CN104752720B - A kind of iron manganese phosphate for lithium and its preparation method and application - Google Patents
A kind of iron manganese phosphate for lithium and its preparation method and application Download PDFInfo
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- CN104752720B CN104752720B CN201310743803.1A CN201310743803A CN104752720B CN 104752720 B CN104752720 B CN 104752720B CN 201310743803 A CN201310743803 A CN 201310743803A CN 104752720 B CN104752720 B CN 104752720B
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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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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a kind of application of preparation method of iron manganese phosphate for lithium, the iron manganese phosphate for lithium and the iron manganese phosphate for lithium that are prepared by this method as positive electrode active materials.The preparation method of the iron manganese phosphate for lithium includes reacting after the first solution containing watersoluble divalent manganese source, watersoluble divalent source of iron and water-soluble phosphorus source is mixed with the second solution cocurrent containing water-soluble lithium source, during the cocurrent mixes, the pH value of obtained cocurrent mix products is controlled 6.5 7.5 all the time by controlling the flow velocity of first solution and the second solution, the water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or is phosphoric acid and/or dihydric phosphate and dibasic alkaliine and/or the mixture of neutral phosphate；At least partly described water-soluble lithium source is lithium hydroxide.Using this method can obtain particle diameter is small, particle diameter distribution uniformly and electrochemical performance iron manganese phosphate for lithium.
Description
Technical field
The present invention relates to a kind of preparation method of iron manganese phosphate for lithium, the iron manganese phosphate for lithium being prepared by this method and institute
State application of the iron manganese phosphate for lithium as positive electrode active materials.
Background technology
Power-type lithium ion battery has the advantages of high-energy-density, high-specific-power, high security and long circulation life, is not
Carry out the ideal source of electric vehicle and other various electric tools.Wherein, iron manganese phosphate for lithium is of greatest concern at present and before most having
One of the positive electrode active materials for preparing power-type lithium ion battery on way.It is miscellaneous in the iron manganese phosphate for lithium positive electrode active materials
Matter content is low, particle diameter is small and even particle size distribution is to improve the key of its chemical property.
For iron manganese phosphate for lithium, it is typically to be reacted using by manganese sulfate, ferrous sulfate, phosphoric acid and lithium hydroxide
It is prepared.For example, CN101807698A, which discloses a kind of super/subcritical water thermal process, prepares power type lithium-ion battery anode
Material technology, it is characterised in that this method comprises the following steps：（1）By raw material lithium source and by source of iron/manganese source, source of phosphoric acid
The mixed liquor two fluids formed is continuously injected into blender respectively to be mixed；（2）The 3rd be made up of deionized water
Fluid streams are first injected into preheater and heated, and described after 80-200 DEG C, heating of the temperature control of the preheater goes
Ionized water is entered in the blender, and and step（1）In the two fluids mixed；（3）From step（2）Middle institute
The mixed liquor for stating three fluid streams that blender comes out enters hydrothermal crystallizing reaction is carried out in high-temperature high-pressure reaction kettle, and reaction temperature is
150-500 DEG C, reaction pressure 5-50MPa, reaction time 10s-1h；（4）The product for reacting to obtain through the hydrothermal crystallizing
First pass through heat exchanger to be exchanged heat, cooled down with the external world, then after filtering large-grain particles and impurity via filter, enter solid
In liquid/gas separator, particulate deposits are got off；（5）The particulate to be precipitated in the solid-liquid separator is continuously collected and dried,
Obtain the dry powder of anode material for lithium-ion batteries.In addition, step（1）In the mixed liquor that is made up of source of iron/manganese source and source of phosphoric acid
The metal ion as modifying agent, and lithium, iron/manganese, the metal as modifying agent in the mixed liquor can also be contained
Ion, the mol ratio of phosphoric acid are 1:1-x:x:1, wherein, x 0-0.1.Although can using method disclosed in CN101807698A
The less iron manganese phosphate for lithium of particle diameter is obtained, but needs strictly to control reaction temperature and pressure in whole preparation process, and
The impurity content of the iron manganese phosphate for lithium of acquisition is higher, and particle diameter distribution is also not uniform enough.
Therefore, in order to obtain the more excellent iron manganese phosphate for lithium positive electrode active materials of chemical property, reduction is needed badly at present
Its impurity content, reduce its particle diameter and improve its particle size distribution.
The content of the invention
The purpose of the present invention is to overcome the particle diameter distribution for the iron manganese phosphate for lithium being prepared using existing method not equal enough
The defects of even and chemical property is not excellent enough, and a kind of preparation method of new iron manganese phosphate for lithium is provided, prepared by this method
Application of the obtained iron manganese phosphate for lithium and the iron manganese phosphate for lithium as positive electrode active materials.The phosphoric acid obtained using this method
The particle diameter of ferromanganese lithium is small and particle diameter distribution is uniform, so as to have more excellent chemical property.
The invention provides a kind of preparation method of iron manganese phosphate for lithium, wherein, this method includes that watersoluble divalent will be contained
First solution of manganese source, watersoluble divalent source of iron and water-soluble phosphorus source mixes with the second solution cocurrent containing water-soluble lithium source
After react, during the cocurrent mixes, will be obtained by controlling the flow velocity of first solution and the second solution
The pH value of cocurrent mix products controls in 6.5-7.5 all the time, and the water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, Huo Zhewei
Phosphoric acid and/or dihydric phosphate and dibasic alkaliine and/or the mixture of neutral phosphate；At least partly described water-soluble lithium source
For lithium hydroxide.
Present invention also offers the iron manganese phosphate for lithium being prepared by the above method.
In addition, present invention also offers application of the iron manganese phosphate for lithium as positive electrode active materials.
