CN104752717A - 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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- CN104752717A CN104752717A CN201310740269.9A CN201310740269A CN104752717A CN 104752717 A CN104752717 A CN 104752717A CN 201310740269 A CN201310740269 A CN 201310740269A CN 104752717 A CN104752717 A CN 104752717A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention 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 the application as positive electrode active materials of a kind of preparation method of LiFePO4, the LiFePO4 prepared by the method and described LiFePO4.
Background technology
In recent years, lithium-ion-power cell is paid close attention to widely because having important application prospect in electric automobile (EVs), hybrid-electric car (HEVs) etc.The price of lithium-ion-power cell practical application, fail safe, environmental protection and useful life are the focal issues of research always.LiFePO4 (LiFePO
4) owing to having the high (170mAhg of specific capacity
-1), the advantage such as high, the good cycle of low, the environmental friendliness of the prices of raw and semifnished materials, fail safe, become the positive electrode active materials of the lithium-ion-power cell of most potentiality.
But, in LiFePO4 structure, FeO
6octahedra by PO
4tetrahedron is separated, LiO
6octahedra along b direction of principal axis limit altogether, form chain, the electronic conductivity causing pure ferric phosphate lithium is lower by (10
-9scm
-1).In addition, Li
+spread along the one dimension passage in [010] direction in olivine crystal structure, such one dimension passage can because Li
2fe misplaces and hinders Li
+long-range migration, cause lithium ion diffusion coefficient less by (1.8 × 10
-14cm
2s
-1), and because which limit its use under high power conditions.Two effective ways of the electrical conductance of current raising LiFePO4 be reduce its particle diameter and carbon carry out to it coated.
Wherein, the LiFePO4 of water heat transfer receives much concern owing to having the feature of little, the narrow diameter distribution in material footpath.During water heat transfer LiFePO4, normally first prepare presoma by source of iron, lithium source and phosphorus source, then presoma is carried out reaction under high pressure thus obtains LiFePO4.Current research shows, in the process of water heat transfer LiFePO4, the pH value of presoma, the concentration of reactant, reducing agent, surfactant and hydrothermal temperature, reaction time etc. are the principal elements affecting end product.Wherein, the pH value of presoma, because decide the dissolving of presoma and the growth course of crystal in course of reaction and becoming the factor of most critical, is the most important process control parameters of water heat transfer LiFePO4 product consistency.
But in existing technology, people are often only concerned about its pH value of adjustment when controlling presoma.Such as, disclose a kind of hydrothermal synthesis method of LiFePO4, first mixed with phosphoric acid by lithium hydroxide in CN101752564A, then add ferrous sulfate when 40-50 DEG C, then with lithium hydroxide or sulphur acid for adjusting pH, and obtaining product, to carry out carbon coated.But the particle diameter of the LiFePO4 adopting the method to obtain is still micron order, and impurity content is still higher, therefore can not effectively improve its chemical property.
Summary of the invention
The object of the invention is to overcome the comparatively large and defect that chemical property is poor of the particle diameter of LiFePO4 adopting existing method to prepare, and a kind of preparation method of new LiFePO4, the LiFePO4 prepared by the method and described LiFePO4 are as the application of positive electrode active materials.Adopt the method can obtain the little and good LiFePO4 of chemical property of particle diameter.
The invention provides a kind of preparation method of LiFePO4, the method comprises and watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source is mixed and reacted, described water-soluble phosphorus source is phosphoric acid and/or water-soluble phosphate, wherein, the mode of described mixing comprises carries out being atomized and mixing with the aqueous solution B containing described water-soluble lithium source by the water solution A containing described watersoluble divalent source of iron and described water-soluble phosphorus source, and is controlled the pH value of mix products at 5-7.5 by the described water solution A of control and the atomization rates of described aqueous solution B in atomization process.
Present invention also offers the LiFePO4 prepared by said method.
In addition, present invention also offers the application of described LiFePO4 as positive electrode active materials.
Prepare in the process of LiFePO4 in existing employing hydro thermal method, the presoma normally first watersoluble divalent source of iron, water-soluble phosphorus source and the mixing of water-soluble lithium source generated rapidly containing the multiple intermediate sedimentation product such as ferrous phosphate, lithium phosphate, and then under pyroreaction condition, make the multiple intermediate sedimentation product conversion in described presoma be LiFePO4.And the present inventor is found by further investigation, in high-temperature reaction process, the precipitation in described presoma can be dissolved and recrystallization again, and the particle diameter of particle size on the final LiFePO4 obtained of described presoma has very important impact.The presoma that particle is too large can cause that the lithium iron phosphate particles that finally obtains is large, efficiency for charge-discharge is low; And the too little presoma of particle can cause the LiFePO4 finally obtained easily to occur the phenomenon of reuniting.
