CN102530906A - Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries - Google Patents

Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries Download PDF

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CN102530906A
CN102530906A CN201110261181XA CN201110261181A CN102530906A CN 102530906 A CN102530906 A CN 102530906A CN 201110261181X A CN201110261181X A CN 201110261181XA CN 201110261181 A CN201110261181 A CN 201110261181A CN 102530906 A CN102530906 A CN 102530906A
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microwave
lithium
hydrothermal
water
reaction
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卢灿忠
常金晶
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention provides a microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries, which includes the following steps that water-soluble lithium source compounds, iron source compounds and phosphorus source compounds serve as main reactants and are added with reaction additives, and are arranged in a microwave reaction instrument to have a microwave-hydrothermal reaction after being uniformly fixed in water or mixed solvent of water and other solvent, thereby obtaining ideal cathode materials of the nano lithium iron phosphate batteries under mild conditions (the temperature is 100-250 DEG C and the intensity of pressure is 0.1-1.5MPa ). The microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries has the advantages of being simple in process, energy-saving, high in efficiency, mild in conditions, low in cost, excellent in purity of products, uniform and fine in particles, high in controllability and excellent in reproducibility.

Description

A kind of microwave-hydrothermal method for preparing the nano ferric phosphate anode material of lithium battery
Technical field
The present invention relates to a kind of microwave-hydrothermal method for preparing the nano ferric phosphate anode material of lithium battery, belong to the anode material for lithium-ion batteries technical field.
Background technology
The modern life is advocated low-carbon (LC) life, green consumption.2009; China becomes world's second largest Carbon emission state; The energy-saving and emission-reduction important task is arduous unusually; And the external import interdependency of crude oil surpasses 50% first, and the new forms of energy industry has become China and one of development key field is focused in countries in the world, and wherein the research and development of power cell become the center of new forms of energy industry contention.
Lithium ion battery owing to have in light weight, advantages such as capacity big, memory-less effect, nontoxic pollution-free, becomes the first-selection of power cell research and development as a kind of new type power power supply.Lithium ion battery mainly comprises positive pole, negative pole, barrier film and electrolytic solution four big materials, and can positive electrode material be a part the most key in the lithium ion battery, directly determined the safety performance of battery and battery maximize, and accounts for about 30% of cost.Lithium iron phosphate positive material has the theoretical capacity height because of it, and security and cyclicity are good, and raw material is cheap, and the advantage of safety non-toxic, market demand are soaring year by year.The structural disadvantages of iron lithium phosphate self but distinct issues are, the passage of lithium ion only is a unidimensional, compares the two dimension or the three-dimensional channel of other positive electrode material, its specific conductivity that shows is obviously not enough.To this problem, investigators have proposed in the coated with conductive agent of iron lithium phosphate surface, particle nanometer, multiple improvement approach such as doped conducting metal.Wherein, realize that the particle nanometer can shorten lithium ion battery Li in charge and discharge process greatly +Deviate from and embed passage, thereby effectively improve material activity, improve the battery conductive rate, obtained various countries investigators' further investigation and extensively approval.
At present, the preparation method of ferric phosphate lithium cell positive electrode material has two kinds of solid phase method and liquid phase methods.Wherein solid phase method is under 550～700 ℃ high temperature and inert gas conditions, to carry out, and the production cycle is long, and energy consumption is big, and the product particle is big, and skewness, pattern are difficult to control.Liquid method commonly used has hydrothermal method, coprecipitation method, and sol-gel method etc., though product is higher than solid phase method purity, particle size can reach nano level, and the pattern controllability improves, and also has complex process, and cost is high, and the cycle is long, the shortcoming that preparation condition is harsh.So in recent years, investigators attempt to seek the novel method of preparation high quality nano ferric phosphate anode material of lithium battery under mild conditions always.
Summary of the invention
It is simple that the problem that the objective of the invention is to solve provides a kind of technology, and mild condition is with low cost, and product purity is high, the preparation method of the nano ferric phosphate anode material of lithium battery that the pattern controllability is good, the shortcoming and the limitation of solution traditional method.