The present inventor is had found by furtheing investigate, in the preparation process of the iron manganese phosphate for lithium, prior art
Mainly take following three kinds of feed way：First manganese sulfate and ferrous sulfate are added in phosphate aqueous solution and mixed, is mixed
Liquid, then lithium hydroxide aqueous solution is added in above-mentioned mixed liquor and mixed；Or manganese sulfate and ferrous sulfate are first added into phosphoric acid
Mixed in the aqueous solution, then obtained mixed liquor is added in lithium hydroxide aqueous solution again and mixed；Or phosphoric acid is first added into hydrogen
Mixed in the lithia aqueous solution, obtain mixed liquor, the aqueous solution of manganese sulfate and ferrous sulfate is then added into above-mentioned mixing again
In liquid.However, when using first two feed way, in the mixed process of material, hydroxide ion gradually neutralizes hydrogen ion
Or hydrogen ion gradually neutralizes hydroxide ion, the pH value of mixed slurry constantly changes with the progress of mixed process, so as to
Cause complex reaction occurs in mixed slurry, phosphoric acid hydrogen Asia manganese, phosphoric acid hydrogen ferrous iron, lithium phosphate, phosphoric acid Asia manganese, phosphoric acid may be generated
Ferrous iron, hydroxide manganese, ferrous hydroxide etc. precipitate, and different precipitations can cause the pH value of mixed slurry to change, this
The pH value of sample mixed slurry and deposited components reciprocal effect, so as to cause the deposited components and ratio of mixed slurry before pyroreaction
Example, granular size and uniformity are difficult control, and and then impurity content, the particle diameter of the iron manganese phosphate for lithium that influence finally to obtain it is big
Small and particle diameter distribution.When using the third feed way, lithium phosphate, phosphoric acid Asia manganese and ferrous phosphate skewness can be brought
The problem of, so as to can further influence the chemical property of the iron manganese phosphate for lithium obtained.
However, the present invention is mixed reaction mass by the way of cocurrent mixing, and in whole cocurrent mixed process
In, the pH value of obtained cocurrent mix products is controlled all the time by controlling the flow velocity of first solution and the second solution
6.5-7.5, it can ensure that the thing of mixed slurry is consistent before pyroreaction well, particle diameter is small, particle diameter point so as to obtain
Cloth uniformly and electrochemical performance iron manganese phosphate for lithium.
A preferred embodiment of the invention, when also containing reducing agent in first solution, it can reduce
The oxidation of divalent manganesetion and ferrous ion in cocurrent mixing and course of reaction, so as to further improve obtained manganese phosphate
The chemical property of iron lithium.
According to another preferred embodiment of the present invention, when the preparation method of the iron manganese phosphate for lithium is also included by described in
Cocurrent mix products are stirred 10-30min under 10-50 DEG C, 300-800rpm, then 0.5-3 hours are sanded at 10-50 DEG C
When, enable to mixed slurry to be spreaded more evenly across, so as to the particle diameter of iron manganese phosphate for lithium for further reducing to obtain and carry
Its high particle diameter distribution uniformity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the 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 embodiment 1 obtains and standard sample；
Fig. 3 is the SEM spectrogram for 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 embodiment 2 obtains and standard sample；
Fig. 5 is the X-ray diffraction spectrogram of the iron manganese phosphate for lithium that comparative example 1 obtains and standard sample.
Description of reference numerals
1- reactors；The NaOH solution tank NaOHs of 2- first；The NaOH solution tank NaOHs of 3- second；4-pH controllers；The measuring pumps of 5- first；6- second is measured
Pump；7- agitating paddles.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The preparation method of iron manganese phosphate for lithium provided by the invention includes that watersoluble divalent manganese source, watersoluble divalent iron will be contained
First solution of source and water-soluble phosphorus source reacts after being mixed with the second solution cocurrent containing water-soluble lithium source, in the cocurrent
During mixing, by controlling the flow velocity of first solution and the second solution with the pH value for the cocurrent mix products that will be obtained
All the time control in 6.5-7.5, the water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or is phosphoric acid and/or dihydric phosphate
With dibasic alkaliine and/or the mixture of neutral phosphate；At least partly described water-soluble lithium source is lithium hydroxide.
Wherein, described " cocurrent mixing " refers to the logistics of the logistics of first solution and second solution while drawn
Enter and mixed in same container.
The cocurrent mixing can be carried out in existing various mixing arrangements.For example, the as shown in figure 1, mixing dress
Putting to include：Reactor 1, the first NaOH solution tank NaOH 2, the second NaOH solution tank NaOH 3 and pH controllers 4, first NaOH solution tank NaOH 2 pass through first
Measuring pump 5 is connected with the reactor 1, and second NaOH solution tank NaOH 3 is connected by the second measuring pump 6 with the reactor 1, described
The probe of pH controllers 4 is arranged in the reactor 1 and the pH controllers 4 and first measuring pump 5 or described
Second measuring pump 6 connects.In addition, in order to be more beneficial for the uniform mixing of material, the reactor 1 preferably also includes agitating paddle 7,
And the reactor 1 typically sand mill.
When carrying out cocurrent mixing using above-mentioned mixing arrangement, the method for the cocurrent mixing includes putting first solution
In first NaOH solution tank NaOH 1, second solution is placed in second NaOH solution tank NaOH 2, will not connected with the pH controllers 4
Solution corresponding to logical measuring pump is added in the reactor 1 with constant flow velocity, and is connected by controlling with the pH controllers 4
The flow velocity of solution corresponding to logical measuring pump with by the pH value of the cocurrent mix products control in 6.5-7.5.In addition, by institute
When stating in the first solution and the second solution addition reactor 1, it usually needs open the agitating paddle 7.
The concentration of first solution and the second solution can be with identical, can also be different, and can be each independently
0.1-5mol/L.It should be noted that the concentration of first solution and the second solution includes all solutes wherein contained
Total concentration.Now, the flow velocity of first solution can be 10-150mL/min, and the flow velocity of second solution pass through it is described
The pH value of cocurrent mix products is controlled；Or the flow velocity of second solution is 10-150mL/min, and it is described first molten
The flow velocity of liquid is controlled by the pH value of the cocurrent mix products.
The dihydric phosphate is such as can be lithium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate
In one or more；During the dibasic alkaliine is such as can be potassium phosphate,monobasic, monoammonium phosphate, disodium-hydrogen
It is one or more；The neutral phosphate such as can be sodium phosphate, potassium phosphate, ammonium phosphate in one or more.
The water-soluble lithium source can be the existing various lithium-containing compounds that can be dissolved in water, its instantiation include but
It is not limited to：Lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chlorate, lithium chloride, lithium acetate, lithium fluorosilicate,
One or more in lithium formate, lithium iodide, lithium nitrate, lithium perchlorate and lithium tartrate, preferably lithium hydroxide.Wherein, institute
The crystallization water can also be carried, such as anhydrous lithium hydroxide and/or Lithium hydroxide monohydrate without the crystallization water by stating lithium hydroxide.
