CN104752718A - LiMnxFe1-xPO4 positive electrode active material and preparation method thereof - Google Patents

LiMnxFe1-xPO4 positive electrode active material and preparation method thereof Download PDF

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CN104752718A
CN104752718A CN201310740582.2A CN201310740582A CN104752718A CN 104752718 A CN104752718 A CN 104752718A CN 201310740582 A CN201310740582 A CN 201310740582A CN 104752718 A CN104752718 A CN 104752718A
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positive electrode
electrode active
lithium
limn
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CN104752718B (en
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陈靖华
徐茶清
肖峰
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BYD Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a LiMnxFe1-xPO4 positive electrode active material. The method comprises the following steps that a soluble trivalent manganese salt solution, a soluble ferric iron salt solution and a soluble phosphate radical-containing substance solution are blended to form a mixed solution, the mixed solution undergoes a reaction to produce a MnxFe1-xPO4.2H2O precursor, and LiMnxFe1-xPO4 is prepared from the MnxFe1-xPO4.2H2O precursor. The invention also provides the LiMnxFe1-xPO4 positive electrode active material obtained by the preparation method. The LiMnxFe1-xPO4 positive electrode active material has the advantages of uniform particle size distribution, perfect morphology, no agglomeration, small particle size and material electroconductivity improvement. A cell prepared from the LiMnxFe1-xPO4 positive electrode active material has excellent rate discharge performance, especially has high-rate discharge performance, has a high cell charging-discharging capacity, stable cell charging-discharging performances and good cycle performances, lays the foundation in excellent positive electrode active material development and is conducive to material application and cell development.

Description

A kind of LiMn xfe 1-xpO 4positive electrode active materials and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of LiMn xfe 1-xpO 4positive electrode active materials and preparation method thereof.
Background technology
Lithium ion battery has been widely used in the fields such as mobile communication, notebook computer, video camera, camera, portable instrument as high-energy-density chemical power source, the electric automobile that Ye Shi various countries are studied energetically, the supporting power supply of the first-selection of space power system, become the first-selection of fungible energy source.
Anode material for lithium-ion batteries is focus and the difficult point of prior art research, conventional as LiFePO 4have good chemical property, charge and discharge platform is very steady, Stability Analysis of Structures in charge and discharge process, and there is the advantages such as nontoxic, pollution-free, security performance is good, can use in high temperature environments, raw material sources is extensive, be the material that current battery circle is competitively developed.But LiFePO 4relative to Li +the electrode potential of/Li is only 3.4 V, and energy storage density is low, limits its application and development prospect.And LiMnPO 4relative to Li +the electrode potential of/Li is 4.1 V, and is positioned at the stable electrochemical window of existing electrolyte system, and theoretical capacity is up to 170 mAh/g simultaneously, has potential high-energy-density.In addition, LiMnPO is synthesized 4cost is low, environmentally friendly.But existing synthesis can the LiMnPO of reversible discharge and recharge 4very difficult, electronics is at LiMnPO 4the energy gap of middle generation transition is 2 eV, electron conduction extreme difference, and in discharge process, electrode polarization degree is comparatively large, and therefore in the electric discharge middle and later periods, voltage drops quickly to cut-ff voltage, causes battery capacity lower.Prior art research, by introducing hetero-atoms in material lattice, adopts element doping to improve the conductivity of this material, such as, introduces the atoms such as Fe, form LiMn xfe 1-xpO 4solid-solution material.
Existing synthesis LiMn xfe 1-xpO 4the method of solid-solution material generally comprises high-temperature solid phase reaction method, liquid-phase coprecipitation, hydro thermal method, sol-gel process, oxidation-reduction method, solid phase microwave method and mechanical attrition method etc.Conventional is high-temperature solid phase reaction method and hydro thermal method at present.
Publication number is the preparation method that patent discloses a kind of high-density lithium iron manganese phosphate for lithium ion battery positive electrode material of CN101764203A, the method comprises and is dissolved in water by manganese salt (manganese sulfate and manganese nitrate) and molysite (di-iron trioxide, ferric phosphate), adds phosphoric acid or ammonium dihydrogen phosphate.Add glucose or sucrose is cooked reducing agent simultaneously, regulate pH value, at a certain temperature reduced iron and manganese with ammoniacal liquor, reaction generates NH 4fe 1-xmn xpO 4(0<x<0.4) presoma.Then by NH 4fe 1-xmn xpO 4(0<x<0.4) ball milling is carried out with lithium source (as lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium phosphate etc.) mixing, then sinter under 500-900 DEG C of high temperature, generate the bulky grain LiMn of 8-14um xfe 1-xpO 4(0<x<0.4).This high temperature solid-state method is prepared iron manganese phosphate for lithium and be there is following problem: the NH 1. generated 4fe 1-xmn xpO 4(0<x<0.4) particle is large, has a large amount of NH during late phase reaction 3generate, presoma can decompose and be difficult to do stable skeleton; Eq o ac (zero, 2) 2 generate LiMn xfe 1-xpO 4(0<x<0.4) end product particle is large, reaches 8-14um, cryogenic property and high-multiplying power discharge efficiency extremely low, cannot apply in power type battery.