The present invention adopts following technical scheme:
(1) with water-soluble Li source compound; Fe source compound and P source compound mix according to certain molar ratio, and add doping element compound, the reaction reductive agent; Tensio-active agent is as reaction additives; Be dissolved in the mixed solvent of deionized water or water and other solvent, fully stir, regulate the pH value in 4.5～7.5 scopes;
(2) with the said mixture reaction tubes of packing into, place the microwave reaction appearance in 100～250 ℃ of scopes, to carry out microwave-hydro-thermal reaction, constant temperature 5～150 minutes is cooled to room temperature afterwards;
(3) reaction product is separated, washing, dry then, promptly obtain the loose nano ferric phosphate anode material of lithium battery of pearl.
Water-soluble Li source compound described in the abovementioned steps (1) is a Lithium Hydroxide MonoHydrate, Lithium Sulphate, lithium chloride, lithium nitrate, Quilonum Retard, lithium acetate, monometallic, a kind of in lithium lactate and the lithium oxalate; Described water-soluble iron source compound is a ferrous sulfate, iron protochloride, Iron diacetate, Ferrox, iron lactate, ironic citrate, ferrous phosphate, tertiary iron phosphate, iron nitrate, iron acetate, ironic oxalate, a kind of in ferric sulfate and the iron(ic)chloride; Described water-soluble phosphorus source compound is a phosphoric acid, monometallic, ammonium phosphate, a kind of in Secondary ammonium phosphate and the primary ammonium phosphate.
Doping element compound described in the abovementioned steps (1) is a sodium Metal 99.5, potassium, rubidium, caesium, magnesium, calcium; Strontium, barium, aluminium, titanium, vanadium, chromium; Manganese, cobalt, nickel, copper, zinc, zirconium; Niobium, molybdenum, ruthenium, tungsten, one or both in the water-soluble cpds of tin or thulium, the alloying element x is 0.05～10.0%; Described reaction reductive agent is an xitix, Hydrocerol A, S-WAT, ammoniacal liquor, urea or glucose, a kind of in the recuding sugarses such as fructose; Described tensio-active agent is a kind of of this type of quaternary ammonium salt cationic surfactant of cetyl trimethylammonium bromide.
Other solvent described in the abovementioned steps (1) in the mixed solution is an ethanol, terepthaloyl moietie, polyoxyethylene glycol, Ucar 35, glycol ether, triglycol, glycerine, a kind of in trihydroxybutane and the acetone.
The present invention is used under the mild conditions, the controlled nano-grade lithium iron phosphate anode material for lithium-ion batteries of preparation pattern.The present invention has following characteristics: the nanometer LiFePO of the present invention's preparation 4Cell positive material has subsphaeroidal particulate pattern, and particle size is about 2～4nm.In the step (1), a spot of metallic compound hydrolyzable that mixes goes out the metals ion of high conduction, to improve the conductivity of material, in addition, metal-doped the material microscopic appearance is played refining effect, also can promote the conductivity of material; Adding the reaction reductive agent is can be with the reduction becoming of the ferric ion in water-soluble source of iron divalence ferrous ion, and the protection ferrous ion is not oxidized, advances LiFePO 4Product continues to generate; Add quaternary ammonium salt cationic surfactant, can control the material microscopic appearance effectively, the product particle is regular more tiny, helps material and realizes reliable and stable charge-discharge performance.Compare with traditional hydrothermal method, microwave-hydrothermal method intensification rapid and uniform, can be under gentle more condition (100～250 ℃ of temperature; Pressure 0.1～1.5MPa) obtains the ideal nano-powder material, and technology is simple; Efficient energy-saving, good product purity, evenly tiny; Controllability is high, good reproducibility, and by product is few.Reaction raw materials, preparation process and the equal nontoxic pollution-free of final product.
Description of drawings
Fig. 1 is the powder x-ray diffraction collection of illustrative plates that the embodiment of the invention 1,2 and 3 microwaves-hydro-thermal reaction make product, shows that product is single LiFePO 4Phase;
Fig. 2 is that the Scanning Probe Microscopy of the embodiment of the invention 1 microwave-hydro-thermal reaction product is observed figure, shows product particle form spherical in shape, and particle size is about 2.2nm.
Embodiment
A kind of preparation uniform particles is tiny, the method for high-purity nm ferric phosphate lithium cell positive electrode material.With water miscible Li source compound, P source compound and Fe source compound are raw material, with deionized water or deionized water and other solvent as solvent.Microwave-hydro-thermal reaction is carried out in 100～250 ℃ of scopes, and pressure is 0.1～1.5MPa, adds the controllability that reaction additives can increase the reaction product microscopic appearance.
Fig. 1 is the powder x-ray diffraction collection of illustrative plates of embodiment 1,2 and 3 microwaves-hydro-thermal reaction products therefrom, meets the characteristic diffraction peak of the iron lithium phosphate of olivine structural fully, does not find the corresponding characteristic diffraction peak of other thing.Fig. 2 is that the Scanning Probe Microscopy of embodiment 1 microwave-hydro-thermal reaction products therefrom is observed figure, subglobose LiFePO 4Particle size is about 2.2nm, and size distribution is even, and crystallinity is good.