It should be noted that when the raw material for preparing the LiFePO4 contains lithium dihydrogen phosphate, the lithium dihydrogen phosphate
Regard as the water-soluble phosphate add, and by the dosage of the lithium dihydrogen phosphate simultaneously be included in water-soluble phosphate and
In the dosage of water-soluble lithium source, i.e. lithium contained in the lithium dihydrogen phosphate need to be deducted when adding other water-soluble lithium sources.
In the present invention, the water-soluble phosphorus source is preferably phosphoric acid, and the water-soluble lithium source is preferably lithium hydroxide.This
Outside, it is also an option that property contains potassium hydroxide and/or sodium hydroxide in second solution.
The dosage of raw material of the present invention to preparing the iron manganese phosphate for lithium is not particularly limited, for example, with Mn2+The institute of meter
State watersoluble divalent manganese source and with Fe2+Meter the watersoluble divalent source of iron total dosage with PO4 3-The water-soluble phosphorus of meter
The mol ratio of the dosage in source can be 0.95-1.05:1, and with Li+Meter the water-soluble lithium source dosage with PO4 3-Meter
The mol ratio of the dosage of the water-soluble phosphorus source can be 1.05-3.15:1.Also contain hydrogen-oxygen in addition, working as in second solution
When changing potassium and/or sodium hydroxide, OH- molal quantity and H in the water-soluble phosphorus source in second solution+Molal quantity ratio
Value is usually 0.95-1.05:1.
The watersoluble divalent manganese source can be the existing various compounds containing divalent manganesetion that can be dissolved in water, its
Instantiation includes but is not limited to：Protochloride manganese, manganese bromide, Mn nitrate, perchloric acid Asia manganese, manganese sulfate and acetic acid Asia manganese
In one or more.The watersoluble divalent manganese source can also carry the crystallization water, such as anhydrous slufuric acid without the crystallization water
One or more in sub- manganese, sulfuric acid monohydrate Asia manganese etc..
The watersoluble divalent source of iron can be the existing various compounds containing ferrous ion that can be dissolved in water, its
Instantiation includes but is not limited to：Frerrous chloride, ferrous bromide, ferrous fluosilicate, ferrous nitrate, ferrous perchlorate, sulfuric acid are sub-
One or more in iron and ferrous acetate.In addition, the ferrous sulfate can be without the crystallization water, crystallization can also be carried
One or more in water, such as anhydrous slufuric acid ferrous iron, ferrous sulfate monohydrate, ferrous sulfate heptahydrate.
In accordance with the present invention it is preferred that also contain reducing agent in first solution, can so reduce divalent manganesetion and
Oxidation of the ferrous ion in cocurrent mixing and course of reaction, so as to significantly more reduce the content of impurity in reaction product simultaneously
Further improve its chemical property.The dosage of the reducing agent can be according to watersoluble divalent manganese source and watersoluble divalent source of iron
Total dosage selected, for example, the dosage of the reducing agent with Mn2+Meter the watersoluble divalent manganese source and with Fe 2+Meter
The mol ratio of total dosage of the watersoluble divalent source of iron can be 0.01-0.1:1, preferably 0.01-0.05:1.In addition,
The reducing agent can be existing various divalent manganesetion and the ferrous ions of can reducing in cocurrent mixing and course of reaction
The material of middle oxidation, for example, can be ascorbic acid and/or citric acid.
According to the present invention, although if above-mentioned the first solution with specific composition and the second solution cocurrent are mixed and
Cocurrent mixing in by pH value control 6.5-7.5 can just obtain particle diameter is small, particle diameter distribution uniformly and electrochemical performance
Iron manganese phosphate for lithium, but the particle diameter of the iron manganese phosphate for lithium in order to further reduce to obtain and improve its particle diameter distribution uniformity,
The preparation method of the iron manganese phosphate for lithium also includes stirring the cocurrent mix products under 10-50 DEG C, 300-800rpm mixing
10-30min is closed, then 0.5-3 hours are sanded at 10-50 DEG C.Wherein, the sand milling is carried out generally in sand mill, and it is will
Mixed slurry and a kind of mode being dispersed, is specifically known to the skilled person by shearing force, pressure and impulsive force,
Therefore not to repeat here.
According to the present invention, as a rule, the condition of the reaction includes：Reaction temperature can be 120-240 DEG C, be preferably
140-200℃；Reaction pressure can be 0.1-3.5MPa, preferably 0.3-1.5MPa；Reaction time can be 1-12 hours, excellent
Elect 6-10 hours as.
In the present invention, the pressure refers both to gauge pressure.
In addition, in order to avoid oxidation of the oxygen in air to divalent manganesetion in material and ferrous ion, it is preferable that
The reaction is carried out in an inert atmosphere.Wherein, the mode for keeping inert atmosphere can be that inert gas is passed through into reaction system
In to replace the non-inert gas in the reaction system, then again by after gas displacement reaction system seal.It is described lazy
Property gas can be nitrogen and/or helium.
According to the present invention, the preparation method of the iron manganese phosphate for lithium also includes the reaction product is filtered, washs and done
It is dry.Wherein, the washing first can be washed with deionized 1-3 times, then be washed 1-3 times with absolute ethyl alcohol.
In accordance with the present invention it is preferred that the preparation method of the iron manganese phosphate for lithium is also included reaction product and organic carbon source
Mix and be spray-dried, be then again calcined Spray dried products, the iron manganese phosphate for lithium that can so improve to obtain is led
Electrically.
The present invention is not particularly limited to the species and dosage of the organic carbon source.As a rule, the organic carbon source
Can be the existing various organic matters that can be carbonized below 500 DEG C, its instantiation includes but is not limited to：Glucose, sugarcane
One or more in sugar, lactose, maltose, phenolic resin and epoxy resin.In addition, the dosage of the organic carbon source should root
Selected according to the amount of reaction product, for example, in terms of the dry weight of the reaction product of 100 parts by weight, the organic carbon source
Dosage can be 5-25 parts by weight, preferably 10-20 parts by weight.