Publication number is the hydrothermal synthesis method that CN102249208A discloses a kind of ion battery positive pole material manganese lithium phosphate iron lithium, specifically disclose lithium hydroxide, phosphoric acid, ferrous sulfate and manganese sulfate are uniformly mixed, then transfer in closed reactor, under a certain pressure (0.48-1MPa), filtration washing is carried out after (150-180 DEG C) stoichiometric number hour under uniform temperature, then solubility carbon source is added (as glucose, sucrose, starch, phenolic resins etc.) carry out dispersed with stirring, then spraying dry the latter expansion drying is carried out, finally by dried powder at high temperature (600-750 DEG C) carry out sintering bag carbon and obtain iron manganese phosphate lithium material.This hydro thermal method is prepared iron manganese phosphate for lithium and be there is following problem: 1. adopt ferrous sulfate and manganese sulfate to do raw material, sulfate radical needs the lithium hydroxide of increase by 2 times to carry out proportioning, and lithium source is more expensive, causes preparation cost higher; 2. there is lithium sulfate to remain in filtrate after reaction, need to carry out to wash and the precipitation in later stage extracts lithium sulfate operation, add operation and the cost of preparation process; 3. when preparing precursor solution, ferric phosphate, manganese phosphate, the multiple insoluble molysite of sub-manganese, the lithium phosphate etc. of phosphoric acid one hydrogen, multiple insoluble manganese salt and multiple insoluble lithium salts can be produced, composition is more, be difficult to ensure that various composition evenly, unanimously disperses and reacts to each other in hydrothermal reaction process, cause end product composition may be unanimously uneven; 4. when hydro-thermal reaction, because the Ksp of LiFePO4 and lithium manganese phosphate is different, two kinds of compositions may be caused not to be synchronous homogeneous precipitation, cause end product may not be homogeneous single phase iron manganese phosphate lithium material.
Summary of the invention
The LiMn that the present invention is prepared to solve prior art xfe 1-xpO 4particle diameter is comparatively large, cryogenic property and high-multiplying power discharge efficiency low, the LiMn simultaneously prepared xfe 1-xpO 4the shortcoming of homogeneous single phase iron manganese phosphate lithium material, provide one to have particle diameter is little, cryogenic property and high-multiplying power discharge efficiency high, form single-phase LiMn xfe 1-xpO 4and preparation method thereof.
The invention provides a kind of LiMn xfe 1-xpO 4the preparation method of positive electrode active materials, the method comprises the steps:
S1, phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group substance solution is mixed to form mixed liquor, and to add pH value regulator adjust ph be 3-14, reaction generates Mn xfe 1-xpO 42H 2o presoma;
S2, under an inert atmosphere, Mn prepared by step S1 xfe 1-xpO 42H 2o presoma mixes with lithium source and water, drying, and then roasting obtains LiMn under an inert atmosphere xfe 1-xpO 4;
Wherein, 0 < X < 1.
Present invention also offers the LiMn prepared by said method xfe 1-xpO 4positive electrode active materials.
Mn prepared by the present invention xfe 1-xpO 42H 2o presoma, manganese and iron are all trivalents, and valence state is consistent, can adjust arbitrarily the ratio of manganese between 0-1; In presoma course of reaction, the salt of use is all soluble-salt, ensure that iron, mixing that manganese reaches molecular level level, avoids manganese and iron to mix uneven defect; With Mn xfe 1-xpO 42H 2o is presoma, and as reaction framework, solubility lithium source can be coated on granular precursor surface equably, and during high temperature sintering, lithium directly embeds Mn xfe 1-xpO 42H 2in O, namely generate LiMn xfe 1-xpO 4product, there is not large-scale decomposition in process, material structure is stablized and prepared LiMn xfe 1-xpO 4material is pure phase, is conducive to the deintercalation of lithium ion.
