CN104752718B - A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof - Google Patents
A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof Download PDFInfo
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- CN104752718B CN104752718B CN201310740582.2A CN201310740582A CN104752718B CN 104752718 B CN104752718 B CN 104752718B CN 201310740582 A CN201310740582 A CN 201310740582A CN 104752718 B CN104752718 B CN 104752718B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 kind of LiMnxFe1‑xPO4The preparation method of positive electrode active materials, this method are to mix soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group substance solution, reaction generation MnxFe1‑xPO4·2H2Presoma is recycled to prepare LiMn after O presomasxFe1‑xPO4.Present invention also offers the LiMn being prepared by this methodxFe1‑xPO4Positive electrode active materials.Positive electrode active materials particle diameter distribution prepared by the present invention is homogeneous, and pattern is perfect, soilless sticking, and grain diameter is small, is advantageous to improve the electric conductivity of material, the battery multiplying power discharging property of preparation is excellent, and particularly high-rate discharge ability is excellent；The charge/discharge capacity of battery is high simultaneously, and battery charging and discharging is stable, good cycle, is provided the foundation for the development of excellent positive electrode active materials, is advantageous to the application of such a material and the development of battery.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly to a kind of LiMnxFe1-xPO4Positive electrode active materials and its preparation
Method.
Background technology
Lithium ion battery has been widely used for mobile communication, notebook computer, shooting as high-energy-density electrochmical power source
The fields such as machine, camera, portable instrument, and various countries study energetically electric automobile, space power system it is preferred supporting
Power supply, turn into the first choice of fungible energy source.
Anode material for lithium-ion batteries is the focus and difficult point of prior art research, conventional such as LiFePO4, have good
Chemical property, charge and discharge platform is very steady, Stability Analysis of Structures in charge and discharge process, and has nontoxic, pollution-free, security
Can it is good, can use in high temperature environments, the advantages that raw material sources are extensive, be the material that current battery circle is competitively developed.But
LiFePO4Relative to Li+/ Li electrode potential is only 3.4 V, and energy storage density is low, limits its application field and development prospect.
And LiMnPO4Relative to Li+/ Li electrode potential is 4.1 V, and is located at the stable electrochemical window of existing electrolyte system,
Theoretical capacity is up to 170 mAh/g simultaneously, has potential high-energy-density.In addition, synthesis LiMnPO4Cost is low, to ring
Border is friendly.But the LiMnPO of reversible discharge and recharge is capable of in existing synthesis4Extremely difficult, electronics is in LiMnPO4The middle energy gap that transition occurs
For 2 eV, electron conduction extreme difference, in discharge process, electrode polarization degree is larger, therefore quick in electric discharge middle and later periods, voltage
Blanking voltage is dropped to, causes battery capacity relatively low.Prior art research is by the introducing hetero-atoms in material lattice, using member
Element is adulterated to improve the electrical conductivity of this material, such as introduces the atoms such as Fe, forms LiMnxFe1-xPO4Solid-solution material.
Existing synthesis LiMnxFe1-xPO4The method of solid-solution material generally comprises high-temperature solid phase reaction method, liquid phase coprecipitation
Method, hydro-thermal method, sol-gel process, oxidation-reduction method, solid phase microwave method and mechanical attrition method etc..Currently used is that high temperature is consolidated
Phase reaction method and hydro-thermal method.
Publication No. CN101764203A patent discloses a kind of anode material for lithium-ion batteries high density iron manganese phosphate
The preparation method of lithium, this method are included manganese salt（Manganese sulfate and manganese nitrate）And molysite（Di-iron trioxide, ferric phosphate）It is dissolved in water
In, add phosphoric acid or ammonium dihydrogen phosphate.Add glucose simultaneously or sucrose is cooked reducing agent, pH value is adjusted with ammoniacal liquor, one
Reduced iron and manganese at fixed temperature, reaction generation NH4Fe1-xMnxPO4（0<x<0.4）Presoma.Then by NH4Fe1-xMnxPO4（0
<x<0.4）And lithium source（Such as lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium phosphate）Mixing carries out ball milling, so
It is sintered afterwards under 500-900 DEG C of high temperature, generates 8-14um bulky grain LiMnxFe1-xPO4（0<x<0.4）.The high temperature solid-state
Method prepares iron manganese phosphate for lithium and problems be present：1. the NH generated4Fe1-xMnxPO4（0<x<0.4）Particle is big, has during late phase reaction
A large amount of NH3Generation, presoma, which can decompose, to be difficult to do stable skeleton；The LiMn of generationxFe1-xPO4（0<x<0.4）Final product
Particle is big, reaches 8-14um, and cryogenic property and high-multiplying power discharge are extremely inefficient, can not apply in power type battery.