According to the present invention, the concrete operation method and condition of the spray drying are known to the skilled person.Specifically
Ground, the slurry being made into by the reaction product and organic carbon source and water is added in atomizer and rotated at a high speed to realize that spraying is dry
It is dry.The temperature of the spray drying can be 200-300 DEG C, preferably 230-270 DEG C.It should be noted that the reaction production
Thing can be to pass through dried product, or undried product.When the reaction product is by dry production
During thing, the reaction product of solid-state, organic carbon source and additional water can be mixed to obtain the slurry；When the reaction production
When thing is undried product, the reaction product that itself can be contained to certain water is directly mixed to obtain with organic carbon source
Slurry is stated, now, if the water shortage contained in reaction product, then can also additionally add a certain amount of water.In addition, the slurry
The amount of body reclaimed water can be the conventional selection of this area, this those skilled in the art can be known, therefore not to repeat here.
The present invention is not particularly limited to the condition of the roasting, as long as the organic carbon source can be carbonized,
For example, it can be 550-750 DEG C that the condition of the roasting, which includes sintering temperature, roasting time can be 4-10 hours.In addition, institute
Roasting is stated generally to carry out in an inert atmosphere.
Present invention also offers the iron manganese phosphate for lithium being prepared by the above method.
In addition, present invention also offers application of the iron manganese phosphate for lithium as positive electrode active materials.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, SEM（SEM）For Japanese Shimadzu Corporation（Shimadzu）Production
SSX-550 type SEM, test voltage 5KV.X-ray diffractometer is the general analysis all purpose instrument Limited Liability in Beijing
The XD-2 type X-ray diffractometers of company's production, wherein, test condition includes：Pipe pressure is 200mA, electric current 200mA, and step-length is
1 °, test angle is 10 ° -90 °.
In following examples and comparative example, the preparation of the iron manganese phosphate for lithium is carried out in the mixing arrangement shown in Fig. 1,
The mixing arrangement specifically includes：Reactor 1, the first NaOH solution tank NaOH 2, the second NaOH solution tank NaOH 3 and pH controllers 4, first solution
Tank 2 is connected by the first measuring pump 5 with the reactor 1, and second NaOH solution tank NaOH 3 passes through the second measuring pump 6 and the reaction
Kettle 1 connects, and the probe of the pH controllers 4 is arranged in the reactor 1 and the pH controllers 4 and the described first metering
Pump 5 is connected, and agitating paddle is also included in the reactor 1.
Embodiment 1
The embodiment is used to illustrate iron manganese phosphate for lithium provided by the invention and preparation method thereof.
（1）Prepare the first solution：
By 172.54g（1.5mol, purity are 85.2 weight %, similarly hereinafter）Phosphoric acid is dissolved in 1.65L deionized waters, and past molten
Lead to nitrogen protection in liquid, then add 165.14g（0.975mol）Sulfuric acid monohydrate Asia manganese and 144.66g（0.525mol）Seven water sulphur
Sour ferrous iron simultaneously dissolves；
（2）Prepare the second solution：
By 189.40g（4.5mol）Lithium hydroxide monohydrate is dissolved in 1.85L deionized waters, and logical nitrogen protection；
（3）Cocurrent is mixed and reacted：
First solution is placed in the first NaOH solution tank NaOH 2, second solution is placed in the second NaOH solution tank NaOH 3.Anti-
Pre-add water 1.5L in the storage tank of kettle 1 is answered, the air in storage tank is excluded with nitrogen, then opens the first measuring pump 5 and second simultaneously
For measuring pump 6 to be continuously added to first solution and the second solution, the flow velocity for controlling the second solution is 45mL/min, and will mixing
The pH value of product is controlled 6.5 all the time, and the flow velocity of first solution is controlled by pH value, is constantly stirred during charging
Mix, continue to stir 15min under 30 DEG C, 550rpm after adding two kinds of solution, slurry is then sanded at 30 DEG C 1 hour, obtain
Mixed slurry.Then sealed after the mixed slurry being squeezed into the autoclave for leading to nitrogen exhaust, temperature is risen to 170 DEG C
And by Stress control in 0.75MPaLower reaction 8h, has reacted and has been cooled to 35 DEG C, be filtrated to get sediment.The sediment is first
Washed 2 times with 5L deionized waters, then washed 1 time with 5L absolute ethyl alcohols again, 3h is then dried at 80 DEG C, obtains iron manganese phosphate
Lithium L1.The X-ray diffraction spectrogram of the iron manganese phosphate for lithium L1 and iron manganese phosphate for lithium standard sample（XRD spectra）As shown in Figure 2.From
Fig. 2 result can be seen that the diffraction maximum of the iron manganese phosphate for lithium L1 and the peak position phase of the diffraction maximum of iron manganese phosphate for lithium standard sample
Together, peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, it can be seen that, the purity of the iron manganese phosphate for lithium L1 is very
It is high.
15g glucose is dissolved in 500mL deionized waters, and adds the dried iron manganese phosphate for lithium L1 of 100g, so
Afterwards with Fluko high speed shears dispersion machine stirring 15min, it is spray-dried at being then 250 DEG C in temperature, is then protected in nitrogen
Under, the tubular type kiln roasting 8 hours of obtained product at 700 DEG C will be spray-dried, 45 DEG C is then cooled to, obtains iron manganese phosphate
Lithium composite material TM-1.The microscopic appearance of the iron manganese phosphate for lithium composite TM-1 is observed with SEM, it is tied
Fruit is as shown in Figure 3.From Fig. 3 result can be seen that the iron manganese phosphate for lithium composite TM-1 particle diameter is smaller and particle diameter point
Cloth is more uniform.The iron manganese phosphate for lithium composite TM-1 multiplication factor be 5w SEM photograph in, randomly select 100
Individual particle is contrasted with scale and calculates its average value, as iron manganese phosphate for lithium composite TM-1 primary particle size
And calculate standard deviation（Similarly hereinafter）, the results showed that, iron manganese phosphate for lithium composite TM-1 average primary particle diameter is
39.04nm, size grade scale difference are 8.9.
Embodiment 2
The embodiment is used to illustrate iron manganese phosphate for lithium provided by the invention and preparation method thereof.
