CN104752717B - Lithium iron phosphate and its preparation method and use - Google Patents
Lithium iron phosphate and its preparation method and use Download PDFInfo
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- CN104752717B CN104752717B CN201310740269.9A CN201310740269A CN104752717B CN 104752717 B CN104752717 B CN 104752717B CN 201310740269 A CN201310740269 A CN 201310740269A CN 104752717 B CN104752717 B CN 104752717B
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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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- 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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- 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
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
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- 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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Abstract
The invention provides a preparation method of lithium iron phosphate, the lithium iron phosphate and a use of the lithium iron phosphate in preparation of a positive pole active material. The preparation method of the lithium iron phosphate comprises that a water-soluble divalent iron source, a water-soluble phosphor source and a water-soluble lithium source are mixed and undergo a reaction, wherein the water-soluble phosphor source is phosphoric acid and/or water-soluble phosphate, and the mixing method comprises carrying out atomization on an aqueous solution A containing the water-soluble divalent iron source and the water-soluble phosphor source and an aqueous solution B containing the water-soluble lithium source, carrying out blending and simultaneously, controlling the mixture pH in a range of 5-7.5 by controlling an atomization rate of the aqueous solution A and the aqueous solution B in atomization. The preparation method can control lithium iron phosphate particle size in a submicron level and realize good electrochemical performances of the lithium iron phosphate.
Description
Technical field
The present invention relates to a kind of preparation method of LiFePO4, the LiFePO4 prepared by the method and the phosphorus
Application of the sour ferrum lithium as positive electrode active materials.
Background technology
In recent years, lithium-ion-power cell at aspects such as electric automobile (EVs), hybrid-electric cars (HEVs) because having weight
The application prospect wanted and widely paid close attention to.The price of lithium-ion-power cell practical application, safety, environmental protection and use
The focal issue that life-span is always studied.LiFePO4（LiFePO4）Due to high with specific capacity（170mAh·g-1）, raw material
Price is low, environmental friendliness, safe, good cycle the advantages of, have become most potential lithium-ion-power cell
Positive electrode active materials.
However, in LiFePO4 structure, FeO6Octahedron is by PO4Tetrahedron is separated, LiO6Octahedron is along b axles
The common side in direction, forms chain, and the electronic conductivity for causing pure ferric phosphate lithium is relatively low（10-9S·cm-1）.Additionally, Li+In Fructus Canarii albi
One-dimensional passage in stone crystal structure along [010] direction spreads, and such one-dimensional passage can be because Li2Fe misplaces and hinders Li+'s
Long-range migration, causes lithium ion diffusion coefficient less（1.8×10-14cm2·s-1）, and therefore it is limited in high power conditions
Under use.Two effective ways for improving the electrical conductance of LiFePO4 at present are to reduce its particle diameter and carry out carbon bag to it
Cover.
Wherein, the LiFePO4 of hydro-thermal method synthesis the characteristics of having little material footpath, narrow diameter distribution due to receiving much concern.Water
During full-boiled process synthesizing iron lithium phosphate, typically first presoma prepared by source of iron, lithium source and phosphorus source, then that presoma is entered into horizontal high voltage is anti-
Should be so as to obtaining LiFePO4.Current research shows, during hydro-thermal method synthesizing iron lithium phosphate, the pH value of presoma,
The concentration of reactant, reducing agent, surfactant and hydrothermal temperature, response time etc. are the principal elements for affecting final product.
Wherein, most critical is become the dissolving of presoma and the growth course of crystal during the pH value of presoma is because decide course of reaction
Factor, is the most important process control parameters of hydro-thermal method synthesizing iron lithium phosphate product consistency.
However, in existing technology, people are often only concerned when presoma is controlled and adjust its pH value.For example,
A kind of hydrothermal synthesis method of LiFePO4 is disclosed in CN101752564A, first mixes Lithium hydrate with phosphoric acid, then in 40-
Ferrous sulfate is added when 50 DEG C, then with Lithium hydrate or sulfur acid for adjusting pH, and product will be obtained is carried out carbon coating.So
And, the particle diameter of the LiFePO4 obtained using the method remains as micron order, and impurity content is still higher, therefore can not have
Effect improves its chemical property.
The content of the invention
The invention aims to overcome the particle diameter of the LiFePO4 prepared using existing method larger and electricity
The poor defect of chemical property, and a kind of preparation method of new LiFePO4, the LiFePO4 that prepared by the method with
And the LiFePO4 is used as the application of positive electrode active materials.It is obtained in that particle diameter is little and chemical property is preferable using the method
LiFePO4.
The invention provides a kind of preparation method of LiFePO4, the method is included watersoluble divalent source of iron, water solublity
Phosphorus source and water solublity lithium source mix and react, and the water solublity phosphorus source is phosphoric acid and/or water-soluble phosphate, wherein, it is described
The mode of mixing is included by the water solution A containing the watersoluble divalent source of iron and the water solublity phosphorus source and containing the water
The aqueous solution B of dissolubility lithium source is atomized and is mixed, and is being atomized by controlling the water solution A and the aqueous solution B
Atomization rates in journey control the pH value of mix products in 5-7.5.
Present invention also offers the LiFePO4 prepared by said method.
Additionally, present invention also offers the LiFePO4 as positive electrode active materials application.