Publication No. CN102249208A discloses a kind of Hydrothermal Synthesiss of ion battery positive pole material manganese lithium phosphate iron lithium
Method, specifically disclose and be stirred lithium hydroxide, phosphoric acid, ferrous sulfate and manganese sulfate, be then transferred into confined reaction
In kettle, under a certain pressure（0.48-1MPa）, under certain temperature（150-180℃）Filtration washing is carried out after reaction a few hours, so
After add soluble carbon source（Such as glucose, sucrose, starch, phenolic resin）It is stirred scattered, is then spray-dried
The latter's expansion drying, finally powder by dried at high temperature（600-750℃）It is sintered bag carbon and obtains iron manganese phosphate for lithium
Material.The hydro-thermal method prepares iron manganese phosphate for lithium and problems be present：1. raw material, sulfate radical are done using ferrous sulfate and manganese sulfate
Need the lithium hydroxide of increase by 2 times to match, and lithium source is more expensive, cause to prepare cost higher；2. there is sulfuric acid in filtrate after reaction
Lithium is remained, it is necessary to washed and the precipitation in later stage extraction lithium sulfate process, adds the process and cost of preparation process；3.
When preparing precursor solution, can produce a variety of insoluble molysite such as ferric phosphate, manganese phosphate, the hydrogen Asia manganese of phosphoric acid one, lithium phosphate, it is a variety of not
Molten manganese salt and a variety of insoluble lithium salts, composition is more, and it is uniform, consistent scattered that various composition is difficult to ensure that in hydrothermal reaction process
And react to each other, it is probably uneven consistent to cause final product composition；4. in hydro-thermal reaction, due to LiFePO4 and phosphorus
The Ksp of sour manganese lithium is different, and it is not synchronous homogeneous precipitation to be likely to result in two kinds of compositions, and it may not be uniform to cause final product
Single-phase iron manganese phosphate lithium material.
The content of the invention
The present invention in order to solve prior art preparation LiMnxFe1-xPO4Particle diameter is larger, cryogenic property and high-multiplying power discharge
Efficiency is low, while the LiMn preparedxFe1-xPO4The shortcomings that not being homogeneous single phase iron manganese phosphate lithium material, there is provided one kind has particle diameter
Small, cryogenic property and high-multiplying power discharge efficiency high, form single-phase LiMnxFe1-xPO4And preparation method thereof.
The invention provides a kind of LiMnxFe1-xPO4The preparation method of positive electrode active materials, this method comprise the following steps：
S1, soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group substance solution mixed
Conjunction forms mixed liquor, and it is 3-14 to add pH value regulator regulation pH value, reaction generation MnxFe1-xPO4·2H2O presomas；
S2, under an inert atmosphere, Mn prepared by step S1xFe1-xPO4·2H2O presomas mix with lithium source and water, are dry
It is dry, then it is calcined under an inert atmosphere and LiMn is madexFe1-xPO4；
Wherein, 0 ＜ X ＜ 1.
Present invention also offers the LiMn being prepared by the above methodxFe1-xPO4Positive electrode active materials.
Mn prepared by the present inventionxFe1-xPO4·2H2O presomas, manganese and iron are all trivalents, and valence state is consistent, can be in 0-1
Between any adjustment manganese ratio；In presoma course of reaction, the salt used is all soluble-salt, ensure that iron, manganese reach
The horizontal mixing of molecular level, manganese and iron is avoided to mix the defects of uneven；With MnxFe1-xPO4·2H2O is presoma, and with this
To react framework, soluble lithium source can be uniformly coated on granular precursor surface, and lithium is directly embedded into during high temperature sintering
MnxFe1-xPO4·2H2In O, that is, generate LiMnxFe1-xPO4Large-scale decomposition does not occur for product, process, and material structure is stable
And prepared LiMnxFe1-xPO4Material is pure phase, is advantageous to the deintercalation of lithium ion.
Simultaneously the present invention preparation method take short, energy consumption is low, cost is low, yield is high, prepare material granule uniformly, system
Standby material property is stable, technological process is simply controllable, and large-scale industry cleanly production can be achieved.