（1）Prepare the first solution：
By 172.54g（1.5mol）Phosphoric acid is added in 1.65L deionized waters, and is protected toward logical nitrogen in solution, Ran Houjia
Enter 165.39g（0.956mol）Acetic acid Asia manganese and 89.57g（0.515mol）Ferrous acetate dissolves；
（2）Prepare the second solution：
By 185.62g（4.41mol）Lithium hydroxide is dissolved in 1.85L deionized water dissolvings, and logical nitrogen protection；
（3）Cocurrent is mixed and reacted：
First solution is placed in the first NaOH solution tank NaOH 2, second solution is placed in the second NaOH solution tank NaOH 3.Anti-
Pre-add water 1.5L in the storage tank of kettle 1 is answered, the air in storage tank is excluded with nitrogen, then opens the first measuring pump 5 and second simultaneously
Measuring pump 6 controls the flow velocity 100mL/min of the second solution, and will mix to be continuously added to first solution and the second solution
The pH value of product is controlled 7.5 all the time, and the flow velocity of first solution is controlled by pH value, is constantly stirred during charging
Mix, continue to stir 15min under 50 DEG C, 300rpm after adding two kinds of solution, slurry is then sanded at 10 DEG C 3 hours, obtain
Mixed slurry.Then sealed after the mixed slurry being squeezed into the autoclave for leading to nitrogen exhaust, temperature is risen to 200 DEG C
And Stress control is reacted into 6h under 1.5MPa, react and be cooled to 30 DEG C, be filtrated to get sediment.The sediment is first used
5L deionized waters are washed 2 times, are then washed 1 time with 5L absolute ethyl alcohols again, 3h is then dried at 80 DEG C, obtains iron manganese phosphate for lithium
L2.The X-ray diffraction spectrogram of the iron manganese phosphate for lithium L2 and iron manganese phosphate for lithium standard sample（XRD spectra）As shown in Figure 4.From figure
The diffraction maximum that 4 result can be seen that the iron manganese phosphate for lithium L2 is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample,
Peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, it can be seen that, the purity of the iron manganese phosphate for lithium L2 is very high.
10g sucrose is dissolved in 500mL deionized waters, and adds the dried iron manganese phosphate for lithium L2 of 100g, then
15min is stirred with Fluko high speed shears dispersion machine, is spray-dried at being then 230 DEG C in temperature, then under nitrogen protection,
The tubular type kiln roasting 4 hours of obtained product at 750 DEG C will be spray-dried, 45 DEG C is then cooled to, obtains iron manganese phosphate for lithium
Composite TM-2.The microscopic appearance of the iron manganese phosphate for lithium composite TM-2 is observed with SEM, as a result table
Bright, the particle diameter of the iron manganese phosphate for lithium composite TM-2 is smaller and particle diameter distribution is more uniform, and its average primary particle diameter is
45.75nm, size grade scale difference are 10.6.
Embodiment 3
The embodiment is used to illustrate iron manganese phosphate for lithium provided by the invention and preparation method thereof.
（1）Prepare the first solution：
By 172.54g（1.5mol）Phosphoric acid is added in 1.65L deionized waters, and is protected toward logical nitrogen in solution, Ran Houjia
Enter 177.93g（0.994mol）Mn nitrate and 147.55g（0.536mol）Ferrous sulfate dissolves；
（2）Prepare the second solution：
By 193.19g（4.59mol）Lithium hydroxide is dissolved in 1.85L deionized water dissolvings, and logical nitrogen protection；
（3）Cocurrent is mixed and reacted：
First solution is placed in the first NaOH solution tank NaOH 2, second solution is placed in the second NaOH solution tank NaOH 3.Anti-
Pre-add water 1.5L in the storage tank of kettle 1 is answered, the air in storage tank is excluded with nitrogen, then opens the first measuring pump 5 and second simultaneously
Measuring pump 6 controls the flow velocity 30mL/min of the second solution, and mixing is produced to be continuously added to first solution and the second solution
The pH value of thing is controlled 7 all the time, and the flow velocity of first solution is controlled by pH value, is stirred continuously during charging,
Continue to stir 15min under 50 DEG C, 800rpm after adding two kinds of solution, slurry is then sanded at 50 DEG C 0.5 hour, mixed
Close slurry.Then sealed after the mixed slurry being squeezed into the autoclave for leading to nitrogen exhaust, temperature is risen to 140 DEG C simultaneously
Stress control is reacted into 10h under 0.3MPa, has reacted and has been cooled to 40 DEG C, be filtrated to get sediment.The sediment is first used
5L deionized waters are washed 2 times, are then washed 1 time with 5L absolute ethyl alcohols again, 3h is then dried at 80 DEG C, obtains iron manganese phosphate for lithium
L3.The iron manganese phosphate is can be seen that from the iron manganese phosphate for lithium L3 and the XRD spectra of iron manganese phosphate for lithium standard sample result
Lithium L3 diffraction maximum 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, in diffraction pattern not
It was observed that dephasign peak, it can be seen that, the purity of the iron manganese phosphate for lithium L3 is very high.
20g sucrose is dissolved in 500mL deionized waters, and adds the dried iron manganese phosphate for lithium L2 of 100g, then
15min is stirred with Fluko high speed shears dispersion machine, is spray-dried at being then 270 DEG C in temperature, then under nitrogen protection,
The tubular type kiln roasting 10 hours of obtained product at 650 DEG C will be spray-dried, 45 DEG C is then cooled to, obtains iron manganese phosphate for lithium
Composite TM-3.The microscopic appearance of the iron manganese phosphate for lithium composite TM-3 is observed with SEM, as a result table
Bright, the particle diameter of the iron manganese phosphate for lithium composite TM-3 is smaller and particle diameter distribution is more uniform, and its average primary particle diameter is
42.78nm, size grade scale difference are 9.5.
Embodiment 4
The embodiment is used to illustrate iron manganese phosphate for lithium provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares iron manganese phosphate for lithium, unlike, mole of the manganese sulfate and ferrous sulfate
Than difference, specifically, the dosage of manganese sulfate is 203.25g（1.2mol）, the dosage of ferrous sulfate is 82.66g
（0.30mol）, obtain iron manganese phosphate for lithium L4 and iron manganese phosphate for lithium composite TM-4.From the iron manganese phosphate for lithium L4 and phosphoric acid
The result of the XRD spectra of ferromanganese lithium standard sample can be seen that the diffraction maximum and iron manganese phosphate for lithium standard of the iron manganese phosphate for lithium L4
The peak position of the diffraction maximum of sample is identical, and peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, it can be seen that, the phosphorus
Sour ferromanganese lithium L4 purity is very high.The microcosmic shape of the iron manganese phosphate for lithium composite TM-4 is observed with SEM
Looks, the results showed that, the particle diameter of the iron manganese phosphate for lithium composite TM-4 is smaller and particle diameter distribution is more uniform, and it is average once
Particle diameter is 41.43nm, and size grade scale difference is 9.2.
