CN104752720A - Lithium manganese ferric phosphate, preparation method and application thereof - Google Patents
Lithium manganese ferric phosphate, preparation method and application thereof Download PDFInfo
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- CN104752720A CN104752720A CN201310743803.1A CN201310743803A CN104752720A CN 104752720 A CN104752720 A CN 104752720A CN 201310743803 A CN201310743803 A CN 201310743803A CN 104752720 A CN104752720 A CN 104752720A
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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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- 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 for lithium manganese ferric phosphate, the lithium manganese ferric phosphate prepared by the method and application of the lithium manganese ferric phosphate as an anode active material. The preparation method of the lithium manganese ferric phosphate includes: merging and mixing a first solution containing a water soluble bivalent manganese source, a water soluble bivalent iron source and a water soluble phosphorus source with a second solution containing a water soluble lithium source to carry out reaction, in the merging and mixing process, controlling the flow speed of the first solution and the second solution to control the pH value of the obtained merged mixed product constantly at 6.5-7.5, the water soluble phosphorus source is phosphoric acid/or dihydrogen phosphate salt, or a mixture of phosphoric acid and/or dihydrogen phosphate salt and monohydrogen phosphate salt and/or neutral phosphate, and at least part of the water soluble lithium source is lithium hydroxide. With the method, lithium manganese ferric phosphate with small particle size, uniform particle size distribution and excellent electrochemical performance can be obtained.
Description
Technical field
The present invention relates to the application as positive electrode active materials of a kind of preparation method of iron manganese phosphate for lithium, the iron manganese phosphate for lithium prepared by the method and described iron manganese phosphate for lithium.
Background technology
Power-type lithium ion battery has the advantage of high-energy-density, high-specific-power, high security and long circulation life, is the ideal source of following motor vehicle and other various electric tools.Wherein, iron manganese phosphate for lithium is one of of greatest concern and the most promising positive electrode active materials preparing power-type lithium ion battery at present.In described iron manganese phosphate for lithium positive electrode active materials, impurity content is low, particle diameter is little and even particle size distribution improves the key of its chemical property.
For iron manganese phosphate for lithium, it normally adopts and the reaction of manganese sulfate, ferrous sulfate, phosphoric acid and lithium hydroxide is prepared.Such as, CN101807698A discloses a kind of super/subcritical water thermal process and prepares power type lithium-ion battery anode material technology, it is characterized in that, the method comprises the following steps: raw material lithium source and the mixed liquor two fluids that is made up of source of iron/manganese source, source of phosphoric acid are injected in blender and mix by (1) respectively continuously; (2) the 3rd fluid streams be made up of deionized water is first injected in preheater and heats, the temperature of described preheater controls at 80-200 DEG C, described deionized water after heating enters into described blender, and mixes with the described two fluids in step (1); (3) enter high-temperature high-pressure reaction kettle from the mixed liquor of three fluid streams out of blender described in step (2) and carry out hydrothermal crystallizing reaction, reaction temperature is 150-500 DEG C, reaction pressure is 5-50MPa, the reaction time is 10s-1h; (4) product be obtained by reacting through described hydrothermal crystallizing first carries out heat exchange, cooling by heat exchanger and the external world, then after filter filters large-grain particles and impurity, enters into solid-liquid separator, and particulate deposits is got off; (5) particulate precipitated in described solid-liquid separator is collected continuously also dry, obtain the dry powder of anode material for lithium-ion batteries.In addition, the mixed liquor be made up of source of iron/manganese source and source of phosphoric acid in step (1) can also containing the metal ion as modifier, and lithium in described mixed liquor, iron/manganese, be 1:1-x:x:1 as the metal ion of modifier, the mol ratio of phosphoric acid, wherein, x is 0-0.1.Although adopt method disclosed in CN101807698A can obtain the less iron manganese phosphate for lithium of particle diameter, but need strictly to control reaction temperature and pressure in whole preparation process, and the impurity content of the iron manganese phosphate for lithium obtained is higher, and domain size distribution is also even not.
Therefore, in order to obtain the more excellent iron manganese phosphate for lithium positive electrode active materials of chemical property, needing its impurity content of reduction at present badly, reduce its particle diameter and improve its particle size distribution.
Summary of the invention
The domain size distribution that the object of the invention is to overcome the iron manganese phosphate for lithium adopting existing method to prepare not evenly and the excellent not defect of chemical property, and provides a kind of preparation method of new iron manganese phosphate for lithium, the iron manganese phosphate for lithium prepared by the method and described iron manganese phosphate for lithium as the application of positive electrode active materials.Little and the even particle size distribution of the particle diameter of iron manganese phosphate for lithium adopting the method to obtain, thus there is more excellent chemical property.
The invention provides a kind of preparation method of iron manganese phosphate for lithium, wherein, the method comprises containing watersoluble divalent manganese source, first solution and second solution containing water-soluble lithium source in watersoluble divalent source of iron and water-soluble phosphorus source react after also flowing and mixing, described and stream mixing process in, by the flow velocity that controls described first solution and the second solution with by obtain and the pH value flowing mix products control all the time at 6.5-7.5, described water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or be the mixture of phosphoric acid and/or dihydric phosphate and dibasic alkaliine and/or neutral phosphate, at least part of described water-soluble lithium source is lithium hydroxide.
Present invention also offers the iron manganese phosphate for lithium prepared by said method.
In addition, present invention also offers the application of described iron manganese phosphate for lithium as positive electrode active materials.