Brief description of the drawings
Fig. 1 is Mn prepared by embodiment 10.65Fe0.35PO4Scanning of materials electromicroscopic photograph；
Fig. 2 is LiMn prepared by embodiment 10.65Fe0.35PO4Scanning of materials electromicroscopic photograph；
Fig. 3 is Mn prepared by comparative example 10.65Fe0.35PO4Scanning of materials electromicroscopic photograph；
Fig. 4 is LiMn prepared by comparative example 10.65Fe0.35PO4Scanning of materials electromicroscopic photograph；
Fig. 5 is LiMn prepared by embodiment 10.65Fe0.35PO4Material XRD；
Fig. 6 is the LiMn of the preparation of comparative example 10.65Fe0.35PO4Material XRD；
Fig. 7 is the charging and discharging curve of battery prepared by embodiment 1；
Fig. 8 is the charging and discharging curve of the battery of the preparation of comparative example 1.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
The invention provides a kind of LiMnxFe1-xPO4The preparation method of positive electrode active materials, this method comprise the following steps：
S1, soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group substance solution mixed
Conjunction forms mixed liquor, and it is 3-14 to add pH value regulator regulation pH value, reaction generation MnxFe1-xPO4·2H2O presomas；
S2, under an inert atmosphere, Mn prepared by step S1xFe1-xPO4·2H2O presomas mix with lithium source and water, are dry
It is dry, then it is calcined under an inert atmosphere and LiMn is madexFe1-xPO4；
Wherein, 0 ＜ X ＜ 1.
The LiMn of the present invention simultaneouslyxFe1-xPO4In the preparation method of positive electrode active materials, using the trivalent iron salt of solubility
With the trivalent manganese salt of solubility, iron is consistent with manganese valence, the ratio of iron and manganese can be arbitrarily adjusted, so as to improve
LiMnxFe1-xPO4Energy density, improve its capacity.Secondly, the salt that the present invention uses all is soluble-salt, ensure that iron, manganese
Reach the horizontal mixing of molecular level, avoid manganese and iron from mixing the defects of uneven.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the step S1
Start to disperse mixed liquor while middle formation mixed liquor.Further preferably, the scattered method is sanded for circulation.
Circulation is proceeded by when forming mixed liquor to be sanded, so can be by the Mn of the larger nucleus of generationxFe1-xPO4·2H2O passes through
It is scattered to form more less nucleus, in MnxFe1-xPO4·2H2In the case that O total amounts are constant, what nucleus was more at most formed
MnxFe1-xPO4·2H2O particle size is smaller, obtained presoma MnxFe1-xPO4·2H2O is nano level, so as to ensure
Final products LiMnxFe1-xPO4Particle diameter be nanoscale.LiMnxFe1-xPO4Primary particle size there was only 30 ~ 100nm, particle pole
Carefully, the deintercalation of lithium ion is advantageous to.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the step S2
In in MnxFe1-xPO4·2H2O presomas add carbon source when being mixed with lithium source and water.The content of the carbon source of the addition is
LiMnxFe1-xPO4The 0.1-5% of gross mass.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the step S1
In, the trivalent iron salt is with Fe3+Meter, the trivalent manganese salt is with Mn3+Meter, the phosphorous acid group material of solubility is with PO4 3-Meter, institute
The mol ratio for stating trivalent iron salt, the trivalent manganese salt and the phosphorous acid group material of the solubility is 0-1：0-1：1-1.2；It is and described
The mole of trivalent iron salt and the trivalent manganese salt is not 0.More preferably 0.2-0.5：0.5-0.8：1.Above-mentioned each material
Mol ratio within the range, can be good at ensureing that the trivalent iron salt and the trivalent manganese salt are reacted with phosphate radical, reduce
The generation of impurity, while the content of iron and manganese is within the range, can be good at ensureing LiMnxFe1-xPO4Capacity, energy it is close
Degree and charge-discharge magnification.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, in order to be further ensured that not
Produce other impurities, it is preferable that the trivalent iron salt and the integral molar quantity of the trivalent manganese salt are equal to the soluble phosphoric acid
The mole of root material.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that 0.5≤X≤
0.8.More preferably 0.6≤X≤0.8.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the step S1
PH be 6-8.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the step S1
In reaction temperature be 0-100 DEG C.More preferably 40-60 DEG C.The control of reaction temperature is added in glass reaction kettle
Deionized water, reactor is incubated with thermostatical circulating water.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the roasting
Temperature is 600-800 DEG C.More preferably 650-720 DEG C.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, it is preferable that the solubility
Trivalent manganese salt is water-soluble or ethanol manganese salt, as in manganese chloride, manganous bromide, manganese nitrate, manganese sulfate and manganese acetate extremely
Few one kind, more preferably manganese sulfate；The soluble trivalent iron salt is water-soluble or ethanol molysite, such as chlorination
At least one of iron, ferric bromide, ferric nitrate, ferric sulfate and ferric acetate, more preferably ferric sulfate；The lithium source is solvable
In water or the lithium salts of alcohol, such as lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chloride, lithium fluoride, formic acid
At least one of lithium, lithium iodide, lithium nitrate, lithium perchlorate and lithium tartrate；The phosphorous acid group material of solubility is to be dissolved in
With water or the phosphorous acid group material of ethanol, as in phosphoric acid, lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate and potassium phosphate extremely
Few one kind, more preferably ammonium dihydrogen phosphate；The carbon source is glucose sugar, sucrose, maltose, lactose, graphite, carbon nanometer
At least one of pipe, graphene, phenolic resin and starch；The pH value regulator is soluble bronsted lowry acids and bases bronsted lowry, such as phosphoric acid, salt
At least one of acid, sulfuric acid, nitric acid, ammoniacal liquor, sodium hydroxide, lithium hydroxide and potassium hydroxide.
