CN105140514A - Method for preparing small-size nanometer lithium manganese phosphate material - Google Patents

Method for preparing small-size nanometer lithium manganese phosphate material Download PDF

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Publication number
CN105140514A
CN105140514A CN201510477024.0A CN201510477024A CN105140514A CN 105140514 A CN105140514 A CN 105140514A CN 201510477024 A CN201510477024 A CN 201510477024A CN 105140514 A CN105140514 A CN 105140514A
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solution
manganese phosphate
ethylene glycol
lithium manganese
phosphate material
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孙晓红
胡旭东
杨铭
杨德明
郑春明
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Tianjin University
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Tianjin University
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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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for preparing a small-size nanometer lithium manganese phosphate material. The small-size nanometer lithium manganese phosphate material is prepared in one step by adding a stirring technology in a solvothermal method synthetic process. By using the stirring technology in the solvothermal method synthetic process, ionic migration and diffusion is accelerated to enable rapid nucleating so as to increase the number in the nucleation center, reduce the phenomenon of uneven nucleation and realize the purpose of reducing the crystal size of the synthetic product. The nanometer lithium manganese phosphate material with the size of smaller than 100 nm is prepared successfully by the method; and when the nanometer lithium manganese phosphate material is used as the positive pole material to be assembled in batteries, specific discharge capacity of 145 mAhg<-1> is obtained under current of 0.1 C, representing that the lithium ions are embedded and de-intercalated quite completely in the nanometer lithium manganese phosphate material.