And adopt method of the present invention the size controlling of the LiFePO4 obtained can be had a good chemical property at submicron order.Infer its reason, may be due to: on the one hand, adopt and the water solution A containing described watersoluble divalent source of iron and water-soluble phosphorus source is carried out being atomized and mixing with the aqueous solution B containing described water-soluble lithium source, reactant can be dispersed into microlayer model, each microlayer model is the reactor of a micro volume, because the volume of the microlayer model being atomized rear formation is little, thus not only control reaction mass contact time nucleation and make contact generate particle less, and the brilliant Induction time of the length that can extend precipitated crystal, therefore, just can by the size controlling of presoma and the LiFePO4 finally obtained at submicron order when not grinding, on the other hand, in described atomization and mixing process in, by the atomization rates controlling described water solution A and described aqueous solution B, the pH value of mix products is controlled at 5-7.5, the environment preparing presoma can not only be provided, but also can reduce the risk that in described watersoluble divalent source of iron, ferrous ion is oxidized, and (ferrous ion easily generates Fe (OH) under strongly alkaline conditions finally to reduce the content of impurity in the LiFePO4 obtained
2, and Fe (OH)
2be very easy to be oxidized to Fe (OH)
3, and then make in the product that obtains containing Fe
2o
3).
A preferred embodiment of the invention, when described water solution A is also containing reducing agent, the probability that ferrous ion is oxidized in mixing and course of reaction can be reduced, thus reduce the content of impurity in LiFePO4 and improve its chemical property further.
According to another kind of preferred implementation of the present invention, when described water solution A is also containing surfactant, the volume energy density of the LiFePO4 obtained can also be improved, thus be conducive to obtaining the less positive electrode of volume.
According to another kind of preferred implementation of the present invention, when the preparation method of described LiFePO4 also comprises, product and organic carbon source are carried out mixing and spraying dry, when again the Spray dried products obtained being carried out roasting, due to the carbonization of described organic carbon source, the conductivity of described LiFePO4 can be improved further, and and then improve its chemical property further.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the LiFePO4 of embodiment 1 preparation and the X-ray diffraction spectrogram of LiFePO4 standard sample;
Fig. 2 is the stereoscan photograph of LiFePO4 prepared by embodiment 1;
Fig. 3 is the LiFePO4 of embodiment 4 preparation and the X-ray diffraction spectrogram of 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.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of LiFePO4 provided by the invention comprises and watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source is mixed and reacted, described water-soluble phosphorus source is phosphoric acid and/or water-soluble phosphate, wherein, the mode of described mixing comprises carries out being atomized and mixing with the aqueous solution B containing described water-soluble lithium source by the water solution A containing described watersoluble divalent source of iron and described water-soluble phosphorus source, and is controlled the pH value of mix products at 5-7.5 by the described water solution A of control and the atomization rates of described aqueous solution B in atomization process.
The consumption of the present invention to described watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source is not particularly limited, such as, the consumption in the consumption of described watersoluble divalent source of iron, total consumption in described water-soluble phosphorus source and described water-soluble lithium source makes Fe in the mix products finally obtained
2+, PO
4 3-with Li
+mol ratio can be (0.95-1.05): (0.95-1.05): 3, be preferably (0.98-1): (0.98-1): 3.In addition, in described water solution A, the concentration of described watersoluble divalent source of iron can be 0.2-2.5mol/L, is preferably 0.4-1.5mol/L.In described aqueous solution B, the concentration in described water-soluble lithium source can be 0.2-4.5mol/L, is preferably 3-4mol/L.
In described atomization and mixing process in, first can fix the atomization rates of described water solution A, then be regulated the atomization rates of described aqueous solution B by the pH value of monitoring system; Also first can fix the atomization rates of described aqueous solution B, then be regulated the atomization rates of described water solution A by the pH value of monitoring system; Also can also be regulated the atomization rates of described water solution A and described aqueous solution B by the pH value of monitoring system simultaneously.Preferably, the atomization rates of described water solution A controlled at 0.1-20L/min, more preferably control at 1.5-5L/min, and regulate the atomization rates of described aqueous solution B by the pH value of monitoring system; Or, the atomization rates of described aqueous solution B controlled at 0.1-25L/min, more preferably control at 1.5-8L/min, and the atomization rates of described water solution A is regulated by the pH value of monitoring system, can obtain that particle diameter is less like this and electrochemistry can better LiFePO4.
Described watersoluble divalent source of iron can be existing various can be water-soluble containing the compound of ferrous ion, its instantiation includes but not limited to: one or more in frerrous chloride, ferrous bromide, ferrous nitrate, ferrous sulfate and ferrous acetate.In addition, described ferrous sulfate can be the ferrous sulfate with the crystallization water, as ferrous sulfate monohydrate, anhydrous slufuric acid ferrous iron, ferrous sulfate heptahydrate etc.