According to LiMn provided by the present inventionxFe1-xPO4The preparation method of positive electrode active materials, in order that reaction can be more
Smoothly carry out, it is preferable that molar concentration≤1,0 ＜ solubility trivalents of trivalent manganese salt in 0 ＜ solubility trivalent manganese salt solutions
In iron salt solutions in the soluble phosphorous acid group substance solutions of molar concentration≤1,0 ＜ of trivalent iron salt phosphate radical molar concentration≤
1。
It is in step S1 that soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group material is molten
Liquid mixing method can be soluble trivalent manganese salt solution and soluble ferric salt solution are first mixed, then again with it is solvable
Property the mixing of phosphorous acid group substance solution, or simultaneously by soluble trivalent manganese salt solution, soluble ferric salt solution and can
The phosphorous acid group substance solution mixing of dissolubility, preferably first mixes soluble trivalent manganese salt solution and soluble ferric salt solution
Close, then mixed again with soluble phosphorous acid group substance solution.
The mixture of above-mentioned soluble manganic and soluble trivalent iron salt and soluble phosphorous acid group material are added drop-wise to instead
The feed way in kettle is answered to be not particularly limited, Ke Yishi：A, phosphate solution is added drop-wise in ferromanganese salting liquid；B, by ferromanganese
Salting liquid is added drop-wise in phosphate solution；C, by ferromanganese salt, parallel be added drop-wise in the 3rd container is carried out simultaneously with phosphate solution
Reaction.
Soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group material are added drop-wise to reaction
In kettle, quickly it is dispersed with stirring when being added dropwise, while adds the pH value of pH value regulator regulation reaction system, pH value is controlled in 3-
Between 14, preferably 6-8；PH value regulator used in adjustment pH value is added dropwise mode and had no particular limits, Ke Yishi：A, pH value is adjusted
Agent addition is saved in phosphate solution；B, by pH value regulator addition in ferromanganese salting liquid；C, pH value regulator pH value control
Device processed is individually added dropwise.
The Mn that will be obtained after step S1 reactions fullyxFe1-xPO4·2H2O is filtered, washed, being dried；
In step S2, under an inert atmosphere, Mn prepared by step S1xFe1-xPO4·2H2O presomas and lithium source, carbon source
Mixed with deionized water, then carry out dispersed obtaining slurry；Scattered slurry, which is placed in sand mill, carries out circulation sand milling,
It is incubated in sand grinding process with cooling water, temperature control is between 0-100 DEG C, preferably 0-30 DEG C, and it is that 0.5-4 is small that the time, which is sanded,
When；Then the slurry after sand milling is dried；Dried powder is placed in high temperature process furnances, in inert gas shielding
Under, at 600-800 DEG C, constant temperature 0.5-72 hours at preferably 650-720 DEG C, preferably 8-12 hours are sintered, then naturally cold
But room temperature is arrived, has both obtained the LiMn of bag carbonxFe1-xPO4Material.
The present invention prepares LiMnxFe1-xPO4During the dispersing mode used of each link can be：Mechanical agitation, shearing,
Ball milling, sand milling, hypergravity etc..
The present invention prepares LiMnxFe1-xPO4During the inert gas used of each link can be：Nitrogen, argon gas, helium
One or more of mixing.
The present invention prepares LiMnxFe1-xPO4During the drying mode used can be：Vacuum drying, inert gas shielding
Heat drying, spray drying, freeze-drying, expansion drying etc..
Present invention also offers a kind of LiMnxFe1-xPO4Positive electrode active materials, the positive electrode active materials are by of the present invention
Method be prepared.
According to LiMn provided by the present inventionxFe1-xPO4Positive electrode active materials, it is preferable that the LiMnxFe1-xPO4It is flat
Equal primary particle size is not more than 100nm.
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
1st, the preparation of positive electrode active materials：
The manganese nitrate solution of the ferric nitrate of 1L 0.35mol/l concentration and 1L 0.65mol/l concentration is added drop-wise to respectively
In the sodium radio-phosphate,P-32 solution of 1L 1mol/l concentration, while it is 6.7 to control the pH of reaction solution with citric acid, in 40 DEG C of recirculated water
The lower stirring reaction of insulation 3 hours, filtration washing obtains ecru Mn after drying0.65Fe0.35PO4·2H2O materials.