Simultaneously preparation method of the present invention consuming time short, energy consumption is low, cost is low, productive rate is high, the material granule of preparation evenly, the strong mechanical property of preparation, technological process be simply controlled, can realize large-scale industry cleanly production.
Accompanying drawing explanation
Fig. 1 is Mn prepared by embodiment 1 0.65fe 0.35pO 4scanning of materials electromicroscopic photograph;
Fig. 2 is LiMn prepared by embodiment 1 0.65fe 0.35pO 4scanning of materials electromicroscopic photograph;
Fig. 3 is Mn prepared by comparative example 1 0.65fe 0.35pO 4scanning of materials electromicroscopic photograph;
Fig. 4 is LiMn prepared by comparative example 1 0.65fe 0.35pO 4scanning of materials electromicroscopic photograph;
Fig. 5 is LiMn prepared by embodiment 1 0.65fe 0.35pO 4material XRD schemes;
Fig. 6 is the LiMn of the preparation of comparative example 1 0.65fe 0.35pO 4material XRD schemes;
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 to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of LiMn xfe 1-xpO 4the preparation method of positive electrode active materials, the method comprises the steps:
S1, phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group substance solution is mixed to form mixed liquor, and to add pH value regulator adjust ph be 3-14, reaction generates Mn xfe 1-xpO 42H 2o presoma;
S2, under an inert atmosphere, Mn prepared by step S1 xfe 1-xpO 42H 2o presoma mixes with lithium source and water, drying, and then roasting obtains LiMn under an inert atmosphere xfe 1-xpO 4;
Wherein, 0 < X < 1.
LiMn of the present invention simultaneously xfe 1-xpO 4in the preparation method of positive electrode active materials, adopt the trivalent iron salt of solubility and the manganic salt of solubility, iron is consistent with manganese valence, can adjust arbitrarily the ratio of iron and manganese, thus improves LiMn xfe 1-xpO 4energy density, improve its capacity.Secondly, the salt that the present invention uses is all soluble-salt, ensure that iron, mixing that manganese reaches molecular level level, avoids manganese and iron to mix uneven defect.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, starts while forming mixed liquor to disperse mixed liquor in described step S1.Further preferably, the method for described dispersion is circulation sand milling.Start to carry out circulation sand milling when forming mixed liquor, like this can by the Mn of the larger nucleus of generation xfe 1-xpO 42H 2o forms more less nucleus, at Mn through dispersion xfe 1-xpO 42H 2when O total amount is constant, the Mn that nucleus is formed more at most xfe 1-xpO 42H 2the particle size of O is less, the presoma Mn obtained xfe 1-xpO 42H 2o is nano level, thus ensures final products LiMn xfe 1-xpO 4particle diameter be nanoscale.LiMn xfe 1-xpO 4primary particle size only have 30 ~ 100nm, particle is superfine, is conducive to the deintercalation of lithium ion.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, at Mn in described step S2 xfe 1-xpO 42H 2o presoma adds carbon source when mixing with lithium source and water.The content of the described carbon source added is LiMn xfe 1-xpO 4the 0.1-5% of gross mass.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, in described step S1, described trivalent iron salt is with Fe 3+meter, described manganic salt is with Mn 3+meter, the phosphorous acid group material of described solubility is with PO 4 3-meter, the mol ratio of described trivalent iron salt, described manganic salt and the phosphorous acid group material of described solubility is 0-1:0-1:1-1.2; And the mole of described trivalent iron salt and described manganic salt is not 0.More preferably 0.2-0.5:0.5-0.8:1.The mol ratio of above-mentioned each material, within the scope of this, can be good at ensureing that described trivalent iron salt and described manganic salt and phosphate radical react, and reduces the generation of impurity, and the content of iron and manganese is within the scope of this simultaneously, can be good at ensureing LiMn xfe 1-xpO 4capacity, energy density and charge-discharge magnification.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, in order to ensure not produce other impurity further, preferably, the integral molar quantity of described trivalent iron salt and described manganic salt equals the mole of the phosphorous acid group material of described solubility.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, 0.5≤X≤0.8.More preferably 0.6≤X≤0.8.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, the pH of described step S1 is 6-8.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, the reaction temperature in described step S1 is 0-100 DEG C.More preferably 40-60 DEG C.The control of reaction temperature adds deionized water in glass reaction still, is incubated reactor with thermostatical circulating water.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, the temperature of described roasting is 600-800 DEG C.More preferably 650-720 DEG C.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, preferably, described solubility manganic salt is the manganese salt of water soluble or ethanol, as at least one in manganese chloride, manganous bromide, manganese nitrate, manganese sulfate and manganese acetate, more preferably manganese sulfate; Described solubility trivalent iron salt is the molysite of water soluble or ethanol, as at least one in iron chloride, ferric bromide, ferric nitrate, ferric sulfate and ferric acetate, more preferably ferric sulfate; Described lithium source is the lithium salts of water soluble or alcohol, as at least one in lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chloride, lithium fluoride, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate and lithium tartrate; Described solubility phosphorous acid group material is the phosphorous acid group material be dissolved in water or ethanol, as at least one in phosphoric acid, lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate and potassium phosphate, more preferably ammonium dihydrogen phosphate; Described carbon source is at least one in glucose sugar, sucrose, maltose, lactose, graphite, carbon nano-tube, Graphene, phenolic resins and starch; Described pH value regulator is solubility bronsted lowry acids and bases bronsted lowry, as at least one in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, ammoniacal liquor, NaOH, lithium hydroxide and potassium hydroxide.