The example of described water-soluble phosphate includes but not limited to: one or more of lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
Described water-soluble lithium source can be existing various can be water-soluble lithium-containing compound, its instantiation includes but not limited to: one or more in lithium hydroxide, lithium acetate, lithium bromide, lithium chloride, lithium iodide and lithium nitrate, is particularly preferably lithium hydroxide.
It should be noted that, when the raw material preparing described LiFePO4 contains lithium dihydrogen phosphate, described lithium dihydrogen phosphate is only regarded as and is added as described water-soluble phosphate, namely, using the mixture containing described lithium dihydrogen phosphate and watersoluble divalent source of iron as water solution A, the consumption of described lithium dihydrogen phosphate is counted in the consumption of water-soluble phosphate.
According to the present invention, preferably, described water solution A is also containing reducing agent and/or surfactant.When described water solution A is also containing reducing agent, the oxidation of ferrous ion in mixing and course of reaction can be reduced, thus reduce the content of impurity in the LiFePO4 obtained more significantly.When described water solution A is also containing surfactant, the volume energy density of the LiFePO4 obtained can be improved.
The consumption of described reducing agent and surfactant can be selected according to the consumption of watersoluble divalent source of iron.Such as, the weight ratio of the consumption of described reducing agent and the consumption of described watersoluble divalent source of iron can be (0.0005-0.075): 1, is preferably (0.005-0.02): 1.The weight ratio of the consumption of described surfactant and the consumption of described watersoluble divalent source of iron can be (0.00025-0.005): 1, is preferably (0.0005-0.004): 1.In addition, described reducing agent can be the existing various material that can reduce ferrous ion oxidized probability in mixing and course of reaction, such as, can be ascorbic acid and/or citric acid.The instantiation of described surfactant includes but not limited to: one or more in softex kw (CTAB), laurate quaternary ammonium salt, cetyl benzenesulfonic acid sodium and polyethylene glycol (PEG).
According to the present invention, the condition of described reaction comprises: reaction temperature can be 120-280 DEG C, is preferably 160-200 DEG C; Reaction pressure can be 0.5-3MPa, is preferably 0.8-1.5MPa; Reaction time can be 2-24 hour, is preferably 3-6 hour; The pH value of reaction system can be 6.5-10.5, is preferably 8-9.In the present invention, described pressure all refers to gauge pressure.The pH value of reaction system controlled at 6.5-10.5, preferably control to add acidic materials or alkaline matter in reaction system in the mode of 8-9.Described acidic materials can be such as one or more in phosphoric acid, sulfuric acid, nitric acid and hydrochloric acid.Described alkaline matter can be such as one or more in ammoniacal liquor, potassium hydroxide, NaOH and lithium hydroxide.Described acidic materials and alkaline matter can use with pure state, also can use with the form of its aqueous solution, and its consumption is to control the pH value of reaction system to be as the criterion in above-mentioned scope, and therefore not to repeat here.When described acidic materials are phosphoric acid and/or described alkaline matter is lithium hydroxide, the consumption for the phosphoric acid and lithium hydroxide that regulate pH value of reaction system is not counted in the consumption of reaction raw materials.
In addition, in order to avoid the oxygen in air is to the oxidation of ferrous ion in reaction mass, preferably, described reaction is carried out in an inert atmosphere.Wherein, the mode of inert atmosphere is kept for pass into replace the non-inert gas in described reaction system in reaction system by inert gas, and then the reaction system after gas displacement can be sealed.Described inert gas can be nitrogen and/or helium.
According to the present invention, the preparation method of described LiFePO4 also comprises described product filtration, washing also drying.Wherein, described washing first can spend deionized water 1-3 time, then uses absolute ethanol washing 1-3 time.
According to the present invention, preferably, the preparation method of described LiFePO4 also comprises and product and organic carbon source is carried out mixing and spraying dry, then the Spray dried products obtained is carried out roasting, can improve the conductivity of the LiFePO4 obtained like this.
The present invention is not particularly limited the kind of described organic carbon source and consumption.As a rule, described organic carbon source can be existing various can the organic substance of carbonization below 500 DEG C, its instantiation includes but not limited to: one or more in glucose, sucrose, lactose, maltose, phenolic resins and epoxy resin.In addition, the consumption of described organic carbon source should be selected according to the amount of product, and such as, with the dry weight basis of the described product of 100 weight portions, the consumption of described organic carbon source can be 5-25 weight portion, is preferably 5-15 weight portion.