During existing employing hydro-thermal method prepares LiFePO4, typically first by watersoluble divalent source of iron, water-soluble
Property phosphorus source and water solublity lithium source mixing and be quickly generated the forerunner containing various intermediate sedimentation products such as ferrous phosphate, lithium phosphate
Body, then under the conditions of pyroreaction makes the various intermediate sedimentation products in the presoma be converted into LiFePO4 again.And this
The inventor of invention has found that in high-temperature reaction process, the precipitation in the presoma can dissolve and weigh again by furtheing investigate
Crystallization, the size of the presoma has very important impact to the particle diameter of the final LiFePO4 for obtaining.Granule is too
Big presoma can cause that the lithium iron phosphate particles for finally giving are big, efficiency for charge-discharge is low；And the too little presoma of granule can lead
Easily there is the phenomenon reunited in the LiFePO4 that cause finally gives.
And can be by the size controlling of the LiFePO4 for obtaining is in submicron order and has preferable using the method for the present invention
Chemical property.Speculate its reason, it may be possible to due to：On the one hand, employing will be containing the watersoluble divalent source of iron and water
The water solution A of dissolubility phosphorus source is atomized and is mixed with the aqueous solution B containing the water solublity lithium source, can be disperseed reactant
Into microlayer model, each microlayer model is the reactor of a micro volume, due to the small volume of the microlayer model of formation after atomization,
So as to not only control reaction mass contact when nucleation and cause contact generate granule it is less, and can extend precipitation tie
Brilliant long crystalline substance Induction time, therefore, just can be by presoma and the particle diameter of the LiFePO4 for finally giving when not being ground
Control is in submicron order；On the other hand, in the atomization and during mixing, by controlling the water solution A and the water
The atomization rates of solution B control the pH value of mix products in 5-7.5, can not only provide the environment for preparing presoma, and
The oxidized risk of ferrous ion in the watersoluble divalent source of iron can also be reduced, and finally reduces the LiFePO4 for obtaining
The content of middle impurity（Ferrous ion easily generates under strongly alkaline conditions Fe (OH)2, and Fe (OH)2It is very easy to be oxidized to
Fe(OH)3, and then make to contain Fe in the product for obtaining2O3）.
A preferred embodiment of the invention, when the water solution A also contains reducing agent, can reduce bivalence
Iron ion mixing and course of reaction in be oxidized probability, so as to reduce LiFePO4 in impurity content and further improve
Its chemical property.
Another kind of preferred implementation of the invention, when the water solution A also contains surfactant, additionally it is possible to
The volume energy density of the LiFePO4 that raising is obtained, so as to be conducive to obtaining the less anelectrode of volume.
Another kind of preferred implementation of the invention, when the preparation method of the LiFePO4 also includes producing reaction
Thing is mixed with organic carbon source and is spray-dried, then when the Spray dried products for obtaining are carried out into roasting, due to described organic
The carbonization of carbon source, can further improve the electric conductivity of the LiFePO4, and and then further improve its chemical property.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffraction spectrogram of LiFePO4 prepared by embodiment 1 and LiFePO4 standard sample；
Fig. 2 is the stereoscan photograph of LiFePO4 prepared by embodiment 1；
Fig. 3 is the X-ray diffraction spectrogram of LiFePO4 prepared by embodiment 4 and LiFePO4 standard sample；
Fig. 4 is the stereoscan photograph of LiFePO4 prepared by embodiment 4；
Fig. 5 is the stereoscan photograph of LiFePO4 prepared by comparative example 1；
Fig. 6 is the stereoscan photograph of LiFePO4 prepared by comparative example 2.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The preparation method of the LiFePO4 that the present invention is provided is included watersoluble divalent source of iron, water solublity phosphorus source and water-soluble
Property lithium source mix and react, the water solublity phosphorus source is phosphoric acid and/or water-soluble phosphate, wherein, the mode bag of the mixing
Include the water solution A containing the watersoluble divalent source of iron and the water solublity phosphorus source and the water containing the water solublity lithium source
Solution B is atomized and is mixed, and by controlling the atomization speed of the water solution A and the aqueous solution B in atomization process
Rate controls the pH value of mix products in 5-7.5.
The present invention is not especially limited the consumption of the watersoluble divalent source of iron, water solublity phosphorus source and water solublity lithium source
It is fixed, for example, the use of the consumption of the watersoluble divalent source of iron, total consumption of the water solublity phosphorus source and the water solublity lithium source
Amount makes Fe in the mix products for finally giving2+、PO4 3-With Li+Mol ratio can be（0.95-1.05）:（0.95-1.05）:3,
Preferably（0.98-1）:（0.98-1）:3.Additionally, in the water solution A, the concentration of the watersoluble divalent source of iron can be
0.2-2.5mol/L, preferably 0.4-1.5mol/L.In the aqueous solution B, the concentration of the water solublity lithium source can be
0.2-4.5mol/L, preferably 3-4mol/L.
