CN104183845B - A kind of lithium manganese phosphate nano particle and preparation method thereof - Google Patents
A kind of lithium manganese phosphate nano particle and preparation method thereof Download PDFInfo
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- CN104183845B CN104183845B CN201410413515.4A CN201410413515A CN104183845B CN 104183845 B CN104183845 B CN 104183845B CN 201410413515 A CN201410413515 A CN 201410413515A CN 104183845 B CN104183845 B CN 104183845B
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of lithium manganese phosphate nano particle disclosed by the invention, granular size is 50-100 nanometer, its preparation method is formed the solvent required for solvent thermal reaction with ethylene glycol, with four acetate hydrate manganese, two acetate hydrate lithiums, phosphoric acid for reaction mass, take P123 as surfactant, affect forming core and growth, at high temperature under high pressure, heat-treat.Afterwards under nitrogen or argon gas atmosphere protection, in 300-400 DEG C and 550-650 DEG C of calcine by steps, obtain lithium manganese phosphate nano particle.Constant product quality of the present invention, purity is high, and particle dispersion is good, be conducive to lithium ion diffusion, improve the chemical property of lithium ion battery, and preparation process is simple, and be easy to control, pollution-free, cost is low, is easy to large-scale production.
Description
Technical field
The present invention relates to a kind of lithium manganese phosphate nano material and preparation method thereof, particularly relate to a kind of lithium manganese phosphate nano particle and preparation method thereof.
Background technology
Lithium ion battery fills green power supply as one is high performance, be used widely in various portable type electronic product and communication tool in recent years, and be progressively developed as the electrical source of power of electric automobile, thus promote its future development to safety, environmental protection, low cost and high-energy-density.Wherein, the development of new electrode materials particularly positive electrode is very crucial.The anode material for lithium-ion batteries of extensively research concentrates on the LiMO of transition metal oxide as layer structure of lithium at present
2the LiMn of (M=Co, Ni, Mn) and spinel structure
2o
4.But as positive electrode, they respectively have shortcoming, LiCoO
2cost is high, natural resources shortage, and toxicity is large; Lithium nickelate (LiNiO
2) preparation difficulty, poor heat stability; LiMn
2o
4capacity is lower, and cyclical stability especially high-temperature behavior is poor.In order to solve the defect of above material, people have done large quantity research, and above positive electrode is being carried out to various modification with while improving its performance, the exploitation of novel anode material is also the emphasis paid close attention to always.Research finds, lithium manganese phosphate material operating voltage moderate (4.1V), theoretical capacity height 171mAh/g, good cycle, cost is very low, and his energy density is higher than LiFePO4 by 34%, and its high-energy-density and high safety performance make it in power lithium-ion battery, have outstanding application prospect, weak point is that its poorly conductive and lithium ion diffusion velocity are slow, and this has great association with the particle size of manganese-lithium phosphate anode material.The present invention utilizes simple method to prepare the manganese-lithium phosphate anode material of the less favorable dispersibility of size, is conducive to improving battery performance.
Summary of the invention
The object of the present invention is to provide a kind of favorable dispersibility and simple lithium manganese phosphate nano particle of preparation technology and preparation method thereof.
Lithium manganese phosphate nano particle of the present invention, granular size is 50-100 nanometer.
Prepare the method for above-mentioned lithium manganese phosphate nano particle, step is as follows:
1) poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer P123 is dissolved in ethylene glycol, stir at least 240 minutes, add four acetate hydrate manganese and ascorbic acid again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 0.25mol/L-1.0mol/L, the solution A of ascorbic acid concentrations to be 0.057mol/L-0.114mol/L, P123 concentration be 0.1-0.2g/mL;
2) take phosphoric acid, two acetate hydrate lithiums are dissolved in ethylene glycol, stir more than 30 minutes, formation phosphoric acid concentration is 0.25mol/L-1.0mol/L, and the concentration of lithium acetate is the suspension B of 0.25mol/L-3.0mol/L;
3) by step 2) suspension B under the state stirred, be added drop-wise to step 1) solution A in, form emulsion C, in emulsion C, the mol ratio of Li, Mn, P is 1 ~ 3:1:1;
4) the emulsion C of step 3) is transferred to autoclave, spent glycol regulates its volume to 2/3 ~ 4/5 of reactor volume, makes P concentration be 0.125mol/L-0.50mol/L, continues stirring more than 30 minutes;
5) reactor is airtight; heat-treat be incubated 4-48 hour at 160-230 DEG C after, then, be down to room temperature; take out product; filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 40 ~ 100 DEG C of temperature; again under nitrogen or argon; after 300 ~ 400 DEG C of calcining 3h, at 550-650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle.