According to the present invention, described spray-dired concrete operation method and condition are known to the skilled person.Particularly, the slurry be made into by described product and organic carbon source and water to be joined in atomizer High Rotation Speed to realize spraying dry.Described spray-dired temperature can be 95-120 DEG C, is preferably 100-105 DEG C.It should be noted that, described product can be through dried product, also can be the product of undried.When described product is the product through super-dry, can by the mixing of the product of solid, organic carbon source and additional water to obtain described slurry; When described product is the product of undried, itself directly can be mixed to obtain described slurry with organic carbon source containing the product of certain water, if during water shortage contained by product, also can additionally add a certain amount of water.In addition, in described slurry, the amount of water can be the routine selection of this area, and as well known to those skilled in the art to this, therefore not to repeat here.
The condition of the present invention to described roasting is not particularly limited, as long as can by described organic carbon source carbonization, such as, it can be 600-750 DEG C that the condition of described roasting comprises sintering temperature, and roasting time can be 3-12 hour.In addition, described roasting is carried out usually in an inert atmosphere.
Present invention also offers the LiFePO4 prepared by said method.
In addition, present invention also offers the application of described LiFePO4 as positive electrode active materials.
Below will be described the present invention by embodiment.
In following examples and comparative example, the S4800 type scanning electron microscopy that scanning electron microscopy (SEM) is produced for HIT (Hitachi), test voltage is 5KV.X-ray diffractometer is the XD-2 type X-ray diffractometer that Beijing Puxi General Instrument Co., Ltd produces, and wherein, test condition comprises: pipe pressure is 200mA, and electric current is 200mA, and step-length is 1 °, and test angle is 10 °-90 °.
In following examples and comparative example, volume energy density (mWh/cm
3) obtain according to following formulae discovery: volume energy density (mWh/cm
3)=compacted density (g/cm
3) × discharge capacity (mAh/g).
Embodiment 1
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
(1) presoma is prepared:
Under nitrogen protection; preparation 35L concentration is the ferrous sulfate aqueous solution of 1.485mol/L; and prepare the phosphate aqueous solution that 10L concentration is 5.25mol/L; again phosphate aqueous solution is added in ferrous sulfate aqueous solution and form mixed solution; then add 20g ascorbic acid, 50g citric acid and 20g softex kw, form water solution A.
Under nitrogen protection, preparation 45L concentration is the aqueous solution B of the lithium hydroxide of 3.50mol/L.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then by the injection apparatus in still, water solution A is carried out atomization with aqueous solution B to contact, in the process of described atomization contact, the atomization speed of water solution A is controlled at 2.5L/min, control 6.0 by the pH value of system, the atomization rates of aqueous solution B is controlled by pH controller.After water solution A and all reinforced end of aqueous solution B, the pH value of atomization product of contact is adjusted to 8.5, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
With nitrogen by the air emptying in autoclave, the turbid solution of the presoma then step (1) prepared to move in autoclave and with the speed of 1.3 DEG C/min, temperature is risen to 180 DEG C and carries out hydro-thermal reaction, in the process of hydro-thermal reaction, the mixing speed of autoclave is controlled at 300 revs/min, air pressure is controlled at 1.2MPa, react after 5 hours, pass into cooling water and the temperature of autoclave is down to 25 DEG C, obtain the dirty solution of phosphoric acid iron lithium, filter with putting-down machine, then 3 times are respectively washed with the deionized water of 60kg and the absolute ethyl alcohol of 20L successively, and by the filter cake 95 DEG C of oven dry in vacuum drying oven after washing, obtain iron phosphate powder L1.The X-ray diffraction spectrogram (XRD spectra) of described iron phosphate powder L1 and LiFePO4 standard sample as shown in Figure 1.As can be seen from the figure, the diffraction maximum of iron phosphate powder L1 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L1 has very high purity.
Be that medium mixes by the ratio of above-mentioned iron phosphate powder L1 and glucose 100:10 in mass ratio with deionized water, wherein, the mass ratio of iron phosphate powder and deionized water is 20:100.Mixed slurry moves in sintering furnace after spraying dry at 95 DEG C, and sinters 6 hours under nitrogen protection, at 700 DEG C, and then gas is broken, obtains LiFePO 4 material ML1.Fig. 2 is ESEM (SEM) photo of LiFePO 4 material ML1.As we can see from the figure, the primary particle size of LiFePO 4 material ML1 is 200-500nm substantially, and shape is bar-shaped.