In the atomization and during mixing, can first fix the atomization rates of the water solution A, then by monitoring
The pH value of system is adjusting the atomization rates of the aqueous solution B；The atomization rates of the aqueous solution B can also be first fixed, then
The atomization rates of the water solution A are adjusted by the pH value of monitoring system；Can also by the pH value of monitoring system and simultaneously
Adjust the atomization rates of the water solution A and the aqueous solution B.Preferably, the atomization rates control of the water solution A is existed
0.1-20L/min, more preferably control in 1.5-5L/min, and the mist of the aqueous solution B is adjusted by the pH value of monitoring system
Change speed；Or, the atomization rates of the aqueous solution B are controlled in 0.1-25L/min, more preferably to control in 1.5-8L/min,
And the atomization rates of the water solution A are adjusted by the pH value of monitoring system, can so obtain that particle diameter is less and electrochemistry
The more preferable LiFePO4 of performance.
The watersoluble divalent source of iron can be the existing various compounds containing ferrous ion that can be dissolved in water, its
Instantiation is included but is not limited to：One kind in ferrous chloride, ferrous bromide, ferrous nitrate, ferrous sulfate and Ferrous acetate or
It is various.Additionally, the ferrous sulfate can be the ferrous sulfate with water of crystallization, such as ferrous sulfate monohydrate, anhydrous slufuric acid it is ferrous,
Ferrous sulfate heptahydrate etc..
The example of the water-soluble phosphate is included but is not limited to：Lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium phosphate
One or more.
The water solublity lithium source can be the existing various lithium-containing compounds that can be dissolved in water, its instantiation include but
It is not limited to：One or more in Lithium hydrate, Quilonorm (SKB), lithium bromide, lithium chloride, lithium iodide and lithium nitrate, particularly preferably
Lithium hydrate.
It should be noted that when the raw material for preparing the LiFePO4 contains lithium dihydrogen phosphate, the lithium dihydrogen phosphate
Only regard as and added as the water-soluble phosphate, i.e. will be mixed containing the lithium dihydrogen phosphate and watersoluble divalent source of iron
Compound counts the consumption of the lithium dihydrogen phosphate in the consumption of water-soluble phosphate as water solution A.
In accordance with the present invention it is preferred that, the water solution A is also containing reducing agent and/or surfactant.When the aqueous solution
When A also contains reducing agent, oxidation of the ferrous ion in mixing and course of reaction can be reduced, so as to significantly more reduce
To LiFePO4 in impurity content.When the water solution A also contains surfactant, it is possible to increase the iron phosphate for obtaining
The volume energy density of lithium.
The consumption of the reducing agent and surfactant can be selected according to the consumption of watersoluble divalent source of iron.Example
Such as, the consumption of the reducing agent can be with the weight ratio of the consumption of the watersoluble divalent source of iron（0.0005-0.075）:1,
Preferably（0.005-0.02）:1.The consumption of the surfactant can with the weight ratio of the consumption of the watersoluble divalent source of iron
Think（0.00025-0.005）:1, preferably（0.0005-0.004）:1.Additionally, the reducing agent can be existing various
The material that ferrous ion is oxidized probability in mixing and course of reaction can be reduced, for example, can for ascorbic acid and/or
Citric acid.The instantiation of the surfactant is included but is not limited to：Cetyl trimethylammonium bromide（CTAB）, lauric acid
Ester quat, cetyl benzenesulfonic acid sodium and Polyethylene Glycol（PEG）In one or more.
According to the present invention, the condition of the reaction includes：Reaction temperature can be 120-280 DEG C, preferably 160-200
℃；Reaction pressure can be 0.5-3MPa, preferably 0.8-1.5MPa；Response time can be 2-24 hours, and preferably 3-6 is little
When；The pH value of reaction system can be 6.5-10.5, preferably 8-9.In the present invention, the pressure refers both to gauge pressure.Will reaction
System pH value control 6.5-10.5, be preferably controlled in the mode of 8-9 can add in reaction system acidic materials or
Alkaline matter.The acidic materials for example can be one or more in phosphoric acid, sulphuric acid, nitric acid and hydrochloric acid.The basic species
Matter for example can be one or more in ammonia, potassium hydroxide, sodium hydroxide and Lithium hydrate.The acidic materials and alkalescence
Material can be used with pure state, it is also possible to be used in the form of its aqueous solution, and its consumption is with by the pH value control of reaction system
System is defined in above range, and therefore not to repeat here.When the acidic materials are that phosphoric acid and/or the alkaline matter are Lithium hydrate
When, the consumption of phosphoric acid and Lithium hydrate for adjusting pH value of reaction system is not counted in the consumption of reaction raw materials.
Additionally, the oxidation in order to avoid the oxygen in air to ferrous ion in reaction mass, it is preferable that the reaction
Carry out in an inert atmosphere.Wherein, the mode for keeping inert atmosphere can be that noble gases are passed through in reaction system to replace
Non-inert gas in the reaction system, then again by the reaction system sealing Jing after gas displacement.The noble gases can
Think nitrogen and/or helium.
According to the present invention, the preparation method of the LiFePO4 also includes being filtered, washed and dried the product.
Wherein, the washing first can be washed with deionized 1-3 time, then with absolute ethanol washing 1-3 time.
In accordance with the present invention it is preferred that, the preparation method of the LiFePO4 also includes entering product with organic carbon source
Row mixing is simultaneously spray-dried, then the Spray dried products for obtaining are carried out into roasting, can so improve the LiFePO4 that obtains
Electric conductivity.