The present inventor is found by further investigation, in the preparation process of described iron manganese phosphate for lithium, prior art mainly takes following three kinds of feed way: first manganese sulfate and ferrous sulfate are added in phosphate aqueous solution and mix, obtain mixed liquor, then lithium hydroxide aqueous solution is added in above-mentioned mixed liquor mix; Or, first manganese sulfate and ferrous sulfate are added in phosphate aqueous solution and mix, and then the mixed liquor obtained is added in lithium hydroxide aqueous solution mix; Or, first phosphoric acid is added in lithium hydroxide aqueous solution and mixes, obtain mixed liquor, and then the aqueous solution of manganese sulfate and ferrous sulfate is added in above-mentioned mixed liquor.But, when adopting first two feed way, in the mixed process of material, hydroxide ion gradually in and hydrogen ion or hydrogen ion gradually in and hydroxide ion, the pH value of mixed slurry constantly changes along with the carrying out of mixed process, thus cause, in mixed slurry, complex reaction occurs, the sub-manganese of phosphoric acid hydrogen may be generated, phosphoric acid hydrogen is ferrous, lithium phosphate, the sub-manganese of phosphoric acid, ferrous phosphate, hydroxide manganese, the precipitations such as ferrous hydroxide, and different precipitation can cause the pH value of mixed slurry to change, the pH value of such mixed slurry and deposited components reciprocal effect, thus cause deposited components and the ratio of pyroreaction forward slip value slurry, granular size and uniformity are difficult to control, and and then the impurity content of the final iron manganese phosphate for lithium obtained of impact, particle size and domain size distribution.When adopting the third feed way, the sub-manganese of lithium phosphate, phosphoric acid and ferrous phosphate problem pockety can be brought, thus the chemical property of the iron manganese phosphate for lithium obtained can be affected further.
But, the present invention adopts and flows the mode mixed and mixed by reaction mass, and whole and flow in mixed process, by the flow velocity that controls described first solution and the second solution with by obtain and the pH value flowing mix products control all the time at 6.5-7.5, can ensure that the thing of mixed slurry is consistent before pyroreaction well, thus obtain that particle diameter is little, even particle size distribution and the iron manganese phosphate for lithium of electrochemical performance.
A preferred embodiment of the invention, when also containing reducing agent in described first solution, can reduce divalent manganesetion and ferrous ion and oxidation in stream mixing and course of reaction, thus improve the chemical property of the iron manganese phosphate for lithium obtained further.
According to another kind of preferred implementation of the present invention, when the preparation method of described iron manganese phosphate for lithium also comprise by described and flow mix products 10-50 DEG C, be uniformly mixed 10-30min under 300-800rpm, at 10-50 DEG C, sand milling 0.5-3 is constantly little again, mixed slurry can be made more uniformly to be disperseed, thus reduce the particle diameter of the iron manganese phosphate for lithium obtained further and improve its even particle size distribution.
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 structural representation of mixing arrangement provided by the invention;
Fig. 2 is the X-ray diffraction spectrogram of the iron manganese phosphate for lithium that obtains of embodiment 1 and standard sample;
Fig. 3 is the scanning electron microscopy spectrogram of the iron manganese phosphate for lithium that embodiment 1 obtains;
Fig. 4 is the X-ray diffraction spectrogram of the iron manganese phosphate for lithium that obtains of embodiment 2 and standard sample;
Fig. 5 is the X-ray diffraction spectrogram of the iron manganese phosphate for lithium that obtains of comparative example 1 and standard sample.
Description of reference numerals
1-reactor; 2-first NaOH solution tank NaOH; 3-second NaOH solution tank NaOH; 4-pH controller; 5-first measuring pump; 6-second measuring pump; 7-paddle.
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 iron manganese phosphate for lithium provided by the invention comprises the first solution containing watersoluble divalent manganese source, watersoluble divalent source of iron and water-soluble phosphorus source flow to mix reacted afterwards with the second solution containing water-soluble lithium source, described and stream mixing process in, by the flow velocity that controls described first solution and the second solution with by obtain and the pH value flowing mix products control all the time at 6.5-7.5, described water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or is the mixture of phosphoric acid and/or dihydric phosphate and dibasic alkaliine and/or neutral phosphate; At least part of described water-soluble lithium source is lithium hydroxide.
Wherein, described " and stream mixing " refers to the logistics of described first solution to introduce in same container with the logistics of described second solution simultaneously and mixes.
Described and flow mixing and can carry out in existing various mixing arrangement.Such as, as shown in Figure 1, described mixing arrangement can comprise: reactor 1, first NaOH solution tank NaOH 2, second NaOH solution tank NaOH 3 and pH controller 4, described first NaOH solution tank NaOH 2 is communicated with described reactor 1 by the first measuring pump 5, described second NaOH solution tank NaOH 3 is communicated with described reactor 1 by the second measuring pump 6, and the probe of described pH controller 4 is arranged in described reactor 1 and described pH controller 4 is communicated with described first measuring pump 5 or described second measuring pump 6.In addition, in order to more be conducive to the Homogeneous phase mixing of material, described reactor 1 preferably also comprises paddle 7, and described reactor 1 can be sand mill usually.
When adopting above-mentioned mixing arrangement to carry out and flow mixing, described and method that is stream mixing comprises described first solution is placed in described first NaOH solution tank NaOH 1, described second solution is placed in described second NaOH solution tank NaOH 2, not corresponding with the measuring pump that described pH controller 4 is communicated with solution is added in described reactor 1 with constant flow velocity, and by the flow velocity that controls the solution corresponding with the measuring pump that described pH controller 4 is communicated with so that the described and pH value flowing mix products is controlled at 6.5-7.5.In addition, when described first solution and the second solution are added in described reactor 1, usually need to open described paddle 7.
Described first solution can be identical with the concentration of the second solution, also can be different, and can be 0.1-5mol/L independently of one another.It should be noted that, the concentration of described first solution and the second solution comprises the total concentration of all solutes wherein contained.Now, the flow velocity of described first solution can be 10-150mL/min, and the flow velocity of described second solution is controlled by the described and pH value flowing mix products; Or the flow velocity of described second solution is 10-150mL/min, and the flow velocity of described first solution is controlled by the described and pH value flowing mix products.
