithium material.
The preparation of lithium iron phosphate cathode material can be divided into solid phase method and liquid phase method simply.Solid phase method is divided into direct solid phase method and carbothermic method again.The former generally is to be raw material with ferrous iron, makes finished product through oversintering.The latter generally adopts ferric iron as raw material, by the reduction of the material in the course of reaction, ferric iron is reduced to ferrous iron, makes the LiFePO 4 finished product.Liquid phase method is meant the reaction by ion between solution, generates LiFePO 4 or presoma, makes finished product by heat treatment then.Liquid phase method does not have the diffusion process of atom between powder granule, can realize the synthetic of material under the homodisperse condition of reactive ion, and composition is more even than solid phase method, and is stable, is specially adapted to the preparation of ion doping type ferrousphosphate lithium material.Patents such as CN101209820, CN101209819, CN101106189, CN101117216, CN101121509 have proposed to make the process of presoma and LiFePO 4 finished product respectively.Above method all is to utilize reactor, by certain atmosphere, temperature or pressure condition realization response.But when being used for actual production, exist long, stirring heating time and reaction condition be difficult to control, can not the continous way discharging, problem such as slow, the energy consumption height of conducting heat.Above problem is the key that can not realize industrialized mass production rapidly of liquid phase synthesizing method.When for example utilizing conventional hydro thermal method technology to produce, main energy consumption is used for heating reaction system and container repeatedly, has caused the huge waste of the energy.The large-size reactor inwall is thicker, has more limited control transfer of heat, also is to cause that the system energy consumption is higher, the instability quality principal element.
Summary of the invention
Technical problem to be solved by this invention is, a kind of continuous production is provided, and performance is extremely stable, is suitable for the preparation method of the lithium ferrous phosphate as anode material of lithium ion battery of industrialized mass.
For achieving the above object, the preparation method of a kind of lithium ferrous phosphate as anode material of lithium ion battery of the present invention, may further comprise the steps: reaction liquid is mixed the back pressurization, then by the outer heat pipe that heats, utilize the continuous flow and the outer heating of heat pipe of liquid in the heat pipe, make reaction raw materials in flow process mixing, crystal nucleation, grow up, realize synthesizing lithium iron phosphate materials continuously, terminal in reaction, liquid is after cooling, after filtration, the washing, the oven dry after, obtain the LiFePO 4 finished product.
May further comprise the steps particularly:
1) with analytically pure solvable divalent iron salt, source of phosphoric acid, Li source compound, stoichiometric proportion according to ferrousphosphate lithium material, under the protection of inert gas, in material-compound tank, be dissolved in the pure water of high-speed stirred, form the mixed liquor of 0.05-5M concentration, described concentration is relative ferrous phosphate lithium concentration;
2) with after the mixed liquor process 0.5-5h stirring that obtains, liquid is after the high-pressure pump pressurization, and pressure reaches 5-15Kg/cm
2Utilize high-pressure pump to be pressed into heat pipe, pressure heat pipe dish is folded to be placed in the heating container, there is heat medium heating container inside, maintains 140-200 ℃, and mixing material flows in heat pipe, with heat medium generation heat exchange, through after 2-8 hour the heated at constant temperature, reach the heat pipe end, under the condition of HTHP, formed the LiFePO 4 suspension-turbid liquid this moment;
3) the LiFePO 4 suspension-turbid liquid enters cooling water pipe by adjuster valve, and cooling water pipe is placed in the cooled containers, and the material system is by under the water quench to 100 in the cooled containers ℃;
4) cooled liquid sprays by adjuster valve, wherein contained solid material after filtration, the washing, the oven dry after, obtain the ferrousphosphate lithium material finished product.
Described divalent iron salt is a kind of in ferrous sulfate heptahydrate, frerrous chloride or the ferrous nitrate.
Described source of phosphoric acid is a kind of in industrial phosphoric acid or the lithium dihydrogen phosphate.
Described Li source compound is a kind of in lithium hydroxide or the lithium dihydrogen phosphate.
Described inert gas is a kind of in helium or the argon gas.
Described heat medium is hot-air, superheated vapor or conduction oil.
Described pressure heat pipe is made up of the withstand voltage stainless steel coil pipe of internal diameter 5-25mm, and the heat-pipe constant-temperature section length guarantees the high temperature constant temperature time according to flow design.
Described divalent iron salt is pure for analyzing.
Wherein lithium dihydrogen phosphate can be simultaneously as source of phosphoric acid and lithium source.
Beneficial features of the present invention is: heat the energy huge waste that causes in the time of can avoiding utilizing reactor repeatedly, help energy-conserving and environment-protective.When liquid flowed in heat pipe, mixing of materials was even, and particle diameter is less, narrow diameter distribution, and purity is higher, and the ferrousphosphate lithium material of making has the favorable charge-discharge performance, and owing to produce continuously, performance is extremely stable, is suitable for industrialized mass.