The present invention is not particularly limited to the species and consumption of the organic carbon source.As a rule, the organic carbon source
Can be the existing various Organic substances that can be carbonized below 500 DEG C, its instantiation is included but is not limited to：Glucose, sugarcane
One or more in sugar, Lactose, maltose, phenolic resin and epoxy resin.Additionally, the consumption of the organic carbon source should root
Selected according to the amount of product, for example, in terms of the dry weight of the product of 100 weight portions, the organic carbon source
Consumption can be 5-25 weight portions, preferably 5-15 weight portions.
According to the present invention, the concrete operation method and condition of the spray drying are known to the skilled person.Specifically
Ground, the slurry being made into by the product and organic carbon source and water is added in nebulizer and rotates to realize spray dried at a high speed
It is dry.The temperature of the spray drying can be 95-120 DEG C, preferably 100-105 DEG C.It should be noted that the product
Can be through dried product, or undried product.When the product is through dry product
When, the product of solid, organic carbon source and additional water can be mixed to obtain the slurry；When the product
For undried product when, the product for itself containing certain water directly can be mixed described to obtain with organic carbon source
Slurry, if during contained in product water shortage, it is also possible to additionally add a certain amount of water.Additionally, in the slurry
The amount of water can be the conventional selection of this area, and as well known to those skilled in the art to this, therefore not to repeat here.
The present invention is not particularly limited to the condition of the roasting, as long as the organic carbon source can be carbonized,
For example, the condition of the roasting includes that sintering temperature can be 600-750 DEG C, and roasting time can be 3-12 hours.Additionally, institute
Stating roasting is generally carried out in an inert atmosphere.
Present invention also offers the LiFePO4 prepared by said method.
Additionally, present invention also offers the LiFePO4 as positive electrode active materials application.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, scanning electron microscope（SEM）For HIT（Hitachi）Production
S4800 type scanning electron microscopes, test voltage is 5KV.X-ray diffractometer is Beijing Puxi General Instrument Co., Ltd
The XD-2 type X-ray diffractometers of production, wherein, test condition includes：Pipe pressure is 200mA, and electric current is 200mA, and step-length is 1 °, is surveyed
Examination angle is 10 ° -90 °.
In following examples and comparative example, volume energy density（mWh/cm3）It is calculated according to below equation：Volume energy
Metric density（mWh/cm3）=compacted density（g/cm3）× discharge capacity（mAh/g）.
Embodiment 1
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
（1）Prepare presoma：
Under nitrogen protection, the ferrous sulfate aqueous solution of 35L concentration for 1.485mol/L is prepared, and prepares 10L concentration and be
The phosphate aqueous solution of 5.25mol/L, then mixed solution will be formed in phosphate aqueous solution addition ferrous sulfate aqueous solution, it is subsequently adding
20g ascorbic acid, 50g citric acids and 20g cetyl trimethylammonium bromide, form water solution A.
Under nitrogen protection, aqueous solution B of the 45L concentration for the Lithium hydrate of 3.50mol/L is prepared.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by kettle
Water solution A and aqueous solution B are carried out atomization contact by interior injection apparatus, during the atomization contact, by water solution A
Atomization speed control controls the pH value of system 6.0 in 2.5L/min, and the atomization rates of aqueous solution B are controlled by pH controllers.
After water solution A and aqueous solution B feed and terminate, the pH value of atomization product of contact is adjusted to 8.5, obtain the muddiness of presoma
Liquid.
（2）Prepare LiFePO4：
With nitrogen by the air emptying in autoclave, then by step（1）The turbid solution of the presoma of preparation is moved to
In autoclave and temperature is risen to into 180 DEG C with 1.3 DEG C/min of speed carries out hydro-thermal reaction, in the process of hydro-thermal reaction
In, the mixing speed of autoclave is controlled at 300 revs/min, by air pressure control in 1.2MPa, after reacting 5 hours, it is passed through
The temperature of autoclave is down to 25 DEG C by cooling water, obtains the dirty solution of phosphoric acid ferrum lithium, is filtered with putting-down machine,
Then deionized water successively with 60kg and dehydrated alcohol respectively washing 3 times of 20L, and by the filter cake after washing in vacuum drying oven
95 DEG C of drying, obtain iron phosphate powder L1.The X-ray diffraction spectrum of iron phosphate powder L1 and LiFePO4 standard sample
Figure（XRD spectra）As shown in Figure 1.It can be seen that the diffraction maximum of iron phosphate powder L1 is corresponding with standard sample, and do not see
Observe dephasign peak, it can be seen that, iron phosphate powder L1 has very high purity.
By above-mentioned iron phosphate powder L1 and glucose in mass ratio 100:10 ratio mixes by medium of deionized water
Uniformly, wherein, the mass ratio of iron phosphate powder and deionized water is 20:100.Mixed slurry is spray-dried at 95 DEG C
After move in sintering furnace, and under nitrogen protection, at 700 DEG C sinter 6 hours, then gas is broken, obtains LiFePO 4 material
ML1.Fig. 2 is the scanning electron microscope of LiFePO 4 material ML1（SEM）Photo.From the figure, it can be seen that LiFePO 4 material ML1
Primary particle size is essentially 200-500nm, is shaped as bar-shaped.