Described dihydric phosphate can be such as one or more in lithium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate etc.; Described dibasic alkaliine can be such as one or more in potassium phosphate,monobasic, ammonium hydrogen phosphate, disodium-hydrogen etc.; Described neutral phosphate can be such as one or more in sodium phosphate, potassium phosphate, ammonium phosphate etc.
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 benzoate, lithium bromate, lithium bromide, lithium chlorate, lithium chloride, lithium acetate, lithium fluorosilicate, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate and lithium tartrate, is preferably lithium hydroxide.Wherein, described lithium hydroxide can without the crystallization water, also can with the crystallization water, as anhydrous lithium hydroxide and/or Lithium hydroxide monohydrate.
It should be noted that, when the raw material preparing described LiFePO4 contains lithium dihydrogen phosphate, described lithium dihydrogen phosphate is regarded as and is added as described water-soluble phosphate, and the consumption of described lithium dihydrogen phosphate is counted simultaneously in the consumption in water-soluble phosphate and water-soluble lithium source, that is, lithium contained in described lithium dihydrogen phosphate need be deducted when adding other water-soluble lithium source.
In the present invention, described water-soluble phosphorus source is preferably phosphoric acid, and described water-soluble lithium source is preferably lithium hydroxide.In addition, selectivity potassium hydroxide and/or NaOH can also be contained in described second solution.
The consumption of the present invention to the raw material of the described iron manganese phosphate for lithium of preparation is not particularly limited, such as, with Mn
2+meter described watersoluble divalent manganese source and with Fe
2+meter described watersoluble divalent source of iron total consumption with PO
4 3-the mol ratio of the consumption in the described water-soluble phosphorus source of meter can be 0.95-1.05:1, and with Li
+meter described water-soluble lithium source consumption with PO
4 3-the mol ratio of the consumption in the described water-soluble phosphorus source of meter can be 1.05-3.15:1.In addition, when in described second solution also containing potassium hydroxide and/or NaOH time, H in the molal quantity of OH-and described water-soluble phosphorus source in described second solution
+the ratio of molal quantity be generally 0.95-1.05:1.
Described watersoluble divalent manganese source can be existing various can be water-soluble containing the compound of divalent manganesetion, its instantiation includes but not limited to: one or more in the sub-manganese of protochloride manganese, manganese bromide, Mn nitrate, perchloric acid sub-manganese, manganese sulfate and acetic acid.Described watersoluble divalent manganese source can without the crystallization water, also can with the crystallization water, one or more in manganese as sub-in anhydrous slufuric acid, the sub-manganese of sulfuric acid monohydrate etc.
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 fluosilicate, ferrous nitrate, ferrous perchlorate, ferrous sulfate and ferrous acetate.In addition, described ferrous sulfate can be without the crystallization water, also can with the crystallization water, as one or more in anhydrous slufuric acid ferrous iron, ferrous sulfate monohydrate, ferrous sulfate heptahydrate etc.
According to the present invention, preferably, also containing reducing agent in described first solution, can reduce like this divalent manganesetion and ferrous ion and oxidation in stream mixing and course of reaction, thus reduce the content of impurity in product more significantly and its chemical property of raising further.The consumption of described reducing agent can be selected according to total consumption of watersoluble divalent manganese source and watersoluble divalent source of iron, such as, the consumption of described reducing agent with Mn
2+meter described watersoluble divalent manganese source and with F
e 2+the mol ratio of total consumption of the described watersoluble divalent source of iron of meter can be 0.01-0.1:1, is preferably 0.01-0.05:1.In addition, described reducing agent can for existing various can reduce divalent manganesetion and ferrous ion and the material be oxidized in stream mixing and course of reaction, such as, can be ascorbic acid and/or citric acid.
According to the present invention, as long as although the first solution that there is specific composition by above-mentioned and the second solution stream mixing and and in stream mixing, pH value is controlled just can to obtain that particle diameter is little at 6.5-7.5, even particle size distribution and the iron manganese phosphate for lithium of electrochemical performance, but improve its even particle size distribution in order to the particle diameter that reduces the iron manganese phosphate for lithium obtained further, the preparation method of described iron manganese phosphate for lithium also comprise by described and flow mix products 10-50 DEG C, be uniformly mixed 10-30min under 300-800rpm, then at 10-50 DEG C sand milling 0.5-3 hour.Wherein, described sand milling carries out usually in sand mill, and its a kind of mode for being dispersed by shearing force, pressure and impulsive force by mixed slurry, be specially as well known to those skilled in the art, therefore not to repeat here.
According to the present invention, as a rule, the condition of described reaction comprises: reaction temperature can be 120-240 DEG C, is preferably 140-200 DEG C; Reaction pressure can be 0.1-3.5MPa, is preferably 0.3-1.5MPa; Reaction time can be 1-12 hour, is preferably 6-10 hour.
In the present invention, described pressure all refers to gauge pressure.
In addition, in order to avoid the oxygen in air is to the oxidation of divalent manganesetion in material and ferrous ion, 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 iron manganese phosphate for lithium 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 iron manganese phosphate for lithium also comprises and product being mixed with organic carbon source and spraying dry, and then Spray dried products is carried out roasting, can improve the conductivity of the iron manganese phosphate for lithium 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 10-20 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 200-300 DEG C, is preferably 230-270 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 solid-state product, organic carbon source and additional water to obtain described slurry; When described product is the product of undried, product containing certain water itself directly can be mixed to obtain described slurry with organic carbon source, now, if the water shortage contained in product, then 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 all can know these those skilled in the art, 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 550-750 DEG C that the condition of described roasting comprises sintering temperature, and roasting time can be 4-10 hour.In addition, described roasting is carried out usually in an inert atmosphere.
Present invention also offers the iron manganese phosphate for lithium prepared by said method.