Description of drawings
Fig. 1 is a flow sheet equipment schematic diagram of the present invention.
Embodiment
The preparation method of lithium ferrous phosphate as anode material of lithium ion battery of the present invention, may further comprise the steps: reaction liquid is mixed the back pressurization, then by the outer heat pipe that heats, utilize the outer heating of the continuous flow of liquid in the heat pipe and heat pipe, make reaction raw materials in flow process mixing, crystal nucleation, grow up, realize synthesizing lithium iron phosphate materials continuously, terminal in reaction, liquid through the cooling after, after filtration, the washing, the oven dry after, obtain the LiFePO 4 finished product.
As shown in Figure 1, the present invention may further comprise the steps particularly:
1) with analytically pure solvable divalent iron salt, source of phosphoric acid, Li source compound, stoichiometric proportion according to ferrousphosphate lithium material, under the protection of inert gas, in material-compound tank 1, be dissolved in the pure water of high-speed stirred, form the mixed liquor of 0.05-5M concentration, described concentration is relative ferrous phosphate lithium concentration;
2) with after the mixed liquor process 0.5-5h stirring that obtains, liquid is after high-pressure pump 8 pressurizations, and pressure reaches 5-15Kg/cm
2Utilize high-pressure pump 8 to be pressed into heat pipe 7, folded being placed in the heating container 2 of pressure heat pipe 7 dishes, there is heat medium heating container 2 inside, maintain 140-200 ℃, and mixing material flows in heat pipe 7, with heat medium generation heat exchange, through after 2-8 hour the heated at constant temperature, reach heat pipe 7 ends, under the condition of HTHP, formed the LiFePO 4 suspension-turbid liquid this moment;
3) the LiFePO 4 suspension-turbid liquid enters cooling water pipe 5 by adjuster valve 6, and cooling water pipe 5 is placed in the cooled containers 3, and the material system is by under the water quench to 100 in the cooled containers 3 ℃;
4) cooled liquid is by adjuster valve 4 ejection, and wherein contained solid material after filtration, after the washing, oven dry, obtain the ferrousphosphate lithium material finished product.
Described divalent iron salt is a kind of in ferrous sulfate heptahydrate, frerrous chloride or the ferrous nitrate.
Described source of phosphoric acid is a kind of in industrial phosphoric acid or the lithium dihydrogen phosphate.
Described Li source compound is a kind of in lithium hydroxide or the lithium dihydrogen phosphate.
Described inert gas is a kind of in helium or the argon gas.
Described heat medium is hot-air, superheated vapor or conduction oil.
Described pressure heat pipe is made up of the withstand voltage stainless steel coil pipe of internal diameter 5-25mm, and the heat-pipe constant-temperature section length guarantees the high temperature constant temperature time according to flow design.
Described divalent iron salt is pure for analyzing.
With specific embodiment technology is described below.
With industrial phosphoric acid 111.76g, the monohydrate lithium hydroxide 41.94g of analytically pure ferrous sulfate heptahydrate 277.85g, 85% concentration, under nitrogen protection, in material-compound tank, be dissolved in the 10Kg pure water of high-speed stirred, form the mixed liquor of 0.1M.The mixed solution that obtains utilizes high-pressure pump to be pressed into heat pipe after stirring 0.5h.Liquid pressurization back pressure is 5Kg/cm
2Heat pipe internal diameter 5mm, material is anti-corrosion austenitic stainless steel, 100 meters of heated constant temperature section length.Heating container inner sustain outside the heat pipe is at 140 ℃.The flow of regulating final outlet with adjuster valve reaches 4.089 ml/min, and calculating as can be known, liquid heating process in heat pipe is 8 hours.Liquid by adjuster valve, enters cooling water pipe behind superheater tube.Liquid in the cooling water pipe is cooled under the water cooling to 100 ℃, sprays by adjuster valve.Wherein contained solid material after filtration, the washing, the oven dry after, obtain the ferrousphosphate lithium material finished product.This reaction system product yield reaches more than 99.5%, 2.0 microns of product average grain diameters. gram volume reaches 149mAh/g, fluctuation is less than 3%. (the LiFePO 4 material gram volume of existing hydro thermal method synthetic technology manufacturing is generally 145mAh/g, and the capacity fluctuation ratio is 6-8%) between batch.