The pattern of the phosphate presoma of above-mentioned preparation is observed using Hitachi S4800 types SEM (SEM), such as
Shown in Fig. 1, the grain diameter for the phosphate presoma that observation obtains above-mentioned preparation is homogeneous, and size is basically identical, soilless sticking phenomenon.
By 0.1mol Mn0.65Fe0.35PO4·2H2O powder, 0.1mol lithium hydroxides, 2.355 grams of glucose and 3.14 grams
Solid content is 5% CNT（CNT）It is added separately in 1L deionized waters, it is small that mixed solution is sanded in sand mill to 4
When.Then slurry is spray-dried using spray dryer, the powder after spray drying is placed in high temperature process furnances,
Under N2 protections, Isothermal sinter 24 hours at 680 DEG C, it is homogeneous to naturally cool to i.e. acquisition black bag carbon after room temperature
LiMn0.65Fe0.35PO4Materials A 1.
The pattern of the phosphate presoma of above-mentioned preparation is observed using Hitachi S4800 types SEM (SEM), such as
Shown in Fig. 2, the grain diameter for the iron manganese phosphate for lithium positive electrode active materials that observation obtains above-mentioned preparation is homogeneous, and size is basically identical,
Soilless sticking phenomenon.
Test is using 40KV pipes pressure, electric current 200mA, 1 ° of step-length, 10-90 ° of test LiMn of test angle0.65Fe0.35PO4's
XRD, as a result see Fig. 5.From fig. 5, it can be seen that prepared iron manganese phosphate for lithium peak type it is sharp, without acromion, be pure phase, with phosphorus
The XRD spectra of sour ferromanganese lithium is similar.
Fig. 7 is respectively the charging and discharging curve figure of prepared iron manganese phosphate for lithium.From figure 7 it can be seen that prepared using the method
The discharge capacity of the iron manganese phosphate for lithium gone out is high.
2nd, simulated battery is prepared
Iron manganese phosphate for lithium A1 in mass ratio：Acetylene black：PVDF= 80：10：10 ratio mixing, after being uniformly dispersed with NMP
Smear is made, and pole piece is dried in vacuo more than 24h in 120 DEG C.Simulated battery S1 is using metal lithium sheet as negative pole, with celgard2400
Polypropylene porous film is barrier film, with 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixing
Solution (volume ratio is=1: 1) is electrolyte, and the assembling process of all batteries is carried out in the glove box full of argon gas.
Embodiment 2
1st, positive electrode active materials are prepared
The manganese chloride of 1L 0.4mol/l concentration and the ferric chloride solution of 1L 0.4mol/l concentration are added to 1L's simultaneously
In the ammonium dihydrogen phosphate of 0.8mol/l concentration, while it is 7 to control the PH of reaction solution with ammoniacal liquor, is protected in 20 DEG C of recirculated waters
The lower stirring reaction of temperature 4 hours, when starting to precipitate, that is, starts to carry out circulation sand milling in stirring reaction, will be molten after reaction
After liquid stands aging 48 hours, filtration washing obtains nanoscale Mn after drying0. 5Fe0. 5PO4·2H2O materials.
By 0.5mol Mn0. 5Fe0. 5PO4·2H2O powder, 0.5mol lithium acetates, 7.85 grams of glucose and 15.7 grams are solid
Content is 5% graphene, is added separately in 1.6L deionized waters, mixed solution is sanded into 4 hours in sand mill, then
It is freeze-dried with freeze drier.Powder after freeze-drying is placed in high temperature oven, under Ar gas shieldeds, 700
Isothermal sinter 12 hours at DEG C, naturally cool to and the homogeneous LiMn of black bag carbon is obtained after room temperature0. 5Fe0. 5PO4Materials A 2.
2nd, battery S2 is prepared according to the method for embodiment 1.
Embodiment 3
1st, positive electrode active materials are prepared
The 1mol/l of the manganese sulfate of 1L 0.8mol/l concentration, the ferrum sulfuricum oxydatum solutum of 1L 0.2mol/l concentration and 1L is dense
The potassium phosphate solution of degree is added drop-wise in the reactor of 25 DEG C of circulating water heat insulations simultaneously respectively, while molten with ascorbic acid control reaction
The PH of liquid is 6.5, is stirred when being added dropwise, and sand milling is started the cycle over when starting to occur precipitated product, completes within 2 hours to be added dropwise instead
Should, filtration washing obtains Mn after drying0.8Fe0.2PO4·2H2O precursor powders.