In addition, present invention also offers the application of described iron manganese phosphate for lithium as positive electrode active materials.
Below will be described the present invention by embodiment.
In following examples and comparative example, the SSX-550 type scanning electron microscopy that scanning electron microscopy (SEM) is produced for Japanese Shimadzu Corporation (Shimadzu), 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, the preparation of described iron manganese phosphate for lithium is all carried out in the mixing arrangement shown in Fig. 1, described mixing arrangement specifically comprises: reactor 1, first NaOH solution tank NaOH 2, second NaOH solution tank NaOH 3 and pH controller 4, described first NaOH solution tank NaOH 2 is communicated with described reactor 1 by the first measuring pump 5, described second NaOH solution tank NaOH 3 is communicated with described reactor 1 by the second measuring pump 6, the probe of described pH controller 4 is arranged in described reactor 1 and described pH controller 4 is communicated with described first measuring pump 5, also comprises paddle in described reactor 1.
Embodiment 1
This embodiment is for illustration of iron manganese phosphate for lithium provided by the invention and preparation method thereof.
(1) the first solution is prepared:
By 172.54g(1.5mol, purity is 85.2 % by weight, lower with) phosphoric acid is dissolved in 1.65L deionized water, and logical nitrogen protection toward solution in, then adds 165.14g(0.975mol) sulfuric acid monohydrate Asia manganese and 144.66g(0.525mol) ferrous sulfate heptahydrate dissolving;
(2) the second solution is prepared:
By 189.40g(4.5mol) Lithium hydroxide monohydrate is dissolved in 1.85L deionized water, and logical nitrogen protection;
(3) and stream mix and react:
Described first solution is placed in the first NaOH solution tank NaOH 2, described second solution is placed in the second NaOH solution tank NaOH 3.Add water in advance 1.5L in the storage tank of reactor 1, the air in storage tank is got rid of with nitrogen, then open the first measuring pump 5 and the second measuring pump 6 to add described first solution and the second solution continuously simultaneously, the flow velocity controlling the second solution is 45mL/min, and the pH value of mix products is controlled all the time 6.5, the flow velocity of described first solution is controlled by pH value, constantly stir in reinforced process, add after two kinds of solution 30 DEG C, continue to stir 15min under 550rpm, then sand milling slurry 1 hour at 30 DEG C, obtains mixed slurry.Then seal after described mixed slurry being squeezed into the autoclave of logical nitrogen exhaust, temperature is risen to 170 DEG C and by Stress control at 0.75MP
alower reaction 8h, has reacted and has been cooled to 35 DEG C, filters and is precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5L absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains iron manganese phosphate for lithium L1.The X-ray diffraction spectrogram (XRD spectra) of described iron manganese phosphate for lithium L1 and iron manganese phosphate for lithium standard sample as shown in Figure 2.As can be seen from the result of Fig. 2, the diffraction maximum of described iron manganese phosphate for lithium L1 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, and peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, and as can be seen here, the purity of described iron manganese phosphate for lithium L1 is very high.
15g glucose is dissolved in 500mL deionized water; and add the dried described iron manganese phosphate for lithium L1 of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 250 DEG C; then under nitrogen protection; the product obtained by spraying dry, at the tubular type kiln roasting 8 hours of 700 DEG C, is then cooled to 45 DEG C, obtains iron manganese phosphate for lithium composite material TM-1.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-1 described in sem observation, its result as shown in Figure 3.As can be seen from the result of Fig. 3, the particle diameter of described iron manganese phosphate for lithium composite material TM-1 is less and domain size distribution is comparatively even.Be in the SEM photo of 5w in the multiplication factor of described iron manganese phosphate for lithium composite material TM-1, random selecting 100 particles and scale carry out contrasting and calculate its mean value, it can be used as the primary particle size of iron manganese phosphate for lithium composite material TM-1 and calculate standard deviation (lower same), result shows, the average primary particle diameter of this iron manganese phosphate for lithium composite material TM-1 is 39.04nm, and size grade scale difference is 8.9.
Embodiment 2
This embodiment is for illustration of iron manganese phosphate for lithium provided by the invention and preparation method thereof.
(1) the first solution is prepared:
By 172.54g(1.5mol) phosphoric acid adds in 1.65L deionized water, and logical nitrogen protection in solution, then adds 165.39g(0.956mol) the sub-manganese of acetic acid and 89.57g(0.515mol) ferrous acetate dissolves;
(2) the second solution is prepared:
By 185.62g(4.41mol) lithium hydroxide is dissolved in 1.85L deionized water dissolving, and logical nitrogen protection;
(3) and stream mix and react:
Described first solution is placed in the first NaOH solution tank NaOH 2, described second solution is placed in the second NaOH solution tank NaOH 3.Add water in advance 1.5L in the storage tank of reactor 1, the air in storage tank is got rid of with nitrogen, then open the first measuring pump 5 and the second measuring pump 6 to add described first solution and the second solution continuously simultaneously, control the flow velocity 100mL/min of the second solution, and the pH value of mix products is controlled all the time 7.5, the flow velocity of described first solution is controlled by pH value, constantly stir in reinforced process, add after two kinds of solution 50 DEG C, continue to stir 15min under 300rpm, then sand milling slurry 3 hours at 10 DEG C, obtains mixed slurry.Then seal after described mixed slurry being squeezed into the autoclave of logical nitrogen exhaust, temperature risen to 200 DEG C and Stress control is reacted 6h under 1.5MPa, having reacted and be cooled to 30 DEG C, filtering and be precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5L absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains iron manganese phosphate for lithium L2.The X-ray diffraction spectrogram (XRD spectra) of described iron manganese phosphate for lithium L2 and iron manganese phosphate for lithium standard sample as shown in Figure 4.As can be seen from the result of Fig. 4, the diffraction maximum of described iron manganese phosphate for lithium L2 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, and peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, and as can be seen here, the purity of described iron manganese phosphate for lithium L2 is very high.
