CN104183845A - Lithium manganese phosphate nanoparticles and preparation method thereof - Google Patents

Lithium manganese phosphate nanoparticles and preparation method thereof Download PDF

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Publication number
CN104183845A
CN104183845A CN201410413515.4A CN201410413515A CN104183845A CN 104183845 A CN104183845 A CN 104183845A CN 201410413515 A CN201410413515 A CN 201410413515A CN 104183845 A CN104183845 A CN 104183845A
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mol
lithium
manganese phosphate
concentration
lithium manganese
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CN104183845B (en
Inventor
徐刚
李玲玲
李峰
任召辉
刘涌
李翔
沈鸽
韩高荣
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • 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
    • 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
    • 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
    • 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

The invention discloses lithium manganese phosphate nanoparticles. The nanoparticles have the size of 50-100nm. A preparation method of the nanoparticles comprises the steps that a solvent, required for solvent thermal reaction, is prepared from ethylene glycol, manganese acetate tetrahydrate, lithium acetate dihydrate and phosphoric acid are taken as reacting materials, P123 is taken as a surfactant, so as to influence nucleation and growth, heat treatment is carried out at high temperature and high pressure, then, segmented calcining is carried out at the temperature of 300-400 DEG C and 550-650 DEG C under the protection of a nitrogen or argon atmosphere, and then, the lithium manganese phosphate nanoparticles are obtained. The lithium manganese phosphate nanoparticles and the preparation method thereof have the advantages that the product is stable in quality, high in purity and good in particle dispersibility and is beneficial to the diffusion of lithium ions and the improvement of the electrochemical properties of a lithium-ion battery, and the preparation process is simple in process, easy to control and low in cost and is pollution-free, so that the large-scale production is facilitated.