Embodiment 5
The embodiment is used to illustrate iron manganese phosphate for lithium provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares iron manganese phosphate for lithium, unlike, in the process for preparation of first solution,
By 172.54g（1.5mol）After phosphoric acid is added in 1.65L deionized waters and toward before being passed through nitrogen in solution, addition 5.06g
（0.029mol）Ascorbic acid, obtain iron manganese phosphate for lithium L5 and iron manganese phosphate for lithium composite TM-5.From the iron manganese phosphate for lithium
The result of the XRD spectra of L5 and iron manganese phosphate for lithium standard sample can be seen that the diffraction maximum and phosphoric acid of the iron manganese phosphate for lithium L5
The peak position of the diffraction maximum of ferromanganese lithium standard sample is identical, and peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, thus may be used
See, the purity of the iron manganese phosphate for lithium L5 is very high.The iron manganese phosphate for lithium composite TM-5 is observed with SEM
Microscopic appearance, the results showed that, the particle diameter of the iron manganese phosphate for lithium composite TM-5 is smaller and particle diameter distribution is more uniform, its
Average primary particle diameter is 42.35nm, and size grade scale difference is 9.3.
Embodiment 6
The embodiment is used for the preparation method for illustrating iron manganese phosphate for lithium provided by the invention.
Method according to embodiment 1 prepares iron manganese phosphate for lithium, unlike, first solution and the second solution and
Flow in mixed process, be not included at 30 DEG C the step of slurry 1 hour is sanded, but will directly continue under 30 DEG C, 550rpm
The mixed slurry obtained after stirring 15min, which is squeezed into the autoclave for leading to nitrogen exhaust, to be reacted, and obtains iron manganese phosphate
Lithium L6 and iron manganese phosphate for lithium composite TM-6.From the iron manganese phosphate for lithium L6 and the XRD spectra of iron manganese phosphate for lithium standard sample
Result can be seen that the iron manganese phosphate for lithium L6 diffraction maximum it is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample,
Peak shape is narrow and symmetrical, does not observe dephasign peak in diffraction pattern, it can be seen that, the purity of the iron manganese phosphate for lithium L6 is very high.
The microscopic appearance of the iron manganese phosphate for lithium composite TM-6 is observed with SEM, the results showed that, the manganese phosphate
Iron lithium composite material TM-6 particle diameter is smaller and particle diameter distribution is more uniform, and its average primary particle diameter is 49.15nm, size grade scale
Difference is 11.1.
Embodiment 7
The embodiment is used for the preparation method for illustrating iron manganese phosphate for lithium provided by the invention.
Method according to embodiment 1 prepares iron manganese phosphate for lithium, unlike, the phosphoric acid in first solution is used
The ammonium dihydrogen phosphate of identical molal quantity substitutes, and by the lithium hydroxide in second solution with 1mol Lithium hydroxide monohydrate and
The mixture replacing of 1mol sodium hydroxide, obtain iron manganese phosphate for lithium L7 and iron manganese phosphate for lithium composite TM-7.From the phosphorus
The result of sour ferromanganese lithium L7 and iron manganese phosphate for lithium standard sample XRD spectra can be seen that the diffraction of the iron manganese phosphate for lithium L7
Peak 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 in diffraction pattern
Peak, it can be seen that, the purity of the iron manganese phosphate for lithium L7 is very high.It is compound that the iron manganese phosphate for lithium is observed with SEM
Material TM-7 microscopic appearance, the results showed that, the particle diameter of the iron manganese phosphate for lithium composite TM-7 is smaller and particle diameter distribution compared with
To be uniform, its average primary particle diameter is 46.1nm, and size grade scale difference is 10.9.
Comparative example 1
The comparative example is used to illustrate iron manganese phosphate for lithium of reference and preparation method thereof.
（1）Prepare the first solution：
It is same as Example 6；
（2）Prepare the second solution：
It is same as Example 6；
（3）Mix and react：
By autoclave with the first solution is added after nitrogen exhaust, the second solution is then continuously added to, described in control
The flow velocity of second solution is 45mL/min, and the temperature in autoclave is risen into 170 DEG C and by Stress control after charging
8h is reacted under 0.75MPa, has reacted and has been cooled to 35 DEG C, be filtrated to get sediment.The sediment is first used into 5L deionized waters
Washing 2 times, then washed 1 time with 5 absolute ethyl alcohols again, 3h is then dried at 80 DEG C, obtains the iron manganese phosphate for lithium DL1 of reference.
The X-ray diffraction spectrogram of the iron manganese phosphate for lithium DL1 and iron manganese phosphate for lithium standard sample are as shown in Figure 5.Can be with from Fig. 5 result
Find out, the iron manganese phosphate for lithium DL1 of reference diffraction maximum is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape
It is narrow and symmetrical, 23 ° of diffraction miscellaneous peaks that very little be present, it can be seen that, the iron manganese phosphate for lithium DL1 of reference purity will be less than
Iron manganese phosphate for lithium L1 purity.
15g glucose is dissolved in 500mL deionized waters, and adds the iron manganese phosphate for lithium of the dried references of 100g
DL1,15min then is stirred with Fluko high speed shears dispersion machine, be spray-dried at being then 250 DEG C in temperature, then in nitrogen
Under protection, the tubular type kiln roasting 8 hours of obtained product at 700 DEG C will be spray-dried, 45 DEG C is then cooled to, obtains reference
Iron manganese phosphate for lithium composite DTM-1.The iron manganese phosphate for lithium composite of the reference is observed with SEM
DTM-1 microscopic appearance, the results showed that, the iron manganese phosphate for lithium composite DTM-1 of reference particle diameter is larger and particle diameter divides
Cloth is less uniform, and its average primary particle diameter is 78.15nm, and size grade scale difference is 23.4.
Comparative example 2
The comparative example is used for the iron manganese phosphate for lithium and its reference preparation method for illustrating reference.