Below be specific embodiment, in order to further specifying the present invention, and be not used in qualification the present invention.
Embodiment 1:
Take by weighing 0.333g Lithium Hydroxide MonoHydrate powder, be dissolved in the deionized water, be mixed with the lithium hydroxide aqueous solution of 0.2g/mL.Take by weighing 0.736g ferrous sulfate powder, be dissolved in deionized water and the ethanol mixed solvent, drip 0.15mL phosphoric acid (85%), magnetic agitation 5 minutes, 500 rev/mins of speed form transparent mixing solutions.Lithium hydroxide aqueous solution is joined in this mixing solutions, form the turbid liquid of greyish-green.Take by weighing 0.078g xitix and 0.121g cetyl trimethylammonium bromide respectively, join in this turbid liquid, magnetic agitation 10 minutes, 500 rev/mins of speed, measuring the pH value is 5.8.Then, pressure is 1.5MPa, and this mixture is packed in the crystal reaction tube, places on the microwave reaction appearance microwave heating to 150 ℃, constant temperature 20 minutes.After reaction finished, through spinning, ultrasonic cleaning and vacuum and heating drying finally obtained the loose nano ferric phosphate lithium powder of pearl, and microscopic appearance is subglobose particle, and size is about 2.2nm.
Embodiment 2:
Take by weighing 0.333g Lithium Hydroxide MonoHydrate powder, be dissolved in the deionized water, splash into 0.14mL phosphoric acid (85%), magnetic agitation 5 minutes, 500 rev/mins of speed form white turbid liquid.Take by weighing 0.736g ferrous sulfate and 0.078g xitix powder respectively, together be dissolved in the deionized water, join again in the white turbid liquid, magnetic agitation 10 minutes, 500 rev/mins of speed form the turbid liquid of greyish-green, and measuring the pH value is 6.0.Then, the turbid liquid of this greyish-green is packed in the crystal reaction tube, place on the microwave reaction appearance, microwave heating to 150 ℃, constant temperature 20 minutes, pressure are 1.4MPa.After reaction finished, through spinning, ultrasonic cleaning and heat drying finally obtained the loose nano ferric phosphate lithium powder of pearl, and microscopic appearance is subglobose particle, and size is about 2.0nm.
Embodiment 3:
Take by weighing 0.250g Lithium Hydroxide MonoHydrate powder, be dissolved in the deionized water, splash into 0.11mL phosphoric acid (85%), magnetic agitation 5 minutes, 500 rev/mins of speed form white turbid liquid.Take by weighing 0.524g ferrous sulfate and 0.017g calcium acetate powder respectively, together be dissolved in the deionized water after, join in the white turbid liquid, magnetic agitation 10 minutes, 500 rev/mins of speed form the turbid liquid of greyish-green.Take by weighing the 0.182g cetyl trimethylammonium bromide, add in the turbid liquid and mix, measuring the pH value is 6.0.Then, this is mixed turbid liquid pack in the crystal reaction tube, place on the microwave reaction appearance, microwave heating to 150 ℃, constant temperature 20 minutes, pressure are 1.1MPa.After reaction finished, through spinning, ultrasonic cleaning and heat drying finally obtained the loose nano ferric phosphate lithium powder of pearl.
Embodiment 4:
Take by weighing 0.333g Lithium Hydroxide MonoHydrate powder, be dissolved in the deionized water, splash into 0.14mL phosphoric acid (85%), magnetic agitation 5 minutes, 500 rev/mins of speed form white turbid liquid.Take by weighing 0.736g ferrous sulfate powder, be dissolved in the deionized water after, join in the white turbid liquid, magnetic agitation 10 minutes, 500 rev/mins of speed form the turbid liquid of greyish-green.Take by weighing the 0.121g cetyl trimethylammonium bromide, add in the turbid liquid and mix, measuring the pH value is 6.0.Then, this is mixed turbid liquid pack in the crystal reaction tube, place on the microwave reaction appearance, microwave heating to 150 ℃, constant temperature 20 minutes, pressure are 1.2MPa.After reaction finished, through spinning, ultrasonic cleaning and heat drying finally obtained the loose nano ferric phosphate lithium powder of pearl, and microscopic appearance is subglobose particle, and size is about 2.5nm.
Embodiment 5:
Take by weighing 0.333g Lithium Hydroxide MonoHydrate powder, be dissolved in the deionized water, be mixed with the lithium hydroxide aqueous solution of 0.2g/mL.Take by weighing 0.736g ferrous sulfate powder, be dissolved in the deionized water, drip 0.15mL phosphoric acid (85%), magnetic agitation 5 minutes, 500 rev/mins of speed form transparent mixing solutions.Lithium hydroxide aqueous solution is joined in this mixing solutions, form the turbid liquid of greyish-green.Take by weighing 0.078g xitix powder and join in this turbid liquid, magnetic agitation 10 minutes, 500 rev/mins of speed, measuring the pH value is 6.0.Then, this mixture is packed in the crystal reaction tube, place on the microwave reaction appearance, microwave heating to 130 ℃, constant temperature 20 minutes, pressure are 0.9MPa.After reaction finished, through spinning, ultrasonic cleaning and vacuum and heating drying finally obtained the loose nano ferric phosphate lithium powder of pearl, and microscopic appearance is subglobose particle, and size is about 3.2nm.