By iron phosphate serving as positive active material material ML1, acetylene black, Kynoar（Rich modeling collagen is celebrated purchased from Dongguan City
Material company limited, the trade mark is FR900）By weight it is 90:5:5 are dissolved in N-Methyl pyrrolidone, and at 110 DEG C ± 5 DEG C
Be pressed into after vacuum drying thickness for 0.2mm, the disk of a diameter of Φ 12mm as positive pole.Using metal lithium sheet as negative pole, every
Film is microporous polypropylene membrane（Celgard2300）, for the LiPF6/ (EC+DMC) of 1.0mol/L, (wherein, LiPF6 is six to electrolyte
Lithium fluophosphate, EC is ethylene carbonate, and DMC is dimethyl carbonate, and the volume ratio of EC and DMC is 1:1), in the handss full of argon
Seal in casing, make R2025 button cells.At 30 DEG C of room temperature, the R2025 button cells are carried out into charge and discharge electrical measurement with 0.1C
Its charge/discharge capacity is measured, wherein, end of charge voltage is 3.8V, and discharge cut-off voltage is 2.5V, is as a result shown, the R2025 buttons
First charge-discharge capacity of the formula battery under 0.1C is respectively 161.51mAh/g and 159.96mAh/g, and efficiency for charge-discharge is
99.04%（Efficiency for charge-discharge（%）=discharge capacity ÷ charging capacity × 100%, similarly hereinafter）.Additionally, by calculating, the R2025
The volume energy density of button cell is 1108.36mWh/cm3。
Embodiment 2
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
（1）Prepare presoma：
Under nitrogen protection, bivalence source of iron aqueous solution of the 35L concentration for 1.0mol/L is prepared（Ferrous sulfate is pressed with Ferrous acetate
Mol ratio 9:1 mixed aqueous solution for being formed）, and the phosphate aqueous solution that 10L concentration is 3.57mol/L is prepared, then phosphoric acid is water-soluble
Liquid is added in bivalence source of iron aqueous solution and forms mixed solution, is subsequently adding 20g ascorbic acid, 27.7g citric acids and 4.8g 16
Alkyl trimethyl ammonium bromide, forms water solution A.
It is in molar ratio 10 by Lithium hydrate and Quilonorm (SKB) under nitrogen protection:1 prepares 35L lithium concentrations for 3mol/L
Solution B.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by kettle
Water solution A and aqueous solution B are carried out atomization contact by interior injection apparatus, during the atomization contact, by water solution A
Atomization speed control controls the pH value of system 5.0 in 1.5L/min, and the atomization rates of aqueous solution B are controlled by pH controllers.
After water solution A and aqueous solution B feed and terminate, the pH value of atomization product of contact is adjusted to 8.0, obtain the muddiness of presoma
Liquid.
（2）Prepare LiFePO4：
With nitrogen by the air emptying in autoclave, then by step（1）The turbid solution of the presoma of preparation is moved to
In autoclave and temperature is risen to into 160 DEG C with 1.3 DEG C/min of speed carries out hydro-thermal reaction, in the process of hydro-thermal reaction
In, the mixing speed of autoclave is controlled at 300 revs/min, by air pressure control in 0.8MPa, react 6 hours, it is passed through cold
But the temperature of autoclave is down to 25 DEG C by water, obtains the dirty solution of phosphoric acid ferrum lithium, is filtered with putting-down machine, so
Deionized water successively with 60kg and dehydrated alcohol respectively washing 3 times of 20L afterwards, and by the filter cake after washing 95 in vacuum drying oven
DEG C drying, obtain iron phosphate powder L2.From iron phosphate powder L2 and the knot of the XRD spectra of LiFePO4 standard sample
Fruit is as can be seen that the diffraction maximum of iron phosphate powder L2 is corresponding with standard sample, and does not observe dephasign peak, it can be seen that, it is described
Iron phosphate powder L2 has very high purity.
By phenolic resin（Shanghai Duo Kang Industrial Co., Ltd.s, the trade mark is 2402）Dissolving is in ethanol（Phenolic resin and second
The mass ratio of alcohol is 1:20）, the ethanol solution of phenolic resin is obtained, then by above-mentioned iron phosphate powder L2 and phenolic resin
Ethanol solution with deionized water as medium mix homogeneously, wherein, the mass ratio of iron phosphate powder L2 and phenolic resin is 100:
5, iron phosphate powder L2 is 20 with the mass ratio of deionized water:100.Mixed slurry is moved after being spray-dried at 120 DEG C
Into sintering furnace, and under nitrogen protection, at 600 DEG C sinter 12 hours, then gas is broken, obtains LiFePO 4 material ML2.From
Stereoscan photograph can be seen that the primary particle size of LiFePO 4 material ML2 and be essentially 200-500nm, be shaped as bar-shaped.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
160.58mAh/g and 159.22mAh/g, efficiency for charge-discharge is 99.15%, and volume energy density is 1081.71mWh/cm3。
Embodiment 3
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
（1）Prepare presoma：
Under nitrogen protection, ferrous chloride aqueous solution of the 35L concentration for 2.0mol/L is prepared, and by phosphoric acid and ammonium dihydrogen phosphate
Mol ratio be 10:1 prepares solution of the 20L phosphate concentrations for 3.5mol/L, then the aqueous solution of phosphorous acid group is added into chlorination
Mixed solution is formed in ferrous aqueous solution, 100g ascorbic acid, 90.8g citric acids and 38.15g cetyl front threes is subsequently adding
Base ammonium bromide, forms water solution A.