The purity of raw material phosphoric acid used in said method, four acetate hydrate manganese, two acetate hydrate lithiums, ascorbic acid, P123 and solvent ethylene glycol, deionized water, acetone is all not less than chemical pure.
The present invention with four acetate hydrate manganese, two acetate hydrate lithiums, phosphoric acid for reaction mass, ethylene glycol is reaction dissolvent, by adding P123 surfactant, regulating and controlling forming core and the growth course of lithium manganese phosphate in heat treatment process, realizing the solvent-thermal process of single dispersing lithium manganese phosphate nano particle.The cleaning of the present invention to solvent-thermal process product is that the organic substance in order to be introduced by reaction mass is fully separated with the lithium manganese phosphate of synthesis, obtains the lithium manganese phosphate phase of pure phase.Employing absolute ethyl alcohol dewaters and not higher than the oven dry of 100 DEG C, is to obtain the good lithium manganese phosphate nano-powder of decentralized.In tube furnace, carrying out calcination processing, is to obtain single dispersing lithium manganese phosphate nano particle.
Constant product quality of the present invention, purity is high, and particle dispersion is good, is conducive to lithium ion diffusion, improves the large current density performance of lithium ion battery.Preparation process of the present invention is simple, is easy to control, and pollution-free, cost is low, is easy to large-scale production.
Accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of Fig. 1 lithium manganese phosphate nano particle;
Scanning electron microscopy (SEM) picture of Fig. 2 lithium manganese phosphate nano particle.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Example 1
1) P123 of 2.000g is dissolved in 20ml ethylene glycol, stir 240 minutes, add the four acetate hydrate manganese of 1.225g and the ascorbic acid of 0.200g again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 0.25mol/L, the solution A of ascorbic acid concentrations to be 0.057mol/L, P123 concentration be 0.1g/mL;
2) take 0.490g phosphoric acid, 0.510g bis-acetate hydrate lithium is dissolved in 20ml ethylene glycol, stir 30 minutes, formation phosphoric acid concentration is 0.25mol/L, and the concentration of lithium acetate is the suspension B of 0.25mol/L;
3) by step 2) prepared by suspension B under the state stirred, be added drop-wise to step 1) prepared by solution A in, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 1:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 60ml, spent glycol regulates its volume to 40ml, makes P concentration be 0.125mol/L, continues stirring 30 minutes;
5) by airtight for the reactor being configured with reaction mass in step 4), heat-treat be incubated 12 hours at 230 DEG C after.Then, be down to room temperature, take out product, filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 100 DEG C of temperature.Again under nitrogen or argon, after 350 DEG C of calcining 3h, 600 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle.
As shown in Figure 1, visible prepared material is the lithium manganese phosphate of pure phase to X-ray diffraction (XRD) collection of illustrative plates of the lithium manganese phosphate nanometer ellipsoid that this example is obtained; As shown in Figure 2, the lithium manganese phosphate nano particle size of visible synthesis is 50-100 nanometer to its scanning electron microscopy (SEM) photo.
Example 2
1) P123 of 3.000g is dissolved in 20ml ethylene glycol, stir 300 minutes, add the four acetate hydrate manganese of 2.45g and the ascorbic acid of 0.400g again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 0.5mol/L, the solution A of ascorbic acid concentrations to be 0.114mol/L, P123 concentration be 0.15g/mL;
2) take 0.98g phosphoric acid, 2.04g bis-acetate hydrate lithium is dissolved in 20ml ethylene glycol, stir 90 minutes, formation phosphoric acid concentration is 0.5mol/L, and the concentration of lithium acetate is the suspension B of 1.0mol/L;
3) by step 2) prepared by suspension B under the state stirred, be added drop-wise to step 1) prepared by solution A in, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 2:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 50ml, spent glycol regulates its volume to 40ml, makes P concentration be 0.25mol/L, continues stirring 90 minutes;
5) by airtight for the reactor being configured with reaction mass in step 4), heat-treat be incubated 24 hours at 200 DEG C after.Then, be down to room temperature, take out product, filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 80 DEG C of temperature.Again under nitrogen or argon, after 300 DEG C of calcining 3h, 650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle, size is 50-100 nanometer.