By 0.6mol Mn0.8Fe0.2PO4·2H2O powder, 0.6mol lithium hydroxides, 14.13 grams of sucrose are added separately to
In 1.2L deionized waters, mixed solution is sanded 6 hours in sand mill, is then spray-dried solution after sand milling.
Dried powder is placed in tube furnace, under N2 protections, Isothermal sinter 10 hours, naturally cold at 720 DEG C
But to the i.e. homogeneous LiMn of acquisition bag carbon after room temperature0.8Fe0.2PO4Materials A 3.
2nd, battery S3 is prepared according to the method for embodiment 1.
Embodiment 4
1st, positive electrode active materials are prepared
The 1mol/l of the manganese nitrate of 1L 0.1mol/l concentration, the iron nitrate solution of 1L 0.9mol/l concentration and 1L is dense
The ammonium hydrogen phosphate solution of degree is added drop-wise in the reactor of 60 DEG C of circulating water heat insulations simultaneously respectively, while controls reaction solution with ammoniacal liquor
PH be 8, stir when being added dropwise, starts the cycle over sand milling when starting to occur precipitated product, 2 hours completion dropwise reactions, mistake
Filter washing obtains Mn after drying0.1Fe0.9PO4·2H2O precursor powders.
By 0.6mol Mn0.1Fe0.9PO4·2H2O powder, 0.6mol lithium hydroxides, 4.52 grams of phenolic resin are separately added into
Into 1.2L deionized waters, mixed solution is sanded 6 hours in sand mill, is then spray-dried solution after sand milling.
Dried powder is placed in tube furnace, under N2 protections, Isothermal sinter 12 hours, naturally cold at 650 DEG C
But to the i.e. homogeneous LiMn of acquisition bag carbon after room temperature0.1Fe0.9PO4Materials A 4.
2nd, battery S4 is prepared according to the method for embodiment 1.
Embodiment 5
1st, positive electrode active materials are prepared
The 1mol/l of the manganous bromide of 1L 0.9mol/l concentration, the bromination ferrous solution of 1L 0.1mol/l concentration and 1L is dense
The phosphoric acid solution of degree is added drop-wise in the reactor of 50 DEG C of circulating water heat insulations simultaneously respectively, while controls reaction solution with ascorbic acid
PH be 3, stir when being added dropwise, starts the cycle over sand milling when starting to occur precipitated product, 2 hours completion dropwise reactions, mistake
Filter washing obtains Mn after drying0.9Fe0.1PO4·2H2O precursor powders.
By 0.6mol Mn0.9Fe0.1PO4·2H2O powder, 0.6mol lithium hydroxides, 6.83 grams of starch are added separately to
In 1.2L deionized waters, mixed solution is sanded 6 hours in sand mill, is then spray-dried solution after sand milling.
Dried powder is placed in tube furnace, under N2 protections, Isothermal sinter 10 hours, naturally cold at 800 DEG C
But to the i.e. homogeneous LiMn of acquisition bag carbon after room temperature0.9Fe0.1PO4Materials A 5.
2nd, battery S5 is prepared according to the method for embodiment 1.
Embodiment 6
1st, positive electrode active materials are prepared
The 1mol/l of the manganese chloride of 1L 0.6mol/l concentration, the ferric chloride solution of 1L 0.4mol/l concentration and 1L is dense
The phosphoric acid solution of degree is added drop-wise in the reactor of 100 DEG C of circulating water heat insulations simultaneously respectively, while molten with ascorbic acid control reaction
The PH of liquid is 5.4, is stirred when being added dropwise, and completes within 2 hours dropwise reaction, and filtration washing obtains Mn after drying0.6Fe0.4PO4·2H2O
Precursor powder.
By 0.6mol Mn0.6Fe0.4PO4·2H2O powder, 0.6mol lithium hydroxides, 10.25 grams of lactose are added separately to
In 1.2L deionized waters, mixed solution is sanded 6 hours in sand mill, is then spray-dried solution after sand milling.
Dried powder is placed in tube furnace, under N2 protections, Isothermal sinter 15 hours, naturally cold at 600 DEG C
But to the i.e. homogeneous LiMn of acquisition bag carbon after room temperature0.6Fe0.4PO4Materials A 6.
2nd, battery S6 is prepared according to the method for embodiment 1.
Comparative example 1
1st, positive electrode active materials are prepared
Under N2 protections, by 0.5mol lithium carbonates, 1mol ammonium dihydrogen phosphates, 0.65mol oxalic acid Asia manganese, 0.35mol oxalic acid
Ferrous and 23.55 grams glucose are dispersed in 1L deionized waters respectively, and it is small first to carry out ball milling 24 to mixed solution with ball mill
When, the mixed solution after ball milling is spray-dried, dried powder is placed in tube furnace, under N2 protections, 680
Sintered at DEG C 24 hours, that is, obtain the black LiMn for having wrapped carbon0.65Fe0.35PO4Material C A1.
