CN104183844B - The hydrothermal synthesis method of lithium ion battery anode material manganese lithium phosphate nano particle - Google Patents
The hydrothermal synthesis method of lithium ion battery anode material manganese lithium phosphate nano particle Download PDFInfo
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- CN104183844B CN104183844B CN201410413442.9A CN201410413442A CN104183844B CN 104183844 B CN104183844 B CN 104183844B CN 201410413442 A CN201410413442 A CN 201410413442A CN 104183844 B CN104183844 B CN 104183844B
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Abstract
The hydrothermal synthesis method of lithium ion battery anode material manganese lithium phosphate nano particle disclosed by the invention; taking deionized water as solvent; taking manganese source, lithium source, phosphoric acid be as reaction mass, taking block copolymer as template, potassium hydroxide is mineralizer; promote lithium manganese phosphate forming core and growth; under HTHP, heat-treat, afterwards under nitrogen or argon gas atmosphere protection; 550-650 DEG C of heat preservation sintering processing, obtains 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, improve the chemical property of lithium ion battery, and preparation process is simple, is easy to control, and pollution-free, cost is low, is easy to large-scale production.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery anode material manganese lithium phosphate, relate in particular to a kind of hydrothermal synthesis method of lithium manganese phosphate nano particle.
Background technology
Lithium ion battery is the novel battery after cadmium nickel, nickel metal hydride battery. Because lithium ion battery has the advantages such as operating voltage is high, volume is little, quality is light, 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.
At present, the anode material for lithium-ion batteries of broad research concentrates on the transition metal oxide of lithium as the LiMO of layer structure2The LiMn of (M=Co, Ni, Mn) and spinel structure2O4. But they respectively have shortcoming, LiCoO as positive electrode2Cost is high, natural resources shortage, and toxicity is large, and its discharge platform voltage is about 3.7V; Lithium nickelate (LiNiO2) preparation difficulty, poor heat stability; LiMn2O4Capacity 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 being carried out to various modifications with in improving its performance, 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 its 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 with carbon-coating that size is less, be conducive to improve battery performance, and there is not yet thisly taking block copolymer as template, potassium hydroxide is that mineralizer hydro-thermal method is prepared lithium manganese phosphate nano particle report.
Summary of the invention
The object of the present invention is to provide the hydrothermal synthesis method of the simple lithium ion battery anode material manganese lithium phosphate nano particle of a kind of favorable dispersibility and preparation technology.
The hydrothermal synthesis method of lithium ion battery anode material manganese lithium phosphate nano particle of the present invention, step is as follows:
1) template is dissolved in to deionized water, stir at least 240 minutes, add again inorganic manganese source and ascorbic acid, be stirred to abundant dissolving, obtaining manganese source concentration is that 1.0mol/L-2.0mol/L, ascorbic acid concentrations are 0.076mol/L-0.152mol/L, the solution A that template concentration is 0.1-0.2g/mL;
2) take phosphoric acid, inorganic lithium source is dissolved in deionized water, stir more than 30 minutes, formation phosphoric acid concentration is 1.0mol/L-2.0mol/L, the suspension B that the concentration in lithium source is 1.0mol/L-6.0mol/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, adds KOH, fully stir, regulate its volume to 2/3 ~ 4/5 of reactor volume by deionized water again, making KOH concentration is 0.05-0.15mol/L, and the concentration of P is 0.5mol/L-1.0mol/L, stirs more than 30 minutes;
5) reactor is airtight; at 160-200 DEG C, be incubated 4-48 hour; be down to room temperature; take out product, filter, clean with deionized water, absolute ethyl alcohol or acetone successively; at 40～100 DEG C of temperature, dry; under nitrogen or argon shield, in 550-650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle again.
In said method, raw material phosphoric acid, inorganic manganese source, inorganic lithium source, ascorbic acid, template and deionized water used, the purity of acetone are all not less than chemical pure.
Step 1) described in template can be F127(polyox-yethylene-polyoxypropylene block copolymer PluronicF127) or P123(PEO-PPOX-PEO triblock copolymer P123).
Step 1) described in inorganic manganese source can be manganese sulfate or manganese chloride.
Step 2) described in inorganic lithium source can be lithium sulfate or lithium hydroxide.
The present invention taking manganese source, lithium source, phosphoric acid be as reaction mass, block copolymer is template, KOH is mineralizer, deionized water is reaction dissolvent. By adding template and mineralizer KOH, crystallization and the growth course of lithium manganese phosphate in regulation and control heat treatment process, realize the synthetic of lithium ion battery anode material manganese lithium phosphate nano particle. The present invention is the lithium manganese phosphate phase in order to obtain pure phase to the cleaning of Hydrothermal Synthesis product. Under nitrogen or argon gas atmosphere, calcination processing at 550-650 DEG C, makes the lithium manganese phosphate surface that hydro-thermal obtains have carbon, improves the conductance of material, to increase the performance of lithium ion battery.
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.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of lithium manganese phosphate nano particle.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment.