According to LiMn provided by the present invention xfe 1-xpO 4the preparation method of positive electrode active materials, carry out more smoothly to enable reaction, preferably, molar concentration≤1 of manganic salt in 0 < solubility manganic salting liquid, molar concentration≤1 of trivalent iron salt in 0 < solubility ferric salt solution, molar concentration≤1 of phosphate radical in the phosphorous acid group substance solution of 0 < solubility.
Can for solubility manganic salting liquid and solubility ferric salt solution be first mixed by the method for phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group substance solution mixing in step S1, and then mix with the phosphorous acid group substance solution of solubility, or simultaneously by phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group substance solution mixing, preferably solubility manganic salting liquid and solubility ferric salt solution are first mixed, and then mix with the phosphorous acid group substance solution of solubility.
The feed way that the mixture of above-mentioned solubility manganic and solubility trivalent iron salt and the phosphorous acid group material of solubility are added drop-wise in reactor is not particularly limited, and Ke Yishi: A, phosphate solution is added drop-wise in ferromanganese salting liquid; B, ferromanganese salting liquid is added drop-wise in phosphate solution; C, by ferromanganese salt and phosphate solution simultaneously parallel being added drop-wise in the 3rd container react.
Phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group material is added drop-wise in reactor, the rapid stirring dispersion of dropping limit, limit, add the pH value that pH value regulator regulates reaction system, pH value controls at 3-14, between preferred 6-8 simultaneously; Adjusted to ph pH value regulator used drips mode and has no particular limits, and Ke Yishi: A, pH value regulator is added in phosphate solution; B, pH value regulator is added in ferromanganese salting liquid; C, pH value regulator pH value controller drip separately.
By the Mn obtained after step S1 sufficient reacting xfe 1-xpO 42H 2o carries out filtering, wash, dry;
In step S2, under an inert atmosphere, the Mn prepared by step S1 xfe 1-xpO 42H 2o presoma mixes with lithium source, carbon source and deionized water, then carries out dispersedly obtaining slurry; Scattered slurry is placed in sand mill and carries out circulation sand milling, is incubated in sand grinding process with cooling water, and temperature controls between 0-100 DEG C, preferred 0-30 DEG C, and the sand milling time is 0.5-4 hour; Then the slurry after sand milling is carried out drying; Dried powder is placed in high temperature process furnances, and under inert gas shielding, at 600-800 DEG C, constant temperature 0.5-72 hour at preferred 650-720 DEG C, preferred 8-12 hour sinters, and then naturally cools to room temperature, has both obtained the LiMn of bag carbon xfe 1-xpO 4material.
The present invention prepares LiMn xfe 1-xpO 4the dispersing mode that in process, each link is used can be: mechanical agitation, shearing, ball milling, sand milling, hypergravity etc.
The present invention prepares LiMn xfe 1-xpO 4the inert gas that in process, each link is used can be: one or more mixing of nitrogen, argon gas, helium.
The present invention prepares LiMn xfe 1-xpO 4the drying mode used in process can be: vacuumize, inert gas shielding heat drying, spraying dry, freeze drying, expansion drying etc.
Present invention also offers a kind of LiMn xfe 1-xpO 4positive electrode active materials, this positive electrode active materials is prepared by method of the present invention.
According to LiMn provided by the present invention xfe 1-xpO 4positive electrode active materials, preferably, described LiMn xfe 1-xpO 4average primary particle diameter be not more than 100nm.