Claims (8)

1. microwave-hydrothermal method for preparing the nano ferric phosphate anode material of lithium battery comprises that step is following:
(1) with water-soluble Li source compound; Fe source compound and P source compound mix according to certain molar ratio, and add doping element compound, the reaction reductive agent; Tensio-active agent is as reaction additives; Be dissolved in the mixed solvent of deionized water or water and other solvent, fully stir, regulate the pH value in 4.5～7.5 scopes;
(2) with the said mixture reaction tubes of packing into, in the microwave reaction appearance, carry out microwave-hydro-thermal reaction, be cooled to room temperature afterwards;
(3) reaction product is separated, washing, dry then, promptly obtain the loose nano ferric phosphate anode material of lithium battery of pearl.
2. microwave-the hydrothermal method of preparation nano ferric phosphate anode material of lithium battery as claimed in claim 1 is characterized in that: the water-soluble Li source compound described in the step (1) is a Lithium Hydroxide MonoHydrate, Lithium Sulphate; Lithium chloride; Lithium nitrate, Quilonum Retard, lithium acetate; Monometallic, a kind of in lithium lactate and the lithium oxalate; Described water-soluble iron source compound is a ferrous sulfate, iron protochloride, Iron diacetate, Ferrox, iron lactate, ironic citrate, ferrous phosphate, tertiary iron phosphate, iron nitrate, iron acetate, ironic oxalate, a kind of in ferric sulfate and the iron(ic)chloride; Described water-soluble phosphorus source compound is a phosphoric acid, monometallic, ammonium phosphate, a kind of in Secondary ammonium phosphate and the primary ammonium phosphate.
3. according to claim 1 or claim 2 the microwave-hydrothermal method of preparation nano ferric phosphate anode material of lithium battery, it is characterized in that: the doping element compound described in the step (1) is a sodium Metal 99.5, potassium, rubidium, caesium, magnesium, calcium; Strontium, barium, aluminium, titanium, vanadium, chromium; Manganese, cobalt, nickel, copper, zinc, zirconium; Niobium, molybdenum, ruthenium, tungsten, one or both in the water-soluble cpds of tin or thulium, the alloying element x is 0.05～10.0%; Described reaction reductive agent is an xitix, Hydrocerol A, S-WAT, ammoniacal liquor, urea or glucose, a kind of in the recuding sugarses such as fructose; Described tensio-active agent is a kind of of this type of quaternary ammonium salt cationic surfactant of cetyl trimethylammonium bromide.
4. like the microwave-hydrothermal method of claim 1,2 or 3 described preparation nano ferric phosphate anode material of lithium battery; It is characterized in that: doping element compound described in the step (1); Reaction reductive agent and three types of reaction additives of tensio-active agent; Can add wherein one type or several types simultaneously, also can not add.
5. like the microwave-hydrothermal method of claim 1,2,3 or 4 described preparation nano ferric phosphate anode material of lithium battery, it is characterized in that: other solvent described in the step (1) in the mixed solution is an ethanol, terepthaloyl moietie; Polyoxyethylene glycol; Ucar 35, glycol ether, triglycol; Glycerine, a kind of in trihydroxybutane and the acetone.
6. like the microwave-hydrothermal method of claim 1,2,3,4 or 5 described preparation nano ferric phosphate anode material of lithium battery; It is characterized in that: described in the step (1) with the lithium source; Source of iron and P source compound carry out blended in proper order for earlier lithium source and P source compound being mixed in the mixed solvent of deionized water or water and other solvent; Adding Fe source compound at last evenly stirs; Perhaps earlier source of iron and P source compound are mixed in the mixed solvent of deionized water or water and other solvent, add a kind of in the even stirring of Li source compound at last.
7. like the microwave-hydrothermal method of claim 1,2,3,4,5 or 6 described preparation nano ferric phosphate anode material of lithium battery; It is characterized in that: microwave-hydrothermal temperature is in 100～250 ℃ of scopes described in the step (2); Constant temperature time is 5～150 minutes, and internal pressure is 0.1～1.5MPa.
8. like the microwave-hydrothermal method of claim 1,2,3,4,5,6 or 7 described preparation nano ferric phosphate anode material of lithium battery, it is characterized in that: described in the step (3) be separated into centrifugal with filter in a kind of; Described washing is to be medium with in water and the ethanol one or both; Said drying is a kind of in heat drying and the vacuum and heating drying, and temperature is between 50～200 ℃.。
CN201110261181XA 2010-12-16 2011-09-06 Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries Pending CN102530906A (en)