10g sucrose is dissolved in 500mL deionized water; and add the dried described iron manganese phosphate for lithium L2 of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 230 DEG C; then under nitrogen protection; the product obtained by spraying dry, at the tubular type kiln roasting 4 hours of 750 DEG C, is then cooled to 45 DEG C, obtains iron manganese phosphate for lithium composite material TM-2.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-2 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-2 is less and domain size distribution is comparatively even, and its average primary particle diameter is 45.75nm, and size grade scale difference is 10.6.
Embodiment 3
This embodiment is for illustration of iron manganese phosphate for lithium provided by the invention and preparation method thereof.
(1) the first solution is prepared:
By 172.54g(1.5mol) phosphoric acid adds in 1.65L deionized water, and logical nitrogen protection in solution, then adds 177.93g(0.994mol) Mn nitrate and 147.55g(0.536mol) ferrous sulfate dissolves;
(2) the second solution is prepared:
By 193.19g(4.59mol) lithium hydroxide is dissolved in 1.85L deionized water dissolving, and logical nitrogen protection;
(3) and stream mix and react:
Described first solution is placed in the first NaOH solution tank NaOH 2, described second solution is placed in the second NaOH solution tank NaOH 3.Add water in advance 1.5L in the storage tank of reactor 1, the air in storage tank is got rid of with nitrogen, then open the first measuring pump 5 and the second measuring pump 6 to add described first solution and the second solution continuously simultaneously, control the flow velocity 30mL/min of the second solution, and the pH value of mix products is controlled all the time 7, the flow velocity of described first solution is controlled by pH value, constantly stir in reinforced process, add after two kinds of solution 50 DEG C, continue to stir 15min under 800rpm, then sand milling slurry 0.5 hour at 50 DEG C, obtains mixed slurry.Then seal after described mixed slurry being squeezed into the autoclave of logical nitrogen exhaust, temperature risen to 140 DEG C and Stress control is reacted 10h under 0.3MPa, having reacted and be cooled to 40 DEG C, filtering and be precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5L absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains iron manganese phosphate for lithium L3.As can be seen from the result of the XRD spectra of described iron manganese phosphate for lithium L3 and iron manganese phosphate for lithium standard sample, the diffraction maximum of described iron manganese phosphate for lithium L3 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, dephasign peak is not observed in diffraction pattern, as can be seen here, the purity of described iron manganese phosphate for lithium L3 is very high.
20g sucrose is dissolved in 500mL deionized water; and add the dried described iron manganese phosphate for lithium L2 of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 270 DEG C; then under nitrogen protection; the product obtained by spraying dry, at the tubular type kiln roasting 10 hours of 650 DEG C, is then cooled to 45 DEG C, obtains iron manganese phosphate for lithium composite material TM-3.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-3 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-3 is less and domain size distribution is comparatively even, and its average primary particle diameter is 42.78nm, and size grade scale difference is 9.5.
Embodiment 4
This embodiment is for illustration of iron manganese phosphate for lithium provided by the invention and preparation method thereof.
Iron manganese phosphate for lithium is prepared according to the method for embodiment 1, unlike, described manganese sulfate is different from the mol ratio of ferrous sulfate, particularly, the consumption of manganese sulfate is 203.25g(1.2mol), the consumption of ferrous sulfate is 82.66g(0.30mol), obtain iron manganese phosphate for lithium L4 and iron manganese phosphate for lithium composite material TM-4.As can be seen from the result of the XRD spectra of described iron manganese phosphate for lithium L4 and iron manganese phosphate for lithium standard sample, the diffraction maximum of described iron manganese phosphate for lithium L4 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, dephasign peak is not observed in diffraction pattern, as can be seen here, the purity of described iron manganese phosphate for lithium L4 is very high.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-4 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-4 is less and domain size distribution is comparatively even, and its average primary particle diameter is 41.43nm, and size grade scale difference is 9.2.
Embodiment 5
This embodiment is for illustration of iron manganese phosphate for lithium provided by the invention and preparation method thereof.
Iron manganese phosphate for lithium is prepared according to the method for embodiment 1, unlike, in the process for preparation of described first solution, by 172.54g(1.5mol) phosphoric acid to add in 1.65L deionized water after and before pass into nitrogen in solution, add 5.06g(0.029mol) ascorbic acid, obtain iron manganese phosphate for lithium L5 and iron manganese phosphate for lithium composite material TM-5.As can be seen from the result of the XRD spectra of described iron manganese phosphate for lithium L5 and iron manganese phosphate for lithium standard sample, the diffraction maximum of described iron manganese phosphate for lithium L5 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, dephasign peak is not observed in diffraction pattern, as can be seen here, the purity of described iron manganese phosphate for lithium L5 is very high.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-5 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-5 is less and domain size distribution is comparatively even, and its average primary particle diameter is 42.35nm, and size grade scale difference is 9.3.
Embodiment 6
This embodiment is for illustration of the preparation method of iron manganese phosphate for lithium provided by the invention.
Iron manganese phosphate for lithium is prepared according to the method for embodiment 1, unlike, described first solution and the second solution and flow in mixed process, not included in the sand milling slurry step of 1 hour at 30 DEG C, but directly by 30 DEG C, continue to stir 15min under 550rpm after the mixed slurry that obtains squeeze in the autoclave of logical nitrogen exhaust and react, obtain iron manganese phosphate for lithium L6 and iron manganese phosphate for lithium composite material TM-6.As can be seen from the result of the XRD spectra of described iron manganese phosphate for lithium L6 and iron manganese phosphate for lithium standard sample, the diffraction maximum of described iron manganese phosphate for lithium L6 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, dephasign peak is not observed in diffraction pattern, as can be seen here, the purity of described iron manganese phosphate for lithium L6 is very high.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-6 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-6 is less and domain size distribution is comparatively even, and its average primary particle diameter is 49.15nm, and size grade scale difference is 11.1.