Observed using Hitachi S4800 types SEM (SEM) the phosphate presoma of above-mentioned preparation pattern and
LiMn0.65Fe0.35PO4Pattern, respectively as shown in Figure 3 and Figure 4.As shown in figure 3, observation obtains the presoma one of above-mentioned preparation
Secondary particle is larger, and not of uniform size, there is obvious agglomeration.As shown in figure 4, observation obtains the iron manganese phosphate for lithium of above-mentioned preparation
Positive electrode active materials primary particle size is larger, and size distribution scope is very wide between particle.
Test is using 40KV pipes pressure, electric current 200mA, 1 ° of step-length, 10-90 ° of test LiMn of test angle0.65Fe0.35PO4's
XRD, as a result see Fig. 6.From fig. 6, it can be seen that prepared iron manganese phosphate for lithium has on a small quantity without acromion, illustrate iron manganese phosphate for lithium
In with the presence of impurity.
Fig. 8 is respectively the charging and discharging curve figure of prepared iron manganese phosphate for lithium.From figure 8, it is seen that prepared using the method
The discharge capacity of the iron manganese phosphate for lithium gone out is lower than the discharge capacity that embodiment 1 is.
2nd, battery CS1 is prepared according to the method for embodiment 1.
Comparative example 2
1st, positive electrode active materials are prepared
Lithium ferric manganese phosphate positive electrode active materials are prepared according to the method in CN101764203A embodiments 3, are designated as
CA2。
2nd, battery CS2 is prepared according to the method for embodiment 1.
Comparative example 3
1st, positive electrode active materials are prepared
Iron manganese phosphate for lithium active material is prepared according to the method in CN102249208A embodiments 4, is designated as CA3.
2nd, battery CS3 is prepared according to the method for embodiment 1.
Performance test
1st, average primary particle diameter is tested, positive electrode active materials A1-A6 prepared by testing example 1-6 and comparative example 1-3 and
CA1-CA3 average primary particle diameter, the results are shown in Table 1；
2nd, energy density is tested：Discharge and recharge is carried out under 0.1C multiplying powers, electric discharge C-V curve is integrated, discharge curve institute
The area of encirclement is the mass energy density of the material；It the results are shown in Table 1；
3rd, charge/discharge capacity test,：Embodiment 1-6 and comparative example 1-3 the battery S1-S6 and CS1-CS3 prepared is placed in
Charge/discharge capacity test is carried out on charge-discharge test instrument：At room temperature, 4.3V is charged under 0.1C multiplying powers, cut-off current is
0.01C, 2.5V then is discharged under 0.1C multiplying powers, the results are shown in Table 2；
4th, high rate performance is tested：Electricity prepared by battery S1-S6 and CS1-CS3 prepared by embodiment 1-6 and comparative example 1-3
Pond is placed in progress charge-discharge performance test on charge-discharge test instrument, is charged to 4.3V, cut-off current 0.01C under 0.1C multiplying powers, so
Discharge into 2.5V under 1C, 2C, 5C and 10C multiplying power respectively afterwards, the electric discharge of the discharge capacity under each multiplying power and 0.1C multiplying powers is held
The ratio of amount the results are shown in Table 2 as the multiplying power efficiency under the multiplying power；
5th, low-temperature test：Battery prepared by battery S1-S6 and CS1-CS3 prepared by embodiment 1-6 and comparative example 1-3 exists
Under 0.2C cycle charge-discharge twice after, 4.3V is charged to 0.5C, battery is placed in into 0.5C multiplying power dischargings in -10 DEG C of environment arrives
The ratio of 2.5V, -10 DEG C of discharge capacity and 0.5C discharge capacity at room temperature is the Efficiency at Low Temperature of -10 DEG C of the material, as a result
It is shown in Table 2.
Table 1
。
Table 2
。
The positive electrode active materials particle diameter distribution that as can be seen from Table 1 and Table 2 prepared by the present invention is homogeneous, and pattern is perfect, no group
It is poly-, and grain diameter is small, is advantageous to improve the electric conductivity of material, the battery multiplying power discharging property of preparation is excellent, particularly height
Multiplying power discharging property is excellent；The charge/discharge capacity of battery is high simultaneously, and battery charging and discharging is stable, good cycle, is excellent positive pole
The development of active material provides the foundation, and is advantageous to the application of such a material and the development of battery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (14)
- A kind of 1. LiMnxFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that this method comprises the following steps：S1, soluble trivalent manganese salt solution, soluble ferric salt solution and soluble phosphorous acid group substance solution mixed into shape Into mixed liquor, and it is 3-14 to add pH value regulator regulation pH value, reaction generation MnxFe1-xPO4·2H2O presomas；S2, under an inert atmosphere, Mn prepared by step S1xFe1-xPO4·2H2O presomas are mixed with lithium source and water, dried, so It is calcined under an inert atmosphere afterwards and LiMn is madexFe1-xPO4；Wherein, 0 ＜ X ＜ 1.