Description

A kind of method preparing small size nano manganese phosphate lithium material
Technical field
The invention belongs to inorganic nano material synthesis field.Particularly, the method being prepared small size nano manganese phosphate lithium material by the reaction condition changed in experiment is related to.
Background technology
The mankind are in the modern society of a high speed development, and along with the fast development of World Economics, industry, the impact that the energy develops all trades and professions is also increasing.The mankind rely on for a long time and use the fossil energy being representative with coal, oil, natural gas; but along with the continuous exploitation of the mankind; the exhaustion of fossil energy is inevitable; and a large amount of greenhouse gas and contaminative flue gas can be produced in the use procedure of fossil energy; threaten the biological environment in the whole world, therefore the development of human society is subject to the restriction of energy exhaustion and environmental protection aspect.So, find, develop and utilize environment amenable novel energy to become the hot fields of various countries' research, thus receive the very big attention of people.
Lithium ion battery has the advantages such as operating voltage is high, quality is light, specific energy is high, memory-less effect, pollution-free, self discharge is little and have extended cycle life, and is widely used in the fields such as mobile phone, video camera, electric tool and notebook computer.At present, lithium-ion-power cell adopts LiFePO 4 be positive electrode and progressively realize industrialization, but this material is only 3.4V ~ 3.7V relative to the current potential of lithium metal, by comparison, and LiMnPO 4current potential can be improved 0.7V by material, reaches 4.1V ~ 4.4V, and battery energy density compares LiFePO 4battery exceeds more than 30%, and raw material are cheap abundant, pollution-free, therefore as positive electrode LiMnPO of new generation 4get most of the attention.But, due to LiMnPO 4the reason of this body structure, LiMnPO 4conductivity poor, lithium ion diffusion coefficient is therein low, causes the embedding of lithium ion and deviates from difficulty.According to numerous pertinent literature, LiMnPO 4the nanometer of material makes up LiMnPO effectively by the evolving path reducing lithium ion 4the deficiency that intracrystalline diffusion coefficient is low, improves its chemical property as anode material for lithium-ion batteries.
Solvent-thermal method is that one prepares the effectively method of nano material.In addition, some experiment parameters in solvent-thermal method, as other experiment conditions such as reaction temperature, reaction time, precursor species composition, concentration, ratio and pH values, being easy to regulate, making it be applicable to having for controlling synthesis the crystal structure of different-shape and different size size.
Summary of the invention
The present invention passes through at solvent structure LiMnPO 4process in add the technique of stirring and change temperature retention time and come, achieve the object reducing product crystalline size, provide a kind of synthesis LiMnPO 4brand-new solvent-thermal method.
Technical scheme of the present invention is as follows:
Prepare a method for small size nano manganese phosphate lithium material, be add stirring in solvent structure process, a step prepares undersized nano manganese phosphate lithium material.
The method is on the basis of the hot method of conventional solvent, add stirring technique one-step synthesis lithium manganese phosphate, and this experiment is also by changing reaction time synthesis of nano lithium manganese phosphate material in addition; Concrete steps are as follows:
1). by the H of 85wt.% 3pO 4the aqueous solution joins in ethylene glycol, and obtained concentration is the H of 0.45mol/L – 0.50mol/L 3pO 4solution;
2). by LiOHH 2o is dissolved in ethylene glycol, and obtained concentration is the LiOH solution of 0.70mol/L – 0.80mol/L, then gets the H of preparation in step 1 3pO 4solution, is added drop-wise to wherein, makes H 3pO 4the volume ratio of solution and LiOH solution is 1:2, and dropping limit, limit is stirred, and stir speed (S.S.) is 10r/s, after dropwising, obtains white suspension;
3). first by MnSO 4h 2o is dissolved in distilled water, and then adds ethylene glycol and mix, and the volume ratio of distilled water and ethylene glycol is 1:7, and obtained concentration is the MnSO of 0.2mol/L – 0.3mol/L 4solution, is then added drop-wise in the white suspension that step 2 obtains, MnSO 4the volume ratio of solution and LiOH solution is 1:1, and dropping limit, limit is stirred, and stir speed (S.S.) is 10r/s, obtains presoma mixed liquor;
4). presoma mixed liquor is transferred in polytetrafluoroethylene hydrothermal reaction kettle liner, and one piece of magnet rotor is put in liner, then use stainless steel cauldron sealing;
5) use magnetic force heating stirrer as thermal source, reaching stir speed (S.S.) is 10r/s, and oil bath is heated to 180 DEG C, is incubated 6 – 10 hours;
6) after reaction terminates, under room temperature, be cooled to normal temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, obtain final reacting product.
The invention provides a kind of method preparing the solvent structure nano manganese phosphate lithium material adding stirring technique.By using the technique of stirring in solvent structure process, can accelerate migration and the diffusion of ion, be its fast nucleation, increases the number of nuclearing centre, and reduce the phenomenon of heterogeneous nucleation, realizes the object reducing synthetic product crystalline size.Relative to the hot method of conventional solvent, the lithium manganese phosphate material crystal size distribution of the method synthesis is more even, and size is less.
Effect of the present invention is: relative to the hot method of conventional solvent, and the solvent-thermal method adding stirring can prepare the nanometer LiMnPO of smaller szie 4material.The inventive method have be easy to operation, the simple feature of equipment.
Accompanying drawing explanation
Be respectively the X-ray diffractogram of product prepared by embodiment 1, embodiment 2, embodiment 3 and embodiment 4 in Fig. 1 from down to up, the product prepared by explanation is the LiMnPO of complete crystallization 4pure phase.
Fig. 2 is the LiMnPO that embodiment 1 is synthesized 4sEM figure, as shown in the figure, the product that embodiment 1 is synthesized be fusiformis, and evenly, length is between 500 – 600nm for particle size distribution.
The SEM figure of the product of Fig. 3 obtained by embodiment 4, shows in figure, LiMnPO 4in pelletized form, even size distribution, particle size size is between 50-100nm for crystal.