By iron phosphate serving as positive active material material ML1, acetylene black, Kynoar (purchased from Dongguan City Qing Feng plastic material Co., Ltd, the trade mark is FR900) by weight being dissolved in 1-METHYLPYRROLIDONE for 90:5:5, and at 110 DEG C ± 5 DEG C, after vacuum drying, be pressed into that thickness is 0.2mm, diameter is that the disk of Φ 12mm is as positive pole.Using metal lithium sheet as negative pole, barrier film is microporous polypropylene membrane (Celgard2300), electrolyte be the LiPF6/ (EC+DMC) of 1.0mol/L (wherein, LiPF6 is lithium hexafluoro phosphate, EC is ethylene carbonate, and DMC is dimethyl carbonate, and the volume ratio of EC and DMC is 1:1), seal in the glove box being full of argon gas, make R2025 button cell.At room temperature 30 DEG C, this R2025 button cell is carried out discharge and recharge with 0.1C and measures its charge/discharge capacity, wherein, end of charge voltage is 3.8V, discharge cut-off voltage is 2.5V, and result shows, the first charge-discharge capacity of this R2025 button cell under 0.1C is respectively 161.51mAh/g and 159.96mAh/g, efficiency for charge-discharge is 99.04%(efficiency for charge-discharge (%)=discharge capacity ÷ charging capacity × 100%, lower same).In addition, known by calculating, the volume energy density of this R2025 button cell is 1108.36mWh/cm
3.
Embodiment 2
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
(1) presoma is prepared:
Under nitrogen protection; preparation 35L concentration is the divalence source of iron aqueous solution (ferrous sulfate and ferrous acetate be the mixed aqueous solution that formed of 9:1 in molar ratio) of 1.0mol/L; and prepare the phosphate aqueous solution that 10L concentration is 3.57mol/L; phosphate aqueous solution is added in the divalence source of iron aqueous solution again and form mixed solution; then add 20g ascorbic acid, 27.7g citric acid and 4.8g softex kw, form water solution A.
Under nitrogen protection, be the solution B of 3mol/L for 10:1 prepares 35L lithium concentration in molar ratio by lithium hydroxide and lithium acetate.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then by the injection apparatus in still, water solution A is carried out atomization with aqueous solution B to contact, in the process of described atomization contact, the atomization speed of water solution A is controlled at 1.5L/min, control 5.0 by the pH value of system, the atomization rates of aqueous solution B is controlled by pH controller.After water solution A and all reinforced end of aqueous solution B, the pH value of atomization product of contact is adjusted to 8.0, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
With nitrogen by the air emptying in autoclave, the turbid solution of the presoma then step (1) prepared to move in autoclave and with the speed of 1.3 DEG C/min, temperature is risen to 160 DEG C and carries out hydro-thermal reaction, in the process of hydro-thermal reaction, the mixing speed of autoclave is controlled at 300 revs/min, air pressure is controlled at 0.8MPa, react 6 hours, pass into cooling water and the temperature of autoclave is down to 25 DEG C, obtain the dirty solution of phosphoric acid iron lithium, filter with putting-down machine, then 3 times are respectively washed with the deionized water of 60kg and the absolute ethyl alcohol of 20L successively, and by the filter cake 95 DEG C of oven dry in vacuum drying oven after washing, obtain iron phosphate powder L2.As can be seen from the result of the XRD spectra of described iron phosphate powder L2 and LiFePO4 standard sample, the diffraction maximum of iron phosphate powder L2 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L2 has very high purity.
By phenolic resins (Shanghai Duo Kang Industrial Co., Ltd., the trade mark is 2402) dissolve in ethanol (mass ratio of phenolic resins and ethanol is 1:20), obtain the ethanolic solution of phenolic resins, then be that medium mixes by the ethanolic solution of above-mentioned iron phosphate powder L2 and phenolic resins with deionized water, wherein, the mass ratio of iron phosphate powder L2 and phenolic resins is the mass ratio of 100:5, iron phosphate powder L2 and deionized water is 20:100.Mixed slurry moves in sintering furnace after spraying dry at 120 DEG C, and sinters 12 hours under nitrogen protection, at 600 DEG C, and then gas is broken, obtains LiFePO 4 material ML2.As can be seen from stereoscan photograph, the primary particle size of LiFePO 4 material ML2 is 200-500nm substantially, and shape is bar-shaped.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Embodiment 3
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
(1) presoma is prepared:
Under nitrogen protection; preparation 35L concentration is the ferrous chloride aqueous solution of 2.0mol/L; and be the solution that 10:1 prepares that 20L phosphate concentration is 3.5mol/L by the mol ratio of phosphoric acid and ammonium dihydrogen phosphate; again the aqueous solution of phosphorous acid group is added in ferrous chloride aqueous solution and form mixed solution; then add 100g ascorbic acid, 90.8g citric acid and 38.15g softex kw, form water solution A.