Under nitrogen protection, aqueous solution B of the 52.5L concentration for the Lithium hydrate of 4mol/L is prepared.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by kettle
Water solution A and aqueous solution B are carried out atomization contact by interior injection apparatus, during the atomization contact, by water solution A
Atomization speed control controls the pH value of system 7.5 in 5L/min, and the atomization rates of aqueous solution B are controlled by pH controllers.Treat
Water solution A and aqueous solution B feed after terminating, and the pH value of atomization product of contact is adjusted to 9, obtain the dirty solution of presoma.
（2）Prepare LiFePO4：
With nitrogen by the air emptying in autoclave, then by step（1）The turbid solution of the presoma of preparation is moved to
In autoclave and temperature is risen to into 200 DEG C with 1.3 DEG C/min of speed carries out hydro-thermal reaction, in the process of hydro-thermal reaction
In, the mixing speed of autoclave is controlled at 300 revs/min, by air pressure control in 1.5MPa, after reacting 3 hours, it is passed through
The temperature of autoclave is down to 25 DEG C by cooling water, obtains the dirty solution of phosphoric acid ferrum lithium, is filtered with putting-down machine,
Then with the deionized water wash 3 times of 60kg, and 95 DEG C of drying in vacuum drying oven by the filter cake after washing, obtain LiFePO4
Powder L3.Can be seen that LiFePO4 L3's from the result of the LiFePO4 L3 and the XRD spectra of LiFePO4 standard sample
Diffraction maximum is corresponding with standard sample, and does not observe dephasign peak, it can be seen that, iron phosphate powder L3 has very high pure
Degree.
By above-mentioned iron phosphate powder L3 and glucose in mass ratio 100:15 ratio mixes by medium of deionized water
Uniformly, wherein, the mass ratio of iron phosphate powder and deionized water is 20:100.Mixed slurry spray dried at 105 DEG C
Move to after dry in sintering furnace, and under nitrogen protection, at 750 DEG C sinter 3 hours, then gas is broken, obtains LiFePO 4 material
ML3.From stereoscan photograph as can be seen that the primary particle size of LiFePO4 ML3 is essentially 200-500nm, it is shaped as bar-shaped.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, the R2025 button cells are respectively in the first charge-discharge capacity of 0.1C
159.11mAh/g and 158.96mAh/g, efficiency for charge-discharge is 99.91%, and volume energy density is 1079.69mWh/cm3。
Embodiment 4
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
（1）Prepare presoma：
Under nitrogen protection, the ferrous sulfate aqueous solution of 60L concentration for 0.5mol/L is prepared, and prepares 10L concentration and be
The phosphate aqueous solution of 3.0mol/L, then mixed solution will be formed in phosphate aqueous solution addition ferrous sulfate aqueous solution, it is subsequently adding
30g ascorbic acid, 50g citric acids and 30g Polyethylene Glycol（Qingdao Yi Nuoxin Chemical Co., Ltd.s, the trade mark is PEG300）, formed
Water solution A.
Under nitrogen protection, aqueous solution B of the 60L concentration for the Lithium hydrate of 1.50mol/L is prepared.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by kettle
Water solution A and aqueous solution B are carried out atomization contact by interior injection apparatus, during the atomization contact, by aqueous solution B's
Atomization speed control controls the pH value of system 7.0 in 2.0L/min, and the atomization rates of water solution A are controlled by pH controllers.
After water solution A and aqueous solution B feed and terminate, the pH value of atomization product of contact is adjusted to 7.5, obtain the muddiness of presoma
Liquid.
（2）Prepare LiFePO4：
It is same as Example 1, obtain iron phosphate powder L4 and LiFePO 4 material ML4.Wherein, the LiFePO4 powder
The XRD spectra of last L4 and LiFePO4 standard sample is as shown in Figure 3.It can be seen that the diffraction of iron phosphate powder L4
Peak is corresponding with standard sample, and does not observe dephasign peak, it can be seen that, iron phosphate powder L4 has very high purity.Fig. 4
For the stereoscan photograph of LiFePO 4 material ML4.It can be seen that the primary particle size of LiFePO 4 material ML4 is basic
For 200-600nm, shape is bar-shaped.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
158.65mAh/g and 157.13mAh/g, efficiency for charge-discharge is 99.04%, and volume energy density is 1102.36mWh/cm3。
Embodiment 5
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
Method according to embodiment 4 prepares LiFePO4, except for the difference that, in the water solution A ascorbic acid is added without
And citric acid, obtain iron phosphate powder L5 and LiFePO 4 material ML5.Wherein, from iron phosphate powder L5 and phosphorus
The diffraction maximum that the XRD spectra of sour ferrum lithium standard sample can be seen that iron phosphate powder L5 is corresponding with standard sample, and does not observe miscellaneous
Xiang Feng, it can be seen that, iron phosphate powder L5 has very high purity.From stereoscan photograph as can be seen that iron phosphate
The primary particle size of lithium material ML5 is essentially 200-600nm, is shaped as bar-shaped.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
157.11mAh/g and 155.01mAh/g, efficiency for charge-discharge is 98.66%, and volume energy density is 1032.35mWh/cm3。
Embodiment 6
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
Method according to embodiment 4 prepares LiFePO4, except for the difference that, in the water solution A Polyethylene Glycol is added without,
Obtain iron phosphate powder L6 and LiFePO 4 material ML6.Wherein, from iron phosphate powder L6 and LiFePO4 standard
The diffraction maximum that the XRD spectra of sample can be seen that LiFePO4 L6 is corresponding with standard sample, and does not observe dephasign peak, it can be seen that,
Iron phosphate powder L6 has very high purity.From stereoscan photograph as can be seen that LiFePO 4 material ML6 once
Particle diameter is essentially 200-700nm, is shaped as bar-shaped.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
158.01mAh/g and 156.03mAh/g, efficiency for charge-discharge is 98.75%, and volume energy density is 1059.32mWh/cm3。
Embodiment 7
The embodiment is used to illustrate LiFePO4 of present invention offer and preparation method thereof.