Embodiment 7
This embodiment is for illustration of the preparation method of iron manganese phosphate for lithium provided by the invention.
Iron manganese phosphate for lithium is prepared according to the method for embodiment 1, unlike, described phosphoric acid in described first solution is substituted with the ammonium dihydrogen phosphate of identical molal quantity, and by the mixture replacing of the Lithium hydroxide monohydrate of lithium hydroxide 1mol in described second solution and the NaOH of 1mol, obtain iron manganese phosphate for lithium L7 and iron manganese phosphate for lithium composite material TM-7.As can be seen from the result of the XRD spectra of described iron manganese phosphate for lithium L7 and iron manganese phosphate for lithium standard sample, the diffraction maximum of described iron manganese phosphate for lithium L7 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, dephasign peak is not observed in diffraction pattern, as can be seen here, the purity of described iron manganese phosphate for lithium L7 is very high.With the microscopic appearance of iron manganese phosphate for lithium composite material TM-7 described in sem observation, result shows, the particle diameter of described iron manganese phosphate for lithium composite material TM-7 is less and domain size distribution is comparatively even, and its average primary particle diameter is 46.1nm, and size grade scale difference is 10.9.
Comparative example 1
This comparative example is for illustration of the iron manganese phosphate for lithium and preparation method thereof of reference.
(1) the first solution is prepared:
Identical with embodiment 6;
(2) the second solution is prepared:
Identical with embodiment 6;
(3) mix and react:
The first solution is added after being vented by autoclave nitrogen, then the second solution is added continuously, the flow velocity controlling described second solution is 45mL/min, after reinforced, temperature in autoclave is risen to 170 DEG C and Stress control is reacted 8h under 0.75MPa, react and be cooled to 35 DEG C, filtered and be precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5 absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains the iron manganese phosphate for lithium DL1 of reference.The X-ray diffraction spectrogram of described iron manganese phosphate for lithium DL1 and iron manganese phosphate for lithium standard sample as shown in Figure 5.As can be seen from the result of Fig. 5, the diffraction maximum of the iron manganese phosphate for lithium DL1 of described reference is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, 23 ° exist very little diffraction and to mix peak, as can be seen here, the purity of the iron manganese phosphate for lithium DL1 of described reference will lower than the purity of iron manganese phosphate for lithium L1.
15g glucose is dissolved in 500mL deionized water; and add the iron manganese phosphate for lithium DL1 of the dried described reference of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 250 DEG C; then under nitrogen protection; the product obtained by spraying dry, at the tubular type kiln roasting 8 hours of 700 DEG C, is then cooled to 45 DEG C, obtains the iron manganese phosphate for lithium composite material DTM-1 of reference.With the microscopic appearance of the iron manganese phosphate for lithium composite material DTM-1 of reference described in sem observation, result shows, the particle diameter of the iron manganese phosphate for lithium composite material DTM-1 of described reference is comparatively large and domain size distribution is not too even, and its average primary particle diameter is 78.15nm, and size grade scale difference is 23.4.
Comparative example 2
This comparative example is for illustration of the iron manganese phosphate for lithium of reference and reference preparation method thereof.
(1) the first solution is prepared:
Identical with embodiment 6;
(2) the second solution is prepared:
Identical with embodiment 6;
(3) mix and react:
The second solution is added after being vented by autoclave nitrogen, then the first solution is added continuously, the flow velocity controlling described first solution is 45mL/min, after reinforced, temperature in autoclave is risen to 170 DEG C and Stress control is reacted 8h under 0.75MPa, react and be cooled to 35 DEG C, filtered and be precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5L absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains the iron manganese phosphate lithium material DL2 of reference.As can be seen from the iron manganese phosphate for lithium DL2 of described reference and the XRD spectra of iron manganese phosphate for lithium standard sample, the diffraction maximum of the iron manganese phosphate for lithium DL2 of described reference is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, 23 ° exist very little diffraction and to mix peak, as can be seen here, the purity of the iron manganese phosphate for lithium DL2 of described reference will lower than the purity of iron manganese phosphate for lithium L1.
15g glucose is dissolved in 500mL deionized water; and add the iron manganese phosphate for lithium DL2 of the dried described reference of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 250 DEG C; then under nitrogen protection; by the product that obtains after the spraying dry tubular type kiln roasting 8 hours at 700 DEG C, be then cooled to 45 DEG C, obtain the iron manganese phosphate for lithium composite material DTM-2 of reference.With the microscopic appearance of the iron manganese phosphate for lithium composite material DTM-2 of reference described in sem observation, result shows, the particle diameter of the iron manganese phosphate for lithium composite material DTM-2 of described reference is less and domain size distribution is comparatively even, and its average primary particle diameter is 78.36nm, and size grade scale difference is 24.8.
Comparative example 3
This comparative example is for illustration of the iron manganese phosphate for lithium of reference and reference preparation method thereof.