Under nitrogen protection, preparation 52.5L concentration is the aqueous solution B of the lithium hydroxide of 4mol/L.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then by the injection apparatus in still, water solution A is carried out atomization with aqueous solution B to contact, in the process of described atomization contact, the atomization speed of water solution A is controlled at 5L/min, control 7.5 by the pH value of system, the atomization rates of aqueous solution B is controlled by pH controller.After water solution A and all reinforced end of aqueous solution B, the pH value of atomization product of contact is adjusted to 9, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
With nitrogen by the air emptying in autoclave, the turbid solution of the presoma then step (1) prepared to move in autoclave and with the speed of 1.3 DEG C/min, temperature is risen to 200 DEG C and carries out hydro-thermal reaction, in the process of hydro-thermal reaction, the mixing speed of autoclave is controlled at 300 revs/min, air pressure is controlled at 1.5MPa, react after 3 hours, pass into cooling water and the temperature of autoclave is down to 25 DEG C, obtain the dirty solution of phosphoric acid iron lithium, filter with putting-down machine, then 3 times are washed with the deionized water of 60kg, and by the filter cake 95 DEG C of oven dry in vacuum drying oven after washing, obtain iron phosphate powder L3.As can be seen from the result of the XRD spectra of described LiFePO4 L3 and LiFePO4 standard sample, the diffraction maximum of LiFePO4 L3 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L3 has very high purity.
Be that medium mixes by the ratio of above-mentioned iron phosphate powder L3 and glucose 100:15 in mass ratio with deionized water, wherein, the mass ratio of iron phosphate powder and deionized water is 20:100.Mixed slurry moves in sintering furnace after spraying dry at 105 DEG C, and sinters 3 hours under nitrogen protection, at 750 DEG C, and then gas is broken, obtains LiFePO 4 material ML3.As can be seen from stereoscan photograph, the primary particle size of LiFePO4 ML3 is 200-500nm substantially, and shape is bar-shaped.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, this R2025 button cell is respectively 159.11mAh/g and 158.96mAh/g at the first charge-discharge capacity of 0.1C, efficiency for charge-discharge is 99.91%, and volume energy density is 1079.69mWh/cm
3.
Embodiment 4
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
(1) presoma is prepared:
Under nitrogen protection; preparation 60L concentration is the ferrous sulfate aqueous solution of 0.5mol/L; and prepare the phosphate aqueous solution that 10L concentration is 3.0mol/L; again phosphate aqueous solution is added in ferrous sulfate aqueous solution and form mixed solution; then 30g ascorbic acid, 50g citric acid and 30g polyethylene glycol (Qingdao Yi Nuoxin Chemical Co., Ltd. is added; the trade mark is PEG300), form water solution A.
Under nitrogen protection, preparation 60L concentration is the aqueous solution B of the lithium hydroxide of 1.50mol/L.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then by the injection apparatus in still, water solution A is carried out atomization with aqueous solution B to contact, in the process of described atomization contact, the atomization speed of aqueous solution B is controlled at 2.0L/min, control 7.0 by the pH value of system, the atomization rates of water solution A is controlled by pH controller.After water solution A and all reinforced end of aqueous solution B, the pH value of atomization product of contact is adjusted to 7.5, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
Identical with embodiment 1, obtain iron phosphate powder L4 and LiFePO 4 material ML4.Wherein, the XRD spectra of described iron phosphate powder L4 and LiFePO4 standard sample as shown in Figure 3.As can be seen from the figure, the diffraction maximum of iron phosphate powder L4 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L4 has very high purity.Fig. 4 is the stereoscan photograph of LiFePO 4 material ML4.As can be seen from the figure, the primary particle size of LiFePO 4 material ML4 is 200-600nm substantially, and shape is bar-shaped.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Embodiment 5
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
LiFePO4 is prepared according to the method for embodiment 4, unlike, in described water solution A, do not add ascorbic acid and citric acid, obtain iron phosphate powder L5 and LiFePO 4 material ML5.Wherein, as can be seen from the XRD spectra of described iron phosphate powder L5 and LiFePO4 standard sample, the diffraction maximum of iron phosphate powder L5 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L5 has very high purity.As can be seen from stereoscan photograph, the primary particle size of LiFePO 4 material ML5 is 200-600nm substantially, and shape is bar-shaped.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Embodiment 6
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
LiFePO4 is prepared according to the method for embodiment 4, unlike, in described water solution A, do not add polyethylene glycol, obtain iron phosphate powder L6 and LiFePO 4 material ML6.Wherein, as can be seen from the XRD spectra of described iron phosphate powder L6 and LiFePO4 standard sample, the diffraction maximum of LiFePO4 L6 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder L6 has very high purity.As can be seen from stereoscan photograph, the primary particle size of LiFePO 4 material ML6 is 200-700nm substantially, and shape is bar-shaped.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Embodiment 7
This embodiment is for illustration of LiFePO4 provided by the invention and preparation method thereof.