Method according to embodiment 4 prepares LiFePO4, except for the difference that, do not include by iron phosphate powder and glucose with
And the step of deionized water mixing, spray drying and roasting, but directly using iron phosphate powder L4 as positive electrode active materials.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
156.33mAh/g and 155.21mAh/g, efficiency for charge-discharge is 99.28%, and volume energy density is 1036.85mWh/cm3。
Comparative example 1
The comparative example is used to illustrate LiFePO4 of reference and preparation method thereof.
Method according to embodiment 1 prepares LiFePO4, except for the difference that, does not adopt atomization contact, comprises the following steps that：
（1）Prepare presoma：
Under nitrogen protection, the ferrous sulfate aqueous solution of 35L concentration for 1.485mol/L is prepared, and prepares 10L concentration and be
The phosphate aqueous solution of 5.25mol/L, then mixed solution will be formed in phosphate aqueous solution addition ferrous sulfate aqueous solution, it is subsequently adding
20g ascorbic acid, 50g citric acids and 20g cetyl trimethylammonium bromide, form water solution A.
Under nitrogen protection, aqueous solution B of the 45L concentration for the Lithium hydrate of 3.50mol/L is prepared.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by meter
Amount pump adds water solution A in stirred tank with the charging rate of 1.5L/min, and the pH value of system is controlled 6.0, aqueous solution B's
Charging rate is controlled by pH controllers.After water solution A and aqueous solution B feed and terminate, the pH value of product is adjusted to 8.5,
Obtain the dirty solution of presoma.
（2）Prepare LiFePO4：
It is same as Example 1, obtain iron phosphate powder DL1 and LiFePO 4 material DML1.Wherein, from the iron phosphate
The diffraction maximum that the XRD spectra of lithium powder DL1 and LiFePO4 standard specimen can be seen that LiFePO4 DL1 is corresponding with standard sample, and
Not it was observed that dephasign peak, it can be seen that, iron phosphate powder DL1 has very high purity.The LiFePO 4 material
The stereoscan photograph of DML1 is as shown in Figure 5.From the figure, it can be seen that the primary particle size of the LiFePO 4 material DML1 is basic
For 800-1000nm, it is shaped as spherical.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
152.49mAh/g and 151.11mAh/g, efficiency for charge-discharge is 99.09%, and volume energy density is 1016.54mWh/cm3。
Comparative example 2
The comparative example is used to illustrate LiFePO4 of reference and preparation method thereof.
Method according to embodiment 1 prepares LiFePO4, and except for the difference that, in atomization contact process, control ph, does not have
Body step is as follows：
（1）Prepare presoma：
Under nitrogen protection, the ferrous sulfate aqueous solution of 35L concentration for 1.485mol/L is prepared, and prepares 10L concentration and be
The phosphate aqueous solution of 5.25mol/L, then mixed solution will be formed in phosphate aqueous solution addition ferrous sulfate aqueous solution, it is subsequently adding
20g ascorbic acid, 50g citric acids and 20g cetyl trimethylammonium bromide, form water solution A.
Under nitrogen protection, aqueous solution B of the 45L concentration for the Lithium hydrate of 3.50mol/L is prepared.
10L deionized waters are added in closed stirred tank, and with the air in nitrogen emptying stirred tank, then by kettle
Water solution A and aqueous solution B are carried out atomization contact by interior injection apparatus, during the atomization contact, by water solution A
Atomization speed control controls the atomization speed of aqueous solution B in 1.5L/min in 1.5L/min, and now the pH value of system is in 5.3-
11.2 interior fluctuation.After water solution A and aqueous solution B feed and terminate, the pH value of atomization product of contact is adjusted to 8.5, obtained
The dirty solution of presoma.
（2）Prepare LiFePO4：
It is same as Example 1, obtain iron phosphate powder DL2 and LiFePO 4 material DML2.Wherein, from the iron phosphate
The diffraction maximum that the XRD spectra of lithium DL2 and LiFePO4 standard specimen can be seen that LiFePO4 DL2 is corresponding with standard sample, and has
Li3PO4Occur with the dephasign peak of FeP, it can be seen that, impurity is contained in iron phosphate powder DL1, purity is relatively low.The phosphorus
The stereoscan photograph of sour ferrum lithium material DML2 is as shown in Figure 6.From the figure, it can be seen that the one of the LiFePO 4 material DML2
Secondary particle diameter is essentially 400-600nm, is shaped as spherical.