- 2. LiMn according to claim 1xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that the step Start to disperse mixed liquor while forming mixed liquor in rapid S1.
- 3. LiMn according to claim 2xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that described point Scattered method is sanded for circulation.
- 4. LiMn according to claim 1xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that the step In Mn in rapid S2xFe1-xPO4·2H2O presomas add carbon source when being mixed with lithium source and water.
- 5. according to the LiMn described in claim 1-4 any onexFe1-xPO4The preparation method of positive electrode active materials, its feature exist In in the step S1, the trivalent iron salt is with Fe3+Meter, the trivalent manganese salt is with Mn3+Meter, the phosphorous acid group thing of solubility Matter is with PO4 3-Meter, the mol ratio of the trivalent iron salt, the trivalent manganese salt and the phosphorous acid group material of the solubility is 0-1：0- 1：1-1.2；And the mole of the trivalent iron salt and the trivalent manganese salt is not 0.
- 6. LiMn according to claim 5xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that described three The mol ratio of valency molysite, the trivalent manganese salt and the phosphorous acid group material of the solubility is 0.2-0.5：0.5-0.8：1.
- 7. LiMn according to claim 6xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that described three Valency molysite and the integral molar quantity of the trivalent manganese salt are equal to the mole of the phosphorous acid group material of the solubility.
- 8. LiMn according to claim 7xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that 0.5≤X ≤0.8。
- 9. the LiMn stated according to claim 8xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that the step S1 pH is 6-8.
- 10. the LiMn stated according to claim 9xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that the step Reaction temperature in S1 is 0-100 DEG C.
- 11. LiMn according to claim 1xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that the roasting The temperature of burning is 600-800 DEG C.
- 12. LiMn according to claim 4xFe1-xPO4The preparation method of positive electrode active materials, it is characterised in that it is described can Dissolubility trivalent manganese salt is at least one of manganese chloride, manganous bromide, manganese nitrate, manganese sulfate and manganese acetate；The soluble trivalent Molysite is at least one of iron chloride, ferric bromide, ferric nitrate, ferric sulfate and ferric acetate；The lithium source is lithium hydroxide, acetic acid Lithium, lithium benzoate, lithium bromate, lithium bromide, lithium chloride, lithium fluoride, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate and tartaric acid At least one of lithium；The phosphorous acid group material of solubility is phosphoric acid, lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate and phosphorus At least one of sour potassium；The carbon source is glucose sugar, sucrose, maltose, lactose, graphite, CNT, graphene, phenolic aldehyde At least one of resin and starch；The pH value regulator is phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, ammoniacal liquor, sodium hydroxide, hydrogen-oxygen Change at least one of lithium and potassium hydroxide.
- A kind of 13. LiMnxFe1-xPO4Positive electrode active materials, it is characterised in that the positive electrode active materials are appointed by claim 1-12 Method described in meaning one is prepared.
- 14. LiMn according to claim 13xFe1-xPO4Positive electrode active materials, it is characterised in that the LiMnxFe1-xPO4 Average primary particle diameter be not more than 100nm.
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| CN106517131A (en) * | 2016-11-19 | 2017-03-22 | 天津赫维科技有限公司 | Preparing method of high-rate lithium manganese phosphate |
| CN110323434B (en) * | 2019-07-11 | 2022-07-22 | 江苏力泰锂能科技有限公司 | Method for preparing lithium iron manganese phosphate-carbon composite material and lithium iron manganese phosphate-carbon composite material |
| CN110980682A (en) * | 2019-12-18 | 2020-04-10 | 江苏力泰锂能科技有限公司 | Method for preparing lithium manganese iron phosphate precursor and method for preparing lithium manganese iron phosphate |
| CN113871596B (en) * | 2021-09-27 | 2024-01-02 | 湖南亿普腾科技有限公司 | Lithium composite material, preparation method of lithium ion battery positive electrode material and lithium ion battery |
| CN114394584A (en) * | 2021-12-14 | 2022-04-26 | 云南润久科技有限公司 | Method for preparing ferric manganese phosphate lithium battery anode material by coprecipitation-solid phase combination |
| CN114516626B (en) * | 2022-02-18 | 2023-05-30 | 江苏协鑫锂电科技有限公司 | Preparation method of phosphate positive electrode material |
| CN115020664B (en) * | 2022-06-17 | 2024-04-05 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
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