Prepare LiFePO4 according to the method for embodiment 4, unlike, do not comprise iron phosphate powder is mixed with glucose and deionized water, spraying dry the step of roasting, but directly using iron phosphate powder L4 as positive electrode active materials.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Comparative example 1
This comparative example is for illustration of the LiFePO4 and preparation method thereof of reference.
LiFePO4 is prepared according to the method for embodiment 1, unlike, do not adopt atomization contact, concrete steps are as follows:
(1) presoma is prepared:
Under nitrogen protection; preparation 35L concentration is the ferrous sulfate aqueous solution of 1.485mol/L; and prepare the phosphate aqueous solution that 10L concentration is 5.25mol/L; again phosphate aqueous solution is added in ferrous sulfate aqueous solution and form mixed solution; then add 20g ascorbic acid, 50g citric acid and 20g softex kw, form water solution A.
Under nitrogen protection, preparation 45L concentration is the aqueous solution B of the lithium hydroxide of 3.50mol/L.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then add stirred tank in by water solution A with the charging rate of 1.5L/min by measuring pump, control 6.0 by the pH value of system, the charging rate of aqueous solution B is controlled by pH controller.After water solution A and all reinforced end of aqueous solution B, the pH value of product is adjusted to 8.5, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
Identical with embodiment 1, obtain iron phosphate powder DL1 and LiFePO 4 material DML1.Wherein, as can be seen from the XRD spectra of described iron phosphate powder DL1 and LiFePO4 standard specimen, the diffraction maximum of LiFePO4 DL1 is corresponding with standard sample, and does not observe dephasign peak, and as can be seen here, described iron phosphate powder DL1 has very high purity.The stereoscan photograph of described LiFePO 4 material DML1 as shown in Figure 5.As we can see from the figure, the primary particle size of described LiFePO 4 material DML1 is 800-1000nm substantially, and shape is that class is spherical.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
Comparative example 2
This comparative example is for illustration of the LiFePO4 and preparation method thereof of reference.
LiFePO4 is prepared according to the method for embodiment 1, unlike, in atomization contact process, not control ph, concrete steps are as follows:
(1) presoma is prepared:
Under nitrogen protection; preparation 35L concentration is the ferrous sulfate aqueous solution of 1.485mol/L; and prepare the phosphate aqueous solution that 10L concentration is 5.25mol/L; again phosphate aqueous solution is added in ferrous sulfate aqueous solution and form mixed solution; then add 20g ascorbic acid, 50g citric acid and 20g softex kw, form water solution A.
Under nitrogen protection, preparation 45L concentration is the aqueous solution B of the lithium hydroxide of 3.50mol/L.
10L deionized water is added in airtight stirred tank, and with the air in nitrogen emptying stirred tank, then by the injection apparatus in still, water solution A is carried out atomization with aqueous solution B to contact, in the process of described atomization contact, the atomization speed of water solution A is controlled at 1.5L/min, control at 1.5L/min by the atomization speed of aqueous solution B, now the pH value of system fluctuates in 5.3-11.2.After water solution A and all reinforced end of aqueous solution B, the pH value of atomization product of contact is adjusted to 8.5, obtains the dirty solution of presoma.
(2) LiFePO4 is prepared:
Identical with embodiment 1, obtain iron phosphate powder DL2 and LiFePO 4 material DML2.Wherein, as can be seen from the XRD spectra of described LiFePO4 DL2 and LiFePO4 standard specimen, the diffraction maximum of LiFePO4 DL2 is corresponding with standard sample, and has Li
3pO
4occur with the dephasign peak of FeP, as can be seen here, containing impurity in described iron phosphate powder DL1, purity is lower.The stereoscan photograph of described LiFePO 4 material DML2 as shown in Figure 6.As we can see from the figure, the primary particle size of described LiFePO 4 material DML2 is 400-600nm substantially, and shape is that class is spherical.
Prepare R2025 button cell according to the method for embodiment 1 and measurement and calculation is carried out to charge/discharge capacity, efficiency for charge-discharge and volume energy density, result shows, the first charge-discharge capacity of this R2025 button cell 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/cm
3.
As can be seen from the above results, adopt the method can obtain the little and good LiFePO4 of chemical property of particle diameter, have prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. the preparation method of a LiFePO4, the method comprises and watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source is mixed and reacted, described water-soluble phosphorus source is phosphoric acid and/or water-soluble phosphate, it is characterized in that, the mode of described mixing comprises carries out being atomized and mixing with the aqueous solution B containing described water-soluble lithium source by the water solution A containing described watersoluble divalent source of iron and described water-soluble phosphorus source, and is controlled the pH value of mix products at 5-7.5 by the described water solution A of control and the atomization rates of described aqueous solution B in atomization process.