(1) phosphoric acid solution is prepared:
By 172.54g(1.5mol) phosphoric acid is dissolved in 1.5L deionized water;
(2) mixed solution of manganese sulfate and ferrous sulfate is prepared:
By 165.14g(0.975mol) manganese sulfate and 144.66g(0.525mol) ferrous sulfate is dissolved in 1L water, logical nitrogen protection;
(3) aqueous slkali is prepared:
By 189.40g(4.5mol) lithium hydroxide is dissolved in 2.5L deionized water, logical nitrogen protection;
(4) mix and react:
Aqueous slkali is added after being vented by autoclave nitrogen, then phosphoric acid solution is added continuously, and by its flow control at 45mL/min, the mixed solution of manganese sulfate and ferrous sulfate is added again continuously after phosphoric acid solution adds, and its speed is controlled at 45mL/min, after adding, the temperature of autoclave risen to 170 DEG C and Stress control is reacted 8h under 0.75MPa, having reacted and be cooled to 35 DEG C, filtering and be precipitated thing.Described sediment is first washed 2 times with 5L deionized water, and then with 5L absolute ethanol washing 1 time, then dry 3h at 80 DEG C, obtains the iron manganese phosphate for lithium DL3 of reference.As can be seen from the iron manganese phosphate for lithium DL3 of described reference and the XRD spectra of iron manganese phosphate for lithium standard sample, the diffraction maximum of the iron manganese phosphate for lithium DL3 of described reference is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, there are some dephasign peaks in diffraction pattern, as can be seen here, the purity of the iron manganese phosphate for lithium DL3 of described reference is relatively low.
15g glucose is dissolved in 500mL deionized water; and add the iron manganese phosphate for lithium DL3 of the dried described reference of 100g; then 15min is stirred with Fluko high speed shear dispersion machine; then spraying dry at temperature is 250 DEG C; then under nitrogen protection; the product obtained by spraying dry, at the tubular type kiln roasting 8 hours of 700 DEG C, is then cooled to 45 DEG C, obtains the iron manganese phosphate for lithium composite material DTM-3 of reference.With the microscopic appearance of the iron manganese phosphate for lithium composite material DTM-3 of reference described in sem observation, result shows, the particle diameter of the iron manganese phosphate for lithium composite material DTM-3 of described reference is less and domain size distribution is comparatively even, and its average primary particle diameter is 90.23nm, and size grade scale difference is 26.7.
Comparative example 4
This comparative example is for illustration of the iron manganese phosphate for lithium of reference and reference preparation method thereof.
Iron manganese phosphate for lithium is prepared according to the method for embodiment 6, unlike, described and stream mixing process in, the flow velocity controlling the second solution is 45mL/min, and the pH value of mix products is controlled all the time 8, the flow velocity of described first solution is controlled by pH value, obtains iron manganese phosphate for lithium DL4 and the iron manganese phosphate for lithium composite material DTM-4 of reference.Wherein, as can be seen from the iron manganese phosphate for lithium DL4 of described reference and the XRD spectra of iron manganese phosphate for lithium standard sample, the diffraction maximum of the iron manganese phosphate for lithium DL4 of described reference is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, there are some dephasign peaks in diffraction pattern, as can be seen here, the purity of the iron manganese phosphate for lithium DL4 of described reference is relatively low.With the microscopic appearance of the iron manganese phosphate for lithium composite material DTM-4 of reference described in sem observation, result shows, the particle diameter of the iron manganese phosphate for lithium composite material DTM-4 of described reference is less and domain size distribution is comparatively even, and its average primary particle diameter is 80.01nm, and size grade scale difference is 24.9.
Test case
Test case is for illustration of the test of iron manganese phosphate for lithium chemical property.
By positive electrode active materials (the iron manganese phosphate for lithium composite material DL1-DL4 of the reference that the iron manganese phosphate for lithium composite L 1-L7 that embodiment 1-7 obtains and comparative example 1-4 obtains), 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 80:10:10, be coated in after stirring on aluminium foil, and toast at 110 DEG C ± 5 DEG C, obtain positive plate.Using metal lithium sheet as negative plate, barrier film is microporous polypropylene membrane (Celgard2300), electrolyte be the LiPF6/ (EC+EMC+DMC) of 1.0mol/L (wherein, LiPF6 is lithium hexafluoro phosphate, and EC is ethylene carbonate, and EMC is methyl ethyl carbonate, DMC is dimethyl carbonate, the volume ratio of EC, EMC and DMC is 1:1:1), seal in the glove box being full of argon gas, make R2025 button cell.At room temperature 30 DEG C, R2025 button cell is carried out discharge and recharge with 0.1C, end of charge voltage is 4.3V, and discharge cut-off voltage is 2.5V.The first charge-discharge capacity of this R2025 button cell under 0.1C and efficiency for charge-discharge as shown in table 1, wherein, efficiency for charge-discharge (%)=discharge capacity ÷ charging capacity × 100%.
Table 1
As can be seen from the above results, particle diameter is little, even particle size distribution and the iron manganese phosphate for lithium of electrochemical performance to adopt method provided by the invention to obtain.As can be seen from contrast with embodiment 5 of embodiment 1, when also containing reducing agent in described first solution, can reduce divalent manganesetion and ferrous ion and oxidation in stream mixing and course of reaction, thus improve the chemical property of the iron manganese phosphate for lithium obtained further.As can be seen from the contrast of embodiment 1 and embodiment 6, when the preparation method of described iron manganese phosphate for lithium also comprise by described and flow mix products 10-50 DEG C, be uniformly mixed 10-30min under 300-800rpm, at 10-50 DEG C, sand milling 0.5-3 is constantly little again, mixed slurry can be made more uniformly to be disperseed, thus reduce the particle diameter of the iron manganese phosphate for lithium obtained further and improve its even particle size distribution.
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 (16)
1. the preparation method of an iron manganese phosphate for lithium, it is characterized in that, the method comprises the first solution containing watersoluble divalent manganese source, watersoluble divalent source of iron and water-soluble phosphorus source flow to mix reacted afterwards with the second solution containing water-soluble lithium source, described and in the process of stream mixing, by the flow velocity that controls described first solution and the second solution with by obtain and the pH value flowing mix products control all the time at 6.5-7.5; Described water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or is the mixture of phosphoric acid and/or dihydric phosphate and dibasic alkaliine and/or neutral phosphate; At least part of described water-soluble lithium source is lithium hydroxide.