Description

A kind of lithium manganese phosphate nano particle and preparation method thereof
Technical field
The present invention relates to a kind of lithium manganese phosphate nano material and preparation method thereof, relate in particular to a kind of lithium manganese phosphate nano particle and preparation method thereof.
Background technology
Lithium ion battery is as a kind of high performance green power supply of filling, in various portable type electronic products and communication tool, be used widely in recent years, and be progressively developed as the electrical source of power of electric automobile, thereby promote it to the future development of safety, environmental protection, low cost and high-energy-density.Wherein, particularly the development of positive electrode is very crucial for new electrode materials.The anode material for lithium-ion batteries of broad research concentrates on the transition metal oxide of lithium as the LiMO of layer structure at present 2the LiMn of (M=Co, Ni, Mn) and spinel structure 2o 4.But they respectively have shortcoming, LiCoO as positive electrode 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, above positive electrode are being carried out to various modifications with when improving its performance, and the exploitation of novel anode material is also the emphasis of paying close attention to always.Research is found, lithium manganese phosphate material operating voltage moderate (4.1V), the high 171mAh/g of theoretical capacity, good cycle, cost is very low, and his energy density is higher by 34% than LiFePO4, 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 is slow, and the particle size of this and manganese-lithium phosphate anode material has great associated.The present invention utilizes simple method to prepare the manganese-lithium phosphate anode material of the favorable dispersibility that size is less, is conducive to improve battery performance.
Summary of the invention
The object of the present invention is to provide simple lithium manganese phosphate nano particle of a kind of favorable dispersibility and preparation technology and preparation method thereof.
Lithium manganese phosphate nano particle of the present invention, granular size is 50-100 nanometer.
The method of preparing 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 again four hydration manganese acetate and ascorbic acid, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.25 mol/L-1.0 mol/L, ascorbic acid concentrations are 0.057 mol/L-0.114 mol/L, and P123 concentration is the solution A of 0.1-0.2 g/mL;
2) take phosphoric acid, two hydration lithium acetates are dissolved in ethylene glycol, stir more than 30 minutes, forming phosphoric acid concentration is 0.25 mol/L-1.0 mol/L, the concentration of lithium acetate is the suspension B of 0.25 mol/L-3.0 mol/L;
3) by step 2) suspension B under the state stirring, 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, and making P concentration is 0.125 mol/L-0.50 mol/L, continues to stir more than 30 minutes;
5) reactor is airtight; be incubated 4-48 hour at 160-230 ℃ after, heat-treat, then, be down to room temperature; take out product; filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40～100 ℃ of temperature, dry; again under nitrogen or argon shield; after 300 ~ 400 ℃ of calcining 3h, at 650 ℃ of calcining 4h of 550-, obtain lithium manganese phosphate nano particle.
In said method, the purity of raw material phosphoric acid, four hydration manganese acetates, two hydration lithium acetates, ascorbic acid, P123 and solvent ethylene glycol used, deionized water, acetone is all not less than chemical pure.
It is reaction mass that four hydration manganese acetates, two hydration lithium acetates, phosphoric acid are take in the present invention, ethylene glycol is reaction dissolvent, by adding P123 surfactant, forming core and the growth course of lithium manganese phosphate in regulation and control heat treatment process, realize single solvent heat of lithium manganese phosphate nano particle that disperses synthetic.The present invention is for the organic substance of reaction mass introducing is fully separated with synthetic lithium manganese phosphate to the cleaning of solvent heat synthetic product, obtains the lithium manganese phosphate phase of pure phase.Employing absolute ethyl alcohol dewaters and not higher than the oven dry of 100 ℃, is in order to obtain the good lithium manganese phosphate nano-powder of decentralized.In tube furnace, carry out calcination processing, be in order to obtain single lithium manganese phosphate nano particle that disperses.
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
Below in conjunction with embodiment, further illustrate the present invention.
Example 1
1) P123 of 2.000 g is dissolved in to 20 ml ethylene glycol, stir 240 minutes, add again the four hydration manganese acetates of 1.225g and the ascorbic acid of 0.200g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.25 mol/L, ascorbic acid concentrations are 0.057 mol/L, and P123 concentration is the solution A of 0.1 g/mL;
2) take 0.490g phosphoric acid, 0.510g bis-hydration lithium acetates are dissolved in 20 ml ethylene glycol, stir 30 minutes, forming phosphoric acid concentration is 0.25 mol/L, the concentration of lithium acetate is the suspension B of 0.25 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, 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, and making P concentration is 0.125 mol/L, continues to stir 30 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, heat-treat be incubated 12 hours at 230 ℃ after.Then, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 100 ℃ of temperature, dry.Under nitrogen or argon shield, after 350 ℃ of calcining 3h, 600 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again.
X-ray diffraction (XRD) collection of illustrative plates of the lithium manganese phosphate nanometer ellipsoid that this example makes as shown in Figure 1, the lithium manganese phosphate that visible prepared material is pure phase; As shown in Figure 2, visible synthetic lithium manganese phosphate nano particle size is 50-100 nanometers to its scanning electron microscopy (SEM) photo.
Example 2
1) P123 of 3.000 g is dissolved in to 20 ml ethylene glycol, stir 300 minutes, add again the four hydration manganese acetates of 2.45g and the ascorbic acid of 0.400g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.5 mol/L, ascorbic acid concentrations are 0.114 mol/L, and P123 concentration is the solution A of 0.15 g/mL;
2) take 0.98g phosphoric acid, 2.04g bis-hydration lithium acetates are dissolved in 20 ml ethylene glycol, stir 90 minutes, forming phosphoric acid concentration is 0. 5 mol/L, the concentration of lithium acetate is the suspension B of 1.0 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, 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, and making P concentration is 0.25 mol/L, continues to stir 90 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, heat-treat be incubated 24 hours at 200 ℃ after.Then, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 80 ℃ of temperature, dry.Under nitrogen or argon shield, after 300 ℃ of calcining 3h, 650 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, and size is 50-100 nanometers.
Example 3
1) P123 of 4.000 g is dissolved in to 20 ml ethylene glycol, stir 360 minutes, add again the four hydration manganese acetates of 3.675g and the ascorbic acid of 0.320g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.75 mol/L, ascorbic acid concentrations are 0.909 mol/L, and P123 concentration is the solution A of 0.20 g/mL;
2) take 1.47g phosphoric acid, 4.59g bis-hydration lithium acetates are dissolved in 20 ml ethylene glycol, stir 150 minutes, forming phosphoric acid concentration is 0. 75 mol/L, the concentration of lithium acetate is the suspension B of 2.25 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, 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, and making P concentration is 0.375 mol/L, continues to stir 150 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, heat-treat be incubated 36 hours at 180 ℃ after.Then, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 60 ℃ of temperature, dry.Under nitrogen or argon shield, after 400 ℃ of calcining 3h, 550 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, and size is 50-100 nanometers.
Example 4
1) P123 of 3.500 g is dissolved in to 20 ml ethylene glycol, stir 400 minutes, add again the four hydration manganese acetates of 4.900g and the ascorbic acid of 0.24 g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 1.00mol/L, ascorbic acid concentrations are 0.068 mol/L, and P123 concentration is the solution A of 0.175 g/mL;
2) take 1.960g phosphoric acid, 2.040g bis-hydration lithium acetates are dissolved in 20 ml ethylene glycol, stir 200 minutes, forming phosphoric acid concentration is 1.00 mol/L, the concentration of lithium acetate is the suspension B of 1.00 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, 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, and making P concentration is 0. 5 mol/L, continues to stir 200 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, heat-treat be incubated 48 hours at 160 ℃ after.Then, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40 ℃ of temperature, dry.Under nitrogen or argon shield, after 350 ℃ of calcining 3h, 600 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, and size is 50-100 nanometers.