LiMnPO obtained by Fig. 4 embodiment 4 4material is assembled into as positive pole the voltage ratio capacity curve that battery records, battery is constant current charge under the electric current of 0.1C first, when voltage reaches 4.5V, constant voltage charge, complete charge when being 0.03C to current attenuation, and then under the electric current of 0.1C constant-current discharge, terminate when voltage reduces to 2.5V electric discharge.As can be seen from the figure, the discharge platform of battery is at about 4.1V, and the voltage difference between discharge platform and charging platform, at 0.1 – 0.2V, illustrates that the charge polarization of battery is less.In addition, higher specific discharge capacity 145mAhg -1also illustrate that lithium ion embeds in the material and deviates from more abundant.
Embodiment
Embodiment 1:
By 0.009molH 3pO 4(the H of 1.04g85wt.% 3pO 4the aqueous solution) join in 20mL ethylene glycol, mix; By 0.032molLiOHH 2o joins in 40mL ethylene glycol, heating water bath 50 DEG C stirring (10r/s) to all dissolving, then by its lentamente (1mL/min) be added drop-wise to H 3pO 4in solution, after terminating, obtain white suspension; By 0.01molMnSO 4h 2o is first dissolved in 5mL distilled water, and then adds 35mL ethylene glycol wherein, mixes rear slowly (5mL/min) and is added drop-wise in above-mentioned suspension, remain vigorous stirring (10r/s) in process; Capacity of being transferred to by above-mentioned presoma mixed liquor is in the polytetrafluoroethylene hydrothermal reaction kettle liner of 50mL, and stainless steel cauldron seals; Employing baking oven heats, and is heated to 180 DEG C, insulation 6h; After reaction terminates, be cooled to normal temperature under room temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, 80 DEG C of dry 12h, obtain final reacting product.As shown in Figure 1, product is the LiMnPO of complete crystallization 4pure phase.Fig. 2 SEM result shows, the LiMnPO of synthesis 4crystal is fusiformis, and particle size distribution is even, and length is between 500 – 600nm.
Embodiment 2:
By 0.094molH 3pO 4(the H of 1.08g85wt.% 3pO 4the aqueous solution) join in 20mL ethylene glycol, mix; By 0.03molLiOHH 2o joins in 40mL ethylene glycol, heating water bath 50 DEG C stirring (10r/s) to all dissolving, then by its lentamente (1mL/min) be added drop-wise to H 3pO 4in solution, after terminating, obtain white suspension; By 0.01molMnSO 4h 2o is first dissolved in 5mL distilled water, and then adds 35mL ethylene glycol wherein, mixes rear slow dropping (5mL/min) in above-mentioned suspension, remains stirring (10r/s) in process; Capacity of being transferred to by above-mentioned presoma mixed liquor is in the polytetrafluoroethylene hydrothermal reaction kettle liner of 50mL, and one piece of magnet rotor is put into inner liner of reaction kettle, then uses stainless steel cauldron sealing; Use magnetic force heating stirrer as thermal source, and reach the object of stirring (10r/s); Employing oil bath is heated, and is heated to 180 DEG C, insulation 6h; After reaction terminates, be cooled to normal temperature under room temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, 80 DEG C of dry 12h, obtain final reacting product.
Embodiment 3:
By 0.096molH 3pO 4(the H of 1.10g85wt.% 3pO 4the aqueous solution) join in 20mL ethylene glycol, mix; By 0.03molLiOHH 2o joins in 40mL ethylene glycol, heating water bath 50 DEG C stirring (10r/s) to all dissolving, then by its lentamente (1mL/min) be added drop-wise to H 3pO 4in solution, after terminating, obtain white suspension; By 0.01molMnSO 4h 2o is first dissolved in 5mL distilled water, and then adds 35mL ethylene glycol wherein, mixes rear slow dropping (5mL/min) in above-mentioned suspension, remains vigorous stirring (10r/s) in process; Capacity of being transferred to by above-mentioned presoma mixed liquor is in the polytetrafluoroethylene hydrothermal reaction kettle liner of 50mL, and one piece of magnet rotor is put into inner liner of reaction kettle, then uses stainless steel cauldron sealing; Use magnetic force heating stirrer as thermal source, and reach the object of stirring (10r/s); Employing oil bath is heated, and is heated to 180 DEG C, insulation 8h; After reaction terminates, be cooled to normal temperature under room temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, 80 DEG C of dry 12h, obtain final reacting product.As shown in Figure 1, product is the LiMnPO of complete crystallization 4pure phase.
Embodiment 4:
By 0.01molH 3pO 4(the H of 1.15g85wt.% 3pO 4the aqueous solution) join in 20mL ethylene glycol, mix; By 0.028molLiOHH 2o joins in 40mL ethylene glycol, heating water bath 50 DEG C stirring (10r/s) to all dissolving, then by its lentamente (1mL/min) be added drop-wise to H 3pO 4in solution, after terminating, obtain white suspension; By 0.01molMnSO 4h 2o is first dissolved in 5mL distilled water, and then adds 35mL ethylene glycol wherein, mixes rear slow dropping (5mL/min) in above-mentioned suspension, remains vigorous stirring (10r/s) in process; Capacity of being transferred to by above-mentioned presoma mixed liquor is in the polytetrafluoroethylene hydrothermal reaction kettle liner of 50mL, and one piece of magnet rotor is put into inner liner of reaction kettle, then uses stainless steel cauldron sealing; Use magnetic force heating stirrer as thermal source, and reach the object of stirring (10r/s); Employing oil bath is heated, and is heated to 180 DEG C, insulation 10h; After reaction terminates, be cooled to normal temperature under room temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, 80 DEG C of dry 12h, obtain final reacting product.As shown in Figure 1, product is the LiMnPO of complete crystallization 4pure phase.Fig. 2 SEM result shows, LiMnPO 4in pelletized form, even size distribution, particle size size is between 50-100nm for crystal.By being used in the size using in solvent-thermal method process and stir and significantly can reduce crystal.Fig. 4 is obtained LiMnPO 4material is assembled into as positive pole the voltage ratio capacity curve that battery records, battery is constant current charge under the electric current of 0.1C first, when voltage reaches 4.5V, constant voltage charge, complete charge when being 0.03C to current attenuation, and then under the electric current of 0.1C constant-current discharge, terminate when voltage reduces to 2.5V electric discharge.As can be seen from the figure, the discharge platform of battery is at about 4.1V, and the voltage difference between discharge platform and charging platform, at 0.1 – 0.2V, illustrates that the charge polarization of battery is less.In addition, higher specific discharge capacity 145mAhg -1also illustrate that lithium ion embeds in the material and deviates from more abundant.
To sum up the accompanying drawing of implementation column can clearly be found out, the present invention by using stirring technique in solvent structure process, and has successfully prepared by regulation time the lithium manganese phosphate material that size is less than 100nm.And after material is assembled into battery as positive electrode, under the electric current of 0.1C, obtain 145mAhg -1specific discharge capacity, describe lithium ion and embed in the material and deviate from more abundant.