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN102765708A (en) * 2012-07-09 2012-11-07 陕西科技大学 Microwave hydrothermal method for synthesizing lithium iron phosphate serving as cathode material of lithium ion battery
CN103682338A (en) * 2013-12-23 2014-03-26 向勇 Preparation method for high-conductivity LiFePO4 cathode material
CN103708434A (en) * 2012-10-09 2014-04-09 上海交通大学 Lithium iron phosphate material and preparation method thereof
US20150303473A1 (en) * 2012-12-21 2015-10-22 Murali G. Theivanayagam Co-solvent assisted microwave-solvothermal process for making olivine lithium transition metal phosphate electrode materials
RU2579378C2 (en) * 2014-07-01 2016-04-10 Геннадий Хрисанфович Маркин Method of producing compound metal-phosphate product (versions)
CN106276830A (en) * 2015-05-20 2017-01-04 南开大学 A kind of preparation method of microwave synthesis metal phosphide
CN107619032A (en) * 2017-09-10 2018-01-23 绵阳梨坪科技有限公司 A kind of preparation method with uniform-spherical meso-hole structure lithium iron phosphate positive material
TWI636007B (en) * 2012-08-31 2018-09-21 戶田工業股份有限公司 Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite manganese iron iron particle particle powder, and nonaqueous electrolyte secondary battery using the same
CN109830680A (en) * 2017-11-23 2019-05-31 中国科学院金属研究所 A kind of LiFePO4Hydrothermal synthesis method
CN110342588A (en) * 2019-07-23 2019-10-18 上海应用技术大学 A kind of ternary cathode material of lithium ion battery and preparation method thereof
CN113072052A (en) * 2021-03-29 2021-07-06 山东大学 Waste lithium iron phosphate lithium supplement repair method and application

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102765708A (en) * 2012-07-09 2012-11-07 陕西科技大学 Microwave hydrothermal method for synthesizing lithium iron phosphate serving as cathode material of lithium ion battery
TWI636007B (en) * 2012-08-31 2018-09-21 戶田工業股份有限公司 Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite manganese iron iron particle particle powder, and nonaqueous electrolyte secondary battery using the same
CN103708434A (en) * 2012-10-09 2014-04-09 上海交通大学 Lithium iron phosphate material and preparation method thereof
US20150303473A1 (en) * 2012-12-21 2015-10-22 Murali G. Theivanayagam Co-solvent assisted microwave-solvothermal process for making olivine lithium transition metal phosphate electrode materials
CN103682338A (en) * 2013-12-23 2014-03-26 向勇 Preparation method for high-conductivity LiFePO4 cathode material
CN103682338B (en) * 2013-12-23 2017-02-15 向勇 Preparation method for high-conductivity LiFePO4 cathode material
RU2579378C2 (en) * 2014-07-01 2016-04-10 Геннадий Хрисанфович Маркин Method of producing compound metal-phosphate product (versions)
CN106276830A (en) * 2015-05-20 2017-01-04 南开大学 A kind of preparation method of microwave synthesis metal phosphide
CN107619032A (en) * 2017-09-10 2018-01-23 绵阳梨坪科技有限公司 A kind of preparation method with uniform-spherical meso-hole structure lithium iron phosphate positive material
CN109830680A (en) * 2017-11-23 2019-05-31 中国科学院金属研究所 A kind of LiFePO4Hydrothermal synthesis method
CN110342588A (en) * 2019-07-23 2019-10-18 上海应用技术大学 A kind of ternary cathode material of lithium ion battery and preparation method thereof
CN113072052A (en) * 2021-03-29 2021-07-06 山东大学 Waste lithium iron phosphate lithium supplement repair method and application

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