（1）Prepare the first solution：
It is same as Example 6；
（2）Prepare the second solution：
It is same as Example 6；
（3）Mix and react：
By autoclave with the second solution is added after nitrogen exhaust, the first solution is then continuously added to, described in control
The flow velocity of first solution is 45mL/min, and the temperature in autoclave is risen into 170 DEG C and by Stress control after charging
8h is reacted under 0.75MPa, has reacted and has been cooled to 35 DEG C, be filtrated to get sediment.The sediment is first used into 5L deionized waters
Washing 2 times, then washed 1 time with 5L absolute ethyl alcohols again, 3h is then dried at 80 DEG C, obtains the iron manganese phosphate lithium material of reference
DL2.The XRD spectra of iron manganese phosphate for lithium DL2 and iron manganese phosphate for lithium standard sample from the reference can be seen that the reference
Iron manganese phosphate for lithium DL2 diffraction maximum 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, 23 °
The diffraction miscellaneous peak of very little be present, it can be seen that, the iron manganese phosphate for lithium DL2 of reference purity will be less than iron manganese phosphate for lithium L1's
Purity.
15g glucose is dissolved in 500mL deionized waters, and adds the iron manganese phosphate for lithium of the dried references of 100g
DL2,15min then is stirred with Fluko high speed shears dispersion machine, be spray-dried at being then 250 DEG C in temperature, then in nitrogen
Under protection, by the product obtained after spray drying in 700 DEG C of tubular type kiln roasting 8 hours, 45 DEG C are then cooled to, is joined
The iron manganese phosphate for lithium composite DTM-2 of ratio.The iron manganese phosphate for lithium composite of the reference is observed with SEM
DTM-2 microscopic appearance, the results showed that, the iron manganese phosphate for lithium composite DTM-2 of reference particle diameter is smaller and particle diameter divides
Cloth is more uniform, and its average primary particle diameter is 78.36nm, and size grade scale difference is 24.8.
Comparative example 3
The comparative example is used for the iron manganese phosphate for lithium and its reference preparation method for illustrating reference.
（1）Prepare phosphoric acid solution：
By 172.54g（1.5mol）Phosphoric acid is dissolved in 1.5L deionized waters；
（2）Prepare the mixed solution of manganese sulfate and ferrous sulfate：
By 165.14g（0.975mol）Manganese sulfate and 144.66g（0.525mol）Ferrous sulfate is dissolved in 1L water, leads to nitrogen
Gas shielded；
（3）Prepare aqueous slkali：
By 189.40g（4.5mol）Lithium hydroxide is dissolved in 2.5L deionized waters, leads to nitrogen protection；
（4）Mix and react：
By autoclave with aqueous slkali is added after nitrogen exhaust, phosphoric acid solution is then continuously added to, and by its flow velocity
In 45mL/min, phosphoric acid solution is continuously added to the mixed solution of manganese sulfate and ferrous sulfate again after adding, and it is fast for control
Rate is controlled in 45mL/min, and the temperature of autoclave is risen into 170 DEG C after adding and reacts Stress control under 0.75MPa
8h, react and be cooled to 35 DEG C, be filtrated to get sediment.The sediment is first washed 2 times with 5L deionized waters, then used again
5L absolute ethyl alcohols are washed 1 time, and 3h is then dried at 80 DEG C, obtains the iron manganese phosphate for lithium DL3 of reference.From the phosphoric acid of the reference
The XRD spectra of ferromanganese lithium DL3 and iron manganese phosphate for lithium standard sample can be seen that the iron manganese phosphate for lithium DL3 of reference diffraction
Peak 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, some dephasigns in diffraction pattern be present
Peak, it can be seen that, the iron manganese phosphate for lithium DL3 of reference purity is relatively low.
15g glucose is dissolved in 500mL deionized waters, and adds the iron manganese phosphate for lithium of the dried references of 100g
DL3,15min then is stirred with Fluko high speed shears dispersion machine, be spray-dried at being then 250 DEG C in temperature, then in nitrogen
Under protection, the tubular type kiln roasting 8 hours of obtained product at 700 DEG C will be spray-dried, 45 DEG C is then cooled to, obtains reference
Iron manganese phosphate for lithium composite DTM-3.The iron manganese phosphate for lithium composite of the reference is observed with SEM
DTM-3 microscopic appearance, the results showed that, the iron manganese phosphate for lithium composite DTM-3 of reference particle diameter is smaller and particle diameter divides
Cloth is more uniform, and its average primary particle diameter is 90.23nm, and size grade scale difference is 26.7.
Comparative example 4
The comparative example is used for the iron manganese phosphate for lithium and its reference preparation method for illustrating reference.
Method according to embodiment 6 prepares iron manganese phosphate for lithium, unlike, during the cocurrent mixes, control
The flow velocity of second solution is 45mL/min, and the pH value of mix products is controlled 8 all the time, and the flow velocity of first solution passes through
PH value is controlled, and obtains the iron manganese phosphate for lithium DL4 and iron manganese phosphate for lithium composite DTM-4 of reference.Wherein, from the reference
Iron manganese phosphate for lithium DL4 and the XRD spectra of iron manganese phosphate for lithium standard sample can be seen that the iron manganese phosphate for lithium DL4 of the reference
Diffraction maximum it is identical with the peak position of the diffraction maximum of iron manganese phosphate for lithium standard sample, peak shape is narrow and symmetrical, in diffraction pattern exist one
A little dephasign peaks, it can be seen that, the iron manganese phosphate for lithium DL4 of reference purity is relatively low.Observed with SEM
The iron manganese phosphate for lithium composite DTM-4 of reference microscopic appearance, the results showed that, the iron manganese phosphate for lithium of the reference is compound
Material DTM-4 particle diameter is smaller and particle diameter distribution is more uniform, and its average primary particle diameter is 80.01nm, and size grade scale difference is
24.9。
Test case
Test case is used for the test for illustrating iron manganese phosphate for lithium chemical property.