Example 3
1) P123 of 4.000g is dissolved in 20ml ethylene glycol, stir 360 minutes, add the four acetate hydrate manganese of 3.675g and the ascorbic acid of 0.320g again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 0.75mol/L, the solution A of ascorbic acid concentrations to be 0.909mol/L, P123 concentration be 0.20g/mL;
2) take 1.47g phosphoric acid, 4.59g bis-acetate hydrate lithium is dissolved in 20ml ethylene glycol, stir 150 minutes, formation phosphoric acid concentration is 0.75mol/L, and the concentration of lithium acetate is the suspension B of 2.25mol/L;
3) by step 2) prepared by suspension B under the state stirred, be added drop-wise to step 1) prepared by solution A in, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 3:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 55ml, spent glycol regulates its volume to 40ml, makes P concentration be 0.375mol/L, continues stirring 150 minutes;
5) by airtight for the reactor being configured with reaction mass in step 4), heat-treat be incubated 36 hours at 180 DEG C after.Then, be down to room temperature, take out product, filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 60 DEG C of temperature.Again under nitrogen or argon, after 400 DEG C of calcining 3h, 550 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle, size is 50-100 nanometer.
Example 4
1) P123 of 3.500g is dissolved in 20ml ethylene glycol, stir 400 minutes, add the four acetate hydrate manganese of 4.900g and the ascorbic acid of 0.24g again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 1.00mol/L, the solution A of ascorbic acid concentrations to be 0.068mol/L, P123 concentration be 0.175g/mL;
2) take 1.960g phosphoric acid, 2.040g bis-acetate hydrate lithium is dissolved in 20ml ethylene glycol, stir 200 minutes, formation phosphoric acid concentration is 1.00mol/L, and the concentration of lithium acetate is the suspension B of 1.00mol/L;
3) by step 2) prepared by suspension B under the state stirred, be added drop-wise to step 1) prepared by solution A in, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 1:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 50ml, spent glycol regulates its volume to 40ml, makes P concentration be 0.5mol/L, continues stirring 200 minutes;
5) by airtight for the reactor being configured with reaction mass in step 4), heat-treat be incubated 48 hours at 160 DEG C after.Then, be down to room temperature, take out product, filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 40 DEG C of temperature.Again under nitrogen or argon, after 350 DEG C of calcining 3h, 600 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle, size is 50-100 nanometer.
Claims (2)
1. a preparation method for lithium manganese phosphate nano particle, the size of this lithium manganese phosphate nano particle is 50-100 nanometer, and its preparation process is as follows:
1) P123 is dissolved in ethylene glycol, stir at least 240 minutes, add four acetate hydrate manganese and ascorbic acid again, be stirred to abundant dissolving, obtain that manganese acetate concentration is 0.25mol/L-1.0mol/L, the solution A of ascorbic acid concentrations to be 0.057mol/L-0.114mol/L, P123 concentration be 0.1-0.2g/mL;
2) take phosphoric acid, two acetate hydrate lithiums are dissolved in ethylene glycol, stir more than 30 minutes, formation phosphoric acid concentration is 0.25mol/L-1.0mol/L, and the concentration of lithium acetate is the suspension B of 0.25mol/L-3.0mol/L;
3) by step 2) suspension B under the state stirred, be added drop-wise to step 1) solution A in, form emulsion C, in emulsion C, the mol ratio of Li, Mn, P is 1 ~ 3:1:1;
4) the emulsion C of step 3) is transferred to autoclave, spent glycol regulates its volume to 2/3 ~ 4/5 of reactor volume, makes P concentration be 0.125mol/L-0.50mol/L, continues stirring more than 30 minutes;
5) reactor is airtight; heat-treat be incubated 4-48 hour at 160-230 DEG C after, then, be down to room temperature; take out product; filter, successively with the cleaning of deionized water, absolute ethyl alcohol or acetone, dry at 40 ~ 100 DEG C of temperature; again under nitrogen or argon; after 300 ~ 400 DEG C of calcining 3h, at 550-650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle.
2. the preparation method of lithium manganese phosphate nano particle according to claim 1, it is characterized in that raw material phosphoric acid used, four acetate hydrate manganese, two acetate hydrate lithiums, ascorbic acid, P123 and solvent ethylene glycol, deionized water, acetone purity be all not less than chemical pure.
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