With analytically pure frerrous chloride 91.3Kg, lithium dihydrogen phosphate 103.9Kg, under argon shield, in material-compound tank, be dissolved in the 1000Kg pure water of high-speed stirred, form the 1M mixed aqueous solution.The mixed solution that obtains utilizes high-pressure pump to be pressed into heat pipe after stirring through 5h.Liquid pressurization back pressure reaches 15Kg/cm
2Heat pipe internal diameter 25mm, material is anti-corrosion austenitic stainless steel.20 meters of heated constant temperature section length.The heating container inner sustain is at 200 ℃, and the flow of regulating final outlet with adjuster valve is 81.77 ml/min, can calculate and know that liquid heating process in heat pipe is 2 hours.Liquid enters cooling water pipe by adjuster valve behind superheater tube.Liquid in the cooling water pipe is cooled under the water cooling to 100 ℃, sprays by adjuster valve.Wherein contained solid material after filtration, the washing, the oven dry after, obtain the ferrousphosphate lithium material finished product.This reaction system product yield reaches more than 99.5%, 2.5 microns of product average grain diameters. and gram volume reaches 148mAh/g, and fluctuation is less than 3%, much smaller than the capacity fluctuation ratio of existing hydro thermal method technology 6-8% between batch.
With industrial phosphoric acid 223.52g, the monohydrate lithium hydroxide 83.88g of analytically pure ferrous sulfate heptahydrate 555.7Kg, 85% concentration, under nitrogen protection, in material-compound tank, be dissolved in 4 tons of pure water of high-speed stirred, form the mixed liquor of 0.5M.The mixed solution that obtains utilizes high-pressure pump to be pressed into heat pipe after stirring through 2h.Liquid pressurization back pressure reaches 8Kg/cm
2Heat pipe internal diameter 15mm, material is anti-corrosion austenitic stainless steel, 50 meters of heated constant temperature section length.Heating container inner sustain outside the heat pipe is at 180 ℃, and the flow of regulating final outlet with adjuster valve reaches 36.8 ml/min, and calculating as can be known, liquid heating process in heat pipe is 4 hours.Liquid enters cooling water pipe by adjuster valve behind superheater tube.Liquid in the cooling water pipe is cooled under the water cooling to 100 ℃, sprays by adjuster valve.Wherein contained solid material after filtration, the washing, the oven dry after, obtain the LiFePO 4 material finished product.This reaction system product yield reaches more than 99.5%, 2.4 microns of product average grain diameters. and gram volume reaches 150mAh/g, and fluctuation is less than 3%, much smaller than the capacity fluctuation ratio of existing hydro thermal method technology 6-8% between batch.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. the preparation method of a lithium ferrous phosphate as anode material of lithium ion battery, it is characterized in that, may further comprise the steps: reaction liquid is mixed the back pressurization,, utilize the continuous flow and the outer heating of heat pipe of liquid in the heat pipe then by the heat pipe of outer heating, make reaction raw materials in flow process mixing, crystal nucleation, grow up, realize synthesizing lithium iron phosphate materials continuously, terminal in reaction, liquid is after cooling, after filtration, the washing, the oven dry after, obtain the LiFePO 4 finished product;
Specifically may further comprise the steps:
1) with solvable divalent iron salt, source of phosphoric acid, Li source compound, according to the stoichiometric proportion of ferrousphosphate lithium material, under the protection of inert gas, in material-compound tank, be dissolved in the pure water of high-speed stirred, form the mixed liquor of 0.05-5M concentration, described concentration is relative ferrous phosphate lithium concentration;
2) mixed liquor that obtains is stirred through 0.5-5h, liquid is after the high-pressure pump pressurization, and pressure reaches 5-15Kg/cm
2Utilize high-pressure pump to be pressed into heat pipe, pressure heat pipe dish is folded to be placed in the heating container, there is heat medium heating container inside, maintains 140-200 ℃, and mixing material flows in heat pipe, with heat medium generation heat exchange, through after 2-8 hour the heated at constant temperature, reach the heat pipe end, under the condition of HTHP, formed the LiFePO 4 suspension-turbid liquid this moment;
3) the LiFePO 4 suspension-turbid liquid enters cooling water pipe by adjuster valve, and cooling water pipe is placed in the cooled containers, and the material system is by under the water quench to 100 in the cooled containers ℃;
4) cooled liquid sprays by adjuster valve, wherein contained solid material after filtration, the washing, the oven dry after, obtain the ferrousphosphate lithium material finished product.
2. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described divalent iron salt is a kind of in ferrous sulfate heptahydrate, frerrous chloride or the ferrous nitrate.
3. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described source of phosphoric acid is a kind of in industrial phosphoric acid or the lithium dihydrogen phosphate.
4. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described Li source compound is a kind of in lithium hydroxide or the lithium dihydrogen phosphate.
5. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described inert gas is a kind of in helium or the argon gas.
6. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described heat medium is hot-air, superheated vapor or conduction oil.
7. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that, described pressure heat pipe is made up of the withstand voltage stainless steel coil pipe of internal diameter 5-25mm, and the heat-pipe constant-temperature section length guarantees the high temperature constant temperature time according to flow design.
8. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that, described divalent iron salt is pure for analyzing.
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