2. preparation method according to claim 1, wherein, described and stream is blended in mixing arrangement and carries out, described mixing arrangement comprises: reactor (1), first NaOH solution tank NaOH (2), second NaOH solution tank NaOH (3) and pH controller (4), described first NaOH solution tank NaOH (2) is communicated with described reactor (1) by the first measuring pump (5), described second NaOH solution tank NaOH (3) is communicated with described reactor (1) by the second measuring pump (6), the probe of described pH controller (4) is arranged in described reactor (1) and described pH controller (4) is communicated with described first measuring pump (5) or described second measuring pump (6), described and method that is stream mixing comprises described first solution is placed in described first NaOH solution tank NaOH (1), described second solution is placed in described second NaOH solution tank NaOH (2), not corresponding with the measuring pump that described pH controller (4) is communicated with solution is added in described reactor (1) with constant flow velocity, and by the flow velocity that controls the solution corresponding with the measuring pump that described pH controller (4) is communicated with so that the described and pH value flowing mix products is controlled at 6.5-7.5.
3. preparation method according to claim 1 and 2, wherein, the concentration of described first solution and the second solution is identical or different, and is 0.1-5mol/L independently of one another.
4. preparation method according to claim 3, wherein, the flow velocity of described first solution is 10-150mL/min; Or the flow velocity of described second solution is 10-150mL/min.
5. preparation method according to claim 1, wherein, described water-soluble phosphorus source is phosphoric acid, and described water-soluble lithium source is lithium hydroxide.
6. preparation method according to claim 5, wherein, described second solution is also containing potassium hydroxide and/or NaOH.
7. the preparation method according to claim 5 or 6, wherein, with Mn
2+meter described watersoluble divalent manganese source and with Fe
2+meter described watersoluble divalent source of iron total consumption with PO
4 3-the mol ratio of the consumption in the described water-soluble phosphorus source of meter is 0.95-1.05:1, and with Li
+meter described water-soluble lithium source consumption with PO
4 3-the mol ratio of the consumption in the described water-soluble phosphorus source of meter is 1.05-3.15:1.
8. according to the preparation method in claim 1,2 and 4-6 described in any one, wherein, described watersoluble divalent manganese source is selected from one or more in protochloride manganese, manganese bromide, Mn nitrate, the sub-manganese of perchloric acid sub-manganese, manganese sulfate and acetic acid; Described watersoluble divalent source of iron be selected from frerrous chloride, ferrous bromide, ferrous fluosilicate, ferrous nitrate, ferrous perchlorate, ferrous sulfate and ferrous acetate one or more.
9. according to the preparation method in claim 1,2 and 4-6 described in any one, wherein, also contain reducing agent in described first solution; The consumption of described reducing agent with Mn
2+meter described watersoluble divalent manganese source and with Fe
2+the mol ratio of total consumption of the described watersoluble divalent source of iron of meter is 0.01-0.1:1; Described reducing agent is ascorbic acid and/or citric acid.
10. preparation method according to claim 1, wherein, the method also comprise by described and flow mix products 10-50 DEG C, be uniformly mixed 10-30min under 300-800rpm, then at 10-50 DEG C sand milling 0.5-3 hour.
11. preparation methods according to claim 1 or 10, wherein, described reaction is carried out in an inert atmosphere; The condition of described reaction comprises: reaction temperature is 120-240 DEG C, and reaction pressure is 0.1-3.5MPa, and the reaction time is 1-12 hour.
12. preparation methods according to claim 1, wherein, the method also comprises and product being mixed with organic carbon source and spraying dry, and then Spray dried products is carried out roasting.
13. preparation methods according to claim 12, 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.
14. preparation methods according to claim 12 or 13, wherein, described spray-dired temperature is 200-300 DEG C; It is 550-750 DEG C that the condition of described roasting comprises sintering temperature, and roasting time is 4-10 hour.
15. iron manganese phosphate for lithium prepared by the method in claim 1-14 described in any one.
16. iron manganese phosphate for lithium according to claim 15 are as the application of positive electrode active materials.
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| CN105932249A (en) * | 2016-06-01 | 2016-09-07 | 中南大学 | Preparation method for composite cathode material used for lithium ion battery |
| CN108940183A (en) * | 2018-08-07 | 2018-12-07 | 东北师范大学 | A method of magnetic adsorbent is prepared using water factory's ferrimanganic sludge as raw material |
| CN111333049A (en) * | 2020-03-23 | 2020-06-26 | 蒋央芳 | Preparation method of lithium iron manganese phosphate |
| CN114644329A (en) * | 2022-04-12 | 2022-06-21 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method of nano lithium ferric manganese phosphate |
| CN115180607A (en) * | 2022-07-22 | 2022-10-14 | 江苏容汇通用锂业股份有限公司 | Preparation method of lithium iron manganese phosphate lithium ion battery positive electrode material |
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| CN102381693A (en) * | 2010-09-06 | 2012-03-21 | 李文宝 | Preparation method of lithium iron phosphate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105932249A (en) * | 2016-06-01 | 2016-09-07 | 中南大学 | Preparation method for composite cathode material used for lithium ion battery |
| CN108940183A (en) * | 2018-08-07 | 2018-12-07 | 东北师范大学 | A method of magnetic adsorbent is prepared using water factory's ferrimanganic sludge as raw material |
| CN108940183B (en) * | 2018-08-07 | 2020-12-22 | 东北师范大学 | Method for preparing magnetic adsorbent by using waterworks ferro-manganese sludge as raw material |
| CN111333049A (en) * | 2020-03-23 | 2020-06-26 | 蒋央芳 | Preparation method of lithium iron manganese phosphate |
| CN114644329A (en) * | 2022-04-12 | 2022-06-21 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method of nano lithium ferric manganese phosphate |
| CN115180607A (en) * | 2022-07-22 | 2022-10-14 | 江苏容汇通用锂业股份有限公司 | Preparation method of lithium iron manganese phosphate lithium ion battery positive electrode material |
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