Claims (2)

1. prepare a method for small size nano manganese phosphate lithium material, it is characterized in that adding stirring in solvent structure process, a step prepares undersized nano manganese phosphate lithium material.
2. the method for claim 1, concrete steps are as follows:
1). by the H of 85wt.% 3pO 4the aqueous solution joins in ethylene glycol, and obtained concentration is the H of 0.45mol/L – 0.50mol/L 3pO 4solution;
2). by LiOHH 2o is dissolved in ethylene glycol, and obtained concentration is the LiOH solution of 0.70mol/L – 0.80mol/L, then gets the H of preparation in step 1 3pO 4solution, is added drop-wise to wherein, makes H 3pO 4the volume ratio of solution and LiOH solution is 1:2, and dropping limit, limit is stirred, and stir speed (S.S.) is 10r/s, after dropwising, obtains white suspension;
3). first by MnSO 4h 2o is dissolved in distilled water, and then adds ethylene glycol and mix, and the volume ratio of distilled water and ethylene glycol is 1:7, and obtained concentration is the MnSO of 0.2mol/L – 0.3mol/L 4solution, is then added drop-wise in the white suspension that step 2 obtains, MnSO 4the volume ratio of solution and LiOH solution is 1:1, and dropping limit, limit is stirred, and stir speed (S.S.) is 10r/s, obtains presoma mixed liquor;
4). presoma mixed liquor is transferred in polytetrafluoroethylene hydrothermal reaction kettle liner, and one piece of magnet rotor is put in liner, then use stainless steel cauldron sealing;
5) use magnetic force heating stirrer as thermal source, reaching stir speed (S.S.) is 10r/s, and oil bath is heated to 180 DEG C, is incubated 6 – 10 hours;
6) after reaction terminates, under room temperature, be cooled to normal temperature, take out reactant, use deionized water and ethanol to wash 3 times respectively, obtain final reacting product.
CN201510477024.0A 2015-08-06 2015-08-06 Method for preparing small-size nanometer lithium manganese phosphate material Pending CN105140514A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384813A (en) * 2016-10-14 2017-02-08 中国科学院青岛生物能源与过程研究所 Fast synthesis method of positive electrode material for lithium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103500829A (en) * 2013-08-15 2014-01-08 江苏华东锂电技术研究院有限公司 Preparation method of lithium iron phosphate
CN103996853A (en) * 2014-05-28 2014-08-20 天津大学 Method for preparing nano lithium manganese phosphate material with uniform size
CN104766972A (en) * 2015-03-05 2015-07-08 清华大学 Nanorod-like lithium manganese phosphate anode material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103500829A (en) * 2013-08-15 2014-01-08 江苏华东锂电技术研究院有限公司 Preparation method of lithium iron phosphate
CN103996853A (en) * 2014-05-28 2014-08-20 天津大学 Method for preparing nano lithium manganese phosphate material with uniform size
CN104766972A (en) * 2015-03-05 2015-07-08 清华大学 Nanorod-like lithium manganese phosphate anode material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384813A (en) * 2016-10-14 2017-02-08 中国科学院青岛生物能源与过程研究所 Fast synthesis method of positive electrode material for lithium ion battery

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