Claims (3)

1. a lithium manganese phosphate nano particle, is characterized in that described nano particle size is 50-100 nanometer.
2. prepare the method for lithium manganese phosphate nano particle as claimed in claim 1, it is characterized in that step is as follows:
1) P123 is dissolved in ethylene glycol, stir at least 240 minutes, add again four hydration manganese acetate and ascorbic acid, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.25 mol/L-1.0 mol/L, ascorbic acid concentrations are 0.057 mol/L-0.114 mol/L, and P123 concentration is the solution A of 0.1-0.2 g/mL;
2) take phosphoric acid, two hydration lithium acetates are dissolved in ethylene glycol, stir more than 30 minutes, forming phosphoric acid concentration is 0.25 mol/L-1.0 mol/L, the concentration of lithium acetate is the suspension B of 0.25 mol/L-3.0 mol/L;
3) by step 2) suspension B under the state stirring, 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, and making P concentration is 0.125 mol/L-0.50 mol/L, continues to stir more than 30 minutes;
5) reactor is airtight; be incubated 4-48 hour at 160-230 ℃ after, heat-treat, then, be down to room temperature; take out product; filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40～100 ℃ of temperature, dry; again under nitrogen or argon shield; after 300 ~ 400 ℃ of calcining 3h, at 650 ℃ of calcining 4h of 550-, obtain lithium manganese phosphate nano particle.
3. the preparation method of lithium manganese phosphate nano particle according to claim 2, is characterized in that the purity of raw material phosphoric acid used, four hydration manganese acetates, two hydration lithium acetates, ascorbic acid, P123 and solvent ethylene glycol, deionized water, acetone is all not less than chemical pure.
CN201410413515.4A 2014-08-21 2014-08-21 A kind of lithium manganese phosphate nano particle and preparation method thereof Expired - Fee Related CN104183845B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006569A (en) * 2015-06-03 2015-10-28 浙江大学 Nano-scale lithium manganese phosphate material and preparing method and application thereof
CN113594625A (en) * 2021-07-20 2021-11-02 烟台大学 Preparation and application of 3D self-supporting film for lithium-sulfur battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009544563A (en) * 2006-12-22 2009-12-17 ユミコア ソシエテ アノニム Synthesis of electroactive crystalline nanometric LiMnPO4 powder
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009544563A (en) * 2006-12-22 2009-12-17 ユミコア ソシエテ アノニム Synthesis of electroactive crystalline nanometric LiMnPO4 powder
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUNG-CUONG DINH等: "Large discharge capacities at high current rates for carbon-coated LiMnPO4 nanocrystalline cathodes", 《JOURNAL OF POWER SOURCES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006569A (en) * 2015-06-03 2015-10-28 浙江大学 Nano-scale lithium manganese phosphate material and preparing method and application thereof
CN113594625A (en) * 2021-07-20 2021-11-02 烟台大学 Preparation and application of 3D self-supporting film for lithium-sulfur battery

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