By positive electrode active materials（The iron manganese phosphate for lithium composite L 1-L7 and comparative example 1-4 that embodiment 1-7 is obtained are obtained
Reference iron manganese phosphate for lithium composite DL1-DL4）, acetylene black, Kynoar（Celebrating rich plastic material purchased from Dongguan City has
Limit company, trade mark FR900）It is 80 by weight:10:10 are dissolved in 1-METHYLPYRROLIDONE, and aluminium is coated in after stirring
On paper tinsel, and toasted at 110 DEG C ± 5 DEG C, obtain positive plate.Using metal lithium sheet as negative plate, barrier film is microporous polypropylene membrane
（Celgard2300）, (wherein, LiPF6 is lithium hexafluoro phosphate to the LiPF6/ (EC+EMC+DMC) that electrolyte is 1.0mol/L, EC
For ethylene carbonate, EMC is methyl ethyl carbonate, and DMC is dimethyl carbonate, and EC, EMC and DMC volume ratio are 1:1:1), filling
Sealed in the glove box of full argon gas, R2025 button cells are made.At 30 DEG C of room temperature, R2025 button cells are filled with 0.1C
Electric discharge, end of charge voltage 4.3V, discharge cut-off voltage 2.5V.First charge and discharge of the R2025 button cells under 0.1C
Capacitance and efficiency for charge-discharge are 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, using method provided by the invention can obtain particle diameter is small, particle diameter distribution uniformly and
The iron manganese phosphate for lithium of electrochemical performance.It is can be seen that from the contrast of embodiment 1 and embodiment 5 when in first solution
When also containing reducing agent, the oxidation of divalent manganesetion and ferrous ion in cocurrent mixing and course of reaction can be reduced, from
And further improve the obtained chemical property of iron manganese phosphate for lithium.It can be seen that and work as from the contrast of embodiment 1 and embodiment 6
The preparation method of the iron manganese phosphate for lithium also includes stirring the cocurrent mix products under 10-50 DEG C, 300-800rpm mixing
10-30min is closed, then enables to mixed slurry to be spreaded more evenly across during sand milling 0.5-3 hours at 10-50 DEG C, so as to
Further reduce the particle diameter of obtained iron manganese phosphate for lithium and improve its particle diameter distribution uniformity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of preparation method of iron manganese phosphate for lithium, it is characterised in that this method includes that watersoluble divalent manganese source, water-soluble will be contained
Property divalence source of iron and water-soluble phosphorus source the first solution with containing water-soluble lithium source the second solution cocurrent mix after react,
During the cocurrent mixing, produced by controlling the flow velocity of first solution and the second solution so that obtained cocurrent is mixed
The pH value of thing controls in 6.5-7.5 all the time；The water-soluble phosphorus source is phosphoric acid/or dihydric phosphate, or is phosphoric acid and/or phosphorus
Acid dihydride salt and dibasic alkaliine and/or the mixture of neutral phosphate；At least partly described water-soluble lithium source is lithium hydroxide；
The cocurrent is blended in mixing arrangement and carried out, and the mixing arrangement includes：It is reactor (1), the first NaOH solution tank NaOH (2), second molten
Flow container (3) and pH controllers (4), first NaOH solution tank NaOH (2) are connected by the first measuring pump (5) with the reactor (1), institute
State the second NaOH solution tank NaOH (3) to connect with the reactor (1) by the second measuring pump (6), the probe of the pH controllers (4) is set
In the reactor (1) and the pH controllers (4) and first measuring pump (5) or second measuring pump (6)
Connection；The method of the cocurrent mixing includes first solution being placed in first NaOH solution tank NaOH (1), molten by described second
Liquid is placed in second NaOH solution tank NaOH (2), will not the corresponding solution of measuring pump with the pH controllers (4) connection with constant
Flow velocity is added in the reactor (1), and by controlling the stream of solution corresponding with the measuring pump of the pH controllers (4) connection
Speed with by the pH value of the cocurrent mix products control in 6.5-7.5.
2. preparation method according to claim 1, wherein, the concentration of first solution and the second solution is identical or not
Together, and it is each independently 0.1-5mol/L.
3. preparation method according to claim 2, wherein, the flow velocity of first solution is 10-150mL/min；Or
The flow velocity of second solution is 10-150mL/min.
4. preparation method according to claim 1, wherein, the water-soluble phosphorus source is phosphoric acid, and the water-soluble lithium source
For lithium hydroxide.
5. preparation method according to claim 4, wherein, second solution also contains potassium hydroxide and/or hydroxide
Sodium.
6. the preparation method according to claim 4 or 5, wherein, with Mn2+Meter the watersoluble divalent manganese source and with Fe2+
Meter the watersoluble divalent source of iron total dosage with PO4 3-The mol ratio of the dosage of the water-soluble phosphorus source of meter is 0.95-
1.05:1, and with Li+Meter the water-soluble lithium source dosage with PO4 3-Mole of the dosage of the water-soluble phosphorus source of meter
Than for 1.05-3.15:1.
7. according to the preparation method described in any one in claim 1 and 3-5, wherein, the watersoluble divalent manganese source is selected from
One or more in protochloride manganese, manganese bromide, Mn nitrate, perchloric acid Asia manganese, manganese sulfate and acetic acid Asia manganese；The water
Soluble divalent source of iron is selected from frerrous chloride, ferrous bromide, ferrous fluosilicate, ferrous nitrate, ferrous perchlorate, ferrous sulfate and vinegar
One or more in sour ferrous iron.
8. according to the preparation method described in any one in claim 1 and 3-5, wherein, also containing also in first solution
Former agent；The dosage of the reducing agent with Mn2+Meter the watersoluble divalent manganese source and with Fe2+The watersoluble divalent of meter
The mol ratio of total dosage of source of iron is 0.01-0.1:1；The reducing agent is ascorbic acid and/or citric acid.
9. preparation method according to claim 1, wherein, this method also includes the cocurrent mix products in 10-50
DEG C, 10-30min is stirred under 300-800rpm, then 0.5-3 hours are sanded at 10-50 DEG C.
10. the preparation method according to claim 1 or 9, wherein, the reaction is carried out in an inert atmosphere；The reaction
Condition include：Reaction temperature is 120-240 DEG C, reaction pressure 0.1-3.5MPa, and the reaction time is 1-12 hours.
11. preparation method according to claim 1, wherein, this method also includes mixing reaction product with organic carbon source
And be spray-dried, then Spray dried products are calcined again.
12. preparation method according to claim 11, wherein, in terms of the dry weight of the reaction product of 100 parts by weight, institute
The dosage for stating organic carbon source is 5-25 parts by weight；The organic carbon source is selected from glucose, sucrose, lactose, maltose, phenolic resin
With the one or more in epoxy resin.
13. the preparation method according to claim 11 or 12, wherein, the temperature of the spray drying is 200-300 DEG C；Institute
It is 550-750 DEG C to state the condition of roasting to include sintering temperature, and roasting time is 4-10 hours.
14. the iron manganese phosphate for lithium being prepared as the method described in any one in claim 1-13.
15. application of the iron manganese phosphate for lithium as positive electrode active materials described in claim 14.
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