2. preparation method according to claim 1, wherein, the consumption in the consumption of described watersoluble divalent source of iron, the consumption in described water-soluble phosphorus source and described water-soluble lithium source makes Fe in the mix products finally obtained
2+, PO
4 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 described water solution A, the concentration of described watersoluble divalent source of iron is 0.2-2.5mol/L; In described aqueous solution B, the concentration in described water-soluble lithium source is 0.2-4.5mol/L.
4. preparation method according to claim 3, wherein, the atomization rates of described water solution A is 0.1-20L/min; Or the atomization rates of described aqueous solution B is 0.1-25L/min.
5. preparation method according to claim 4, wherein, the atomization rates of described water solution A is 1.5-5L/min; Or the atomization rates of described aqueous solution B is 1.5-8L/min.
6. preparation method according to claim 1 and 2, wherein, described watersoluble divalent source of iron be selected from frerrous chloride, ferrous bromide, ferrous nitrate, ferrous sulfate and ferrous acetate one or more; Described water-soluble phosphate be selected from lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate one or more; Described water-soluble lithium source be selected from lithium hydroxide, lithium acetate, lithium bromide, lithium chloride, lithium iodide and lithium nitrate one or more.
7. preparation method according to claim 1, wherein, described water solution A is also containing reducing agent; The weight ratio of the consumption of described reducing agent and the consumption of described watersoluble divalent source of iron is (0.0005-0.075): 1; Described reducing agent is ascorbic acid and/or citric acid.
8. the preparation method according to claim 1 or 7, wherein, described water solution A is also containing surfactant; The weight ratio of the consumption of described surfactant and the consumption of described watersoluble divalent source of iron is (0.00025-0.005): 1; Described surfactant be selected from softex kw, laurate quaternary ammonium salt, cetyl benzenesulfonic acid sodium, citric acid and polyethylene glycol one or more.
9. preparation method according to claim 1 and 2, wherein, the condition of described reaction comprises: reaction temperature is 120-280 DEG C, is preferably 160-200 DEG C; Reaction pressure is 0.5-3MPa, is preferably 0.8-1.5MPa; Reaction time is 2-24 hour, is preferably 3-6 hour; The pH value of reaction system is 6.5-10.5, is preferably 8-9.
10. preparation method according to claim 1, wherein, the method also comprises is undertaken mixing and spraying dry by product and organic carbon source, then the Spray dried products obtained is carried out roasting.
11. preparation methods according to claim 10, wherein, with the dry weight basis of the described product of 100 weight portions, the consumption of described organic carbon source is 5-25 weight portion; Described organic carbon source be selected from glucose, sucrose, lactose, maltose, phenolic resins and epoxy resin one or more.
12. preparation methods according to claim 10 or 11, wherein, described spray-dired temperature is 95-120 DEG C.
13. preparation methods according to claim 10 or 11, wherein, the condition of described roasting comprises: sintering temperature is 600-750 DEG C, and roasting time is 3-12 hour.
14. LiFePO4s prepared by the preparation method in claim 1-13 described in any one.
15. LiFePO4s according to claim 14 are as the application of positive electrode active materials.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816581A (en) * | 2015-11-30 | 2017-06-09 | 比亚迪股份有限公司 | A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery |
| CN106876785A (en) * | 2015-12-13 | 2017-06-20 | 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 |
| CN107986253A (en) * | 2017-11-09 | 2018-05-04 | 湖南雅城新材料有限公司 | Ball shape ferric phosphate and its preparation method and application |
| CN114249311A (en) * | 2021-11-26 | 2022-03-29 | 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903708A (en) * | 2006-08-18 | 2007-01-31 | 河南环宇集团有限公司 | Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
| 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 |
-
2013
- 2013-12-27 CN CN201310740269.9A patent/CN104752717B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903708A (en) * | 2006-08-18 | 2007-01-31 | 河南环宇集团有限公司 | Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816581A (en) * | 2015-11-30 | 2017-06-09 | 比亚迪股份有限公司 | A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery |
| CN106816581B (en) * | 2015-11-30 | 2019-06-21 | 比亚迪股份有限公司 | A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and anode and lithium battery |
| CN106876785A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell electrolyte containing additive |
| 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 |
| CN107986253A (en) * | 2017-11-09 | 2018-05-04 | 湖南雅城新材料有限公司 | Ball shape ferric phosphate and its preparation method and application |
| CN114249311A (en) * | 2021-11-26 | 2022-03-29 | 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 |
| WO2023093158A1 (en) * | 2021-11-26 | 2023-06-01 | 广东邦普循环科技有限公司 | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
| 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 |
| US20240067525A1 (en) * | 2021-11-26 | 2024-02-29 | Guangdong Brunp Recycling Technology Co., Ltd. | Preparation method of porous sodium iron phosphate used as sodium ion battery cathode material |
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