Method according to embodiment 1 prepares R2025 button cells and to charge/discharge capacity, efficiency for charge-discharge and volume energy
Metric density is measured and calculates, and as a result shows, first charge-discharge capacity of the R2025 button cells under 0.1C is respectively
153.12mAh/g and 151.85mAh/g, efficiency for charge-discharge is 99.17%, and volume energy density is 1002.95mWh/cm3。
As can be seen from the above results, it is obtained in that particle diameter is little and the preferable iron phosphate of chemical property using the method
Lithium, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The compound mode of energy is no longer separately illustrated.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of preparation method of LiFePO4, the method is included watersoluble divalent source of iron, water solublity phosphorus source and water solublity
Lithium source mixes water-filling thermal response of going forward side by side, and the water solublity phosphorus source is phosphoric acid and/or water-soluble phosphate, it is characterised in that described
The mode of mixing is included by the water solution A containing the watersoluble divalent source of iron and the water solublity phosphorus source and containing the water
The aqueous solution B of dissolubility lithium source is atomized and is mixed, and is being atomized by controlling the water solution A and the aqueous solution B
Atomization rates in journey control the pH value of mix products in 5-7.5.
2. preparation method according to claim 1, wherein, the consumption of the watersoluble divalent source of iron, the water-soluble phosphoruses
The consumption of the consumption in source and the water solublity lithium source makes Fe in the mix products for finally giving2+、PO4 3-With Li+Mol ratio be
(0.95-1.05):(0.95-1.05):3。
3. preparation method according to claim 1 and 2, wherein, in the water solution A, the watersoluble divalent source of iron
Concentration be 0.2-2.5mol/L；In the aqueous solution B, the concentration of the water solublity lithium source is 0.2-4.5mol/L.
4. preparation method according to claim 3, wherein, the atomization rates of the water solution A are 0.1-20L/min；Or
Person, the atomization rates of the aqueous solution B are 0.1-25L/min.
5. preparation method according to claim 4, wherein, the atomization rates of the water solution A are 1.5-5L/min；Or
Person, the atomization rates of the aqueous solution B are 1.5-8L/min.
6. preparation method according to claim 1 and 2, wherein, the watersoluble divalent source of iron is selected from ferrous chloride, bromination
One or more in ferrous iron, ferrous nitrate, ferrous sulfate and Ferrous acetate；The water-soluble phosphate is selected from biphosphate
One or more in lithium, ammonium dihydrogen phosphate and diammonium phosphate；The water solublity lithium source is selected from Lithium hydrate, Quilonorm (SKB), bromine
Change one or more in lithium, lithium chloride, lithium iodide and lithium nitrate.
7. preparation method according to claim 1, wherein, the water solution A also contains reducing agent；The use of the reducing agent
It is (0.0005-0.075) to measure with the weight ratio of the consumption of the watersoluble divalent source of iron:1；The reducing agent is ascorbic acid
And/or citric acid.
8. the preparation method according to claim 1 or 7, wherein, the water solution A also contains surfactant；The table
The consumption of face activating agent is (0.00025-0.005) with the weight ratio of the consumption of the watersoluble divalent source of iron:1；The surface
Activating agent is in cetyl trimethylammonium bromide, laurate quaternary ammonium salt, cetyl benzenesulfonic acid sodium and Polyethylene Glycol
One or more.
9. preparation method according to claim 1 and 2, wherein, the condition of the reaction includes：Reaction temperature is 120-
280 DEG C, reaction pressure is 0.5-3MPa, and the response time is 2-24 hours, and the pH value of reaction system is 6.5-10.5.
10. preparation method according to claim 1 and 2, wherein, the condition of the reaction includes：Reaction temperature is 160-
200 DEG C, reaction pressure is 0.8-1.5MPa, and the response time is 3-6 hours, and the pH value of reaction system is 8-9.
11. preparation methoies according to claim 1, wherein, the method also includes carrying out product with organic carbon source
Mix and be spray-dried, then the Spray dried products for obtaining are carried out into roasting.
12. preparation methoies according to claim 11, wherein, in terms of the dry weight of the product of 100 weight portions, institute
The consumption for stating organic carbon source is 5-25 weight portions；The organic carbon source is selected from glucose, sucrose, Lactose, maltose, phenolic resin
With one or more in epoxy resin.
13. preparation methoies according to claim 11 or 12, wherein, the temperature of the spray drying is 95-120 DEG C.
14. preparation methoies according to claim 11 or 12, wherein, the condition of the roasting includes：Sintering temperature is
600-750 DEG C, roasting time is 3-12 hours.
The LiFePO4 that 15. preparation methoies by described in any one in claim 1-14 are prepared.
Application of the LiFePO4 described in 16. claim 15 as positive electrode active materials.
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| CN106876785B (en) * | 2015-12-13 | 2019-02-19 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell electrolyte containing additive |
| 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 |
| CN107986253B (en) * | 2017-11-09 | 2019-11-12 | 湖南雅城新材料有限公司 | Ball shape ferric phosphate and its preparation method and application |
| GB2616234A (en) * | 2021-11-26 | 2023-08-30 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
| CN114249311B (en) * | 2021-11-26 | 2023-03-07 | 广东邦普循环科技有限公司 | Preparation method of porous sodium ion battery positive electrode material sodium iron phosphate |
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| CN101948103A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Method for preparing ferrous phosphate radical lithium salt of lithium ion battery |
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