Example 1
1) 2.00gP123 is dissolved in to 20ml deionized water, stir 240 minutes, then add 3.38g manganese sulfate and 0.20g ascorbic acid, be stirred to abundant dissolving, obtaining manganese source concentration is that 1.0mol/L, ascorbic acid concentrations are 0.076mol/L, the solution A that template concentration is 0.1g/mL;
2) lithium sulfate that takes 1.96g phosphoric acid, 2.56g is dissolved in 20ml deionized water, stirs 30 minutes, and formation phosphoric acid concentration is 1.0mol/L, the suspension B that the concentration in lithium source is 1.0mol/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 60ml autoclave, adds the KOH of 0.112g, fully stir, then regulate its volume to 40ml by deionized water, making KOH concentration is 0.05mol/L, and the concentration of P is 0.5mol/L, stirs 30 minutes;
5), by airtight the reactor that disposes 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, clean with deionized water, absolute ethyl alcohol or acetone successively, at 100 DEG C of temperature, dry. Under nitrogen or argon shield, in 550 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle, as shown in Figure 1, the lithium manganese phosphate nanoparticulate dispersed that this example makes is as seen good for its stereoscan photograph.
Example 2
1) 4.00gP123 is dissolved in to 20ml deionized water, stir 240 minutes, then add 6.76g manganese sulfate and 0.40g ascorbic acid, be stirred to abundant dissolving, obtaining manganese source concentration is that 2.0mol/L, ascorbic acid concentrations are 0.152mol/L, the solution A that template concentration is 0.2g/mL;
2) lithium hydroxide that takes 3.92g phosphoric acid, 3.36g is dissolved in 20ml deionized water, stirs 30 minutes, and formation phosphoric acid concentration is 2.0mol/L, the suspension B that the concentration in lithium source is 4.0mol/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 50ml autoclave, adds the KOH of 0.224g, fully stir, then regulate its volume to 40ml by deionized water, making KOH concentration is 0.10mol/L, and the concentration of P is 1.0mol/L, stirs 30 minutes;
5), by airtight the reactor that disposes reaction mass in step 4), heat-treat be incubated 24 hours at 180 DEG C after. Then, be down to room temperature, take out product, filter, clean with deionized water, absolute ethyl alcohol or acetone successively, at 80 DEG C of temperature, dry. Under nitrogen or argon shield, in 600 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle.
Example 3
1) 3.00gF127 is dissolved in to 20ml deionized water, stir 240 minutes, then add 5.94g manganese chloride and 0.32g ascorbic acid, be stirred to abundant dissolving, obtaining manganese source concentration is that 1.5mol/L, ascorbic acid concentrations are 0.091mol/L, the solution A that template concentration is 0.15g/mL;
2) lithium hydroxide that takes 2.94g phosphoric acid, 3.78g is dissolved in 20ml deionized water, stirs 30 minutes, and formation phosphoric acid concentration is 1.5mol/L, the suspension B that the concentration in lithium source is 4.5mol/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 60ml autoclave, adds the KOH of 0.336g, fully stir, then regulate its volume to 40ml by deionized water, making KOH concentration is 0.15mol/L, and the concentration of P is 0.75mol/L, stirs 90 minutes;
5), by airtight the reactor that disposes reaction mass in step 4), heat-treat be incubated 12 hours at 200 DEG C after. Then, be down to room temperature, take out product, filter, clean with deionized water, absolute ethyl alcohol or acetone successively, at 60 DEG C of temperature, dry. Under nitrogen or argon shield, in 650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle.
Claims (2)
1. the hydrothermal synthesis method of lithium ion battery anode material manganese lithium phosphate nano particle, is characterized in that step is as follows:
1) template is dissolved in to deionized water, stir at least 240 minutes, add again inorganic manganese source and ascorbic acid, be stirred to abundant dissolving, obtaining manganese source concentration is that 1.0mol/L-2.0mol/L, ascorbic acid concentrations are 0.076mol/L-0.152mol/L, the solution A that template concentration is 0.1-0.2g/mL; Described template is F127 or P123, and described inorganic manganese source is manganese sulfate or manganese chloride;
2) take phosphoric acid, inorganic lithium source is dissolved in deionized water, stir more than 30 minutes, formation phosphoric acid concentration is 1.0mol/L-2.0mol/L, the suspension B that the concentration in lithium source is 1.0mol/L-6.0mol/L; Described inorganic lithium source is lithium sulfate or lithium hydroxide;
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, adds KOH, fully stir, regulate its volume to 2/3 ~ 4/5 of reactor volume by deionized water again, making KOH concentration is 0.05-0.15mol/L, and the concentration of P is 0.5mol/L-1.0mol/L, stirs more than 30 minutes;
5) reactor is airtight; at 160-200 DEG C, be incubated 4-48 hour; be down to room temperature; take out product, filter, clean with deionized water, absolute ethyl alcohol or acetone successively; at 40～100 DEG C of temperature, dry; under nitrogen or argon shield, in 550-650 DEG C of calcining 4h, obtain lithium manganese phosphate nano particle again.
2. according to the hydrothermal synthesis method of the lithium manganese phosphate nano particle described in claim l, it is characterized in that the purity of raw material phosphoric acid used, inorganic manganese source, inorganic lithium source, ascorbic acid, template and deionized water, acetone is all not less than chemical pure.
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