Below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment 1
1, the preparation of positive electrode active materials:
The manganese nitrate solution of the ferric nitrate of the 0.35mol/l concentration of 1L and the 0.65mol/l concentration of 1L is added drop-wise in the sodium radio-phosphate,P-32 solution of 1mol/l concentration of 1L respectively, control the pH of reaction solution with citric acid is 6.7 simultaneously, under the circulating water heat insulation of 40 DEG C, stirring reaction 3 hours, obtains ecru Mn after filtration washing drying 0.65fe 0.35pO 42H 2o material.
Adopt Hitachi S4800 type scanning electron microscopy (SEM) to observe the pattern of the phosphate presoma of above-mentioned preparation, as shown in Figure 1, observe the grain diameter obtaining the phosphate presoma of above-mentioned preparation homogeneous, size is basically identical, soilless sticking phenomenon.
By the Mn of 0.1mol 0.65fe 0.35pO 42H 2o powder, 0.1mol lithium hydroxide, 2.355 grams of glucose and 3.14 grams of solid contents are the CNT(carbon nano-tube of 5%) join in 1L deionized water respectively, by mixed solution sand milling 4 hours in sand mill.Then adopt spray dryer to carry out spraying dry to slurry, be placed in high temperature process furnances by the powder after spraying dry, under N2 protection, Isothermal sinter 24 hours at 680 DEG C, namely obtains black bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0.65fe 0.35pO 4materials A 1.
Hitachi S4800 type scanning electron microscopy (SEM) is adopted to observe the pattern of the phosphate presoma of above-mentioned preparation, as shown in Figure 2, observe the grain diameter obtaining the iron manganese phosphate for lithium positive electrode active materials of above-mentioned preparation homogeneous, size is basically identical, soilless sticking phenomenon.
Test adopts 40KV pipe pressure, electric current 200mA, step-length 1 °, test angle 10-90 ° of test LiMn 0.65fe 0.35pO 4xRD figure, the results are shown in Figure 5.As can be seen from Figure 5, prepared iron manganese phosphate for lithium peak type is sharp-pointed, without acromion, is pure phase, similar to the XRD spectra of iron manganese phosphate for lithium.
Fig. 7 is respectively the charging and discharging curve figure of prepared iron manganese phosphate for lithium.As can be seen from Figure 7, the discharge capacity of the iron manganese phosphate for lithium adopting the method to prepare is high.
2, simulated battery is prepared
The ratio mixing of iron manganese phosphate for lithium A1 in mass ratio: acetylene black: PVDF=80:10:10, after being uniformly dispersed with NMP, smear is made, and pole piece is in 120 DEG C of more than vacuumize 24h.Simulated battery S1 take metal lithium sheet as negative pole, with celgard2400 polypropylene porous film for barrier film, with 1mol/L LiPF 6ethylene carbonate (EC) and the mixed solution (volume ratio is=1: 1) of dimethyl carbonate (DMC) be electrolyte, the assembling process of all batteries is all carried out in the glove box being full of argon gas.
embodiment 2
1, positive electrode active materials is prepared
The ferric chloride solution of the manganese chloride of the 0.4mol/l concentration of 1L and the 0.4mol/l concentration of 1L is added in the ammonium dihydrogen phosphate of 0.8mol/l concentration of 1L simultaneously, control the PH of reaction solution with ammoniacal liquor is 7 simultaneously, stirring reaction 4 hours under the circulating water heat insulation of 20 DEG C, when starting to occur precipitation, namely start stirring reaction limit, limit and carry out circulation sand milling, after reacting, solution left standstill is after aging 48 hours, obtains nanoscale Mn after filtration washing drying 0. 5fe 0. 5pO 42H 2o material.
By the Mn of 0.5mol 0. 5fe 0. 5pO 42H 2o powder, 0.5mol lithium acetate, 7.85 grams of glucose and 15.7 grams of solid contents are the Graphene of 5%, join in 1.6L deionized water respectively, by mixed solution sand milling 4 hours in sand mill, then carry out freeze drying with freeze drier.Be placed in high temperature oven by the powder after freeze drying, under Ar gas shielded, Isothermal sinter 12 hours at 700 DEG C, namely obtains black bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0. 5fe 0. 5pO 4materials A 2.
2, battery S2 is prepared according to the method for embodiment 1.
embodiment 3
1, positive electrode active materials is prepared
The potassium phosphate solution of the manganese sulfate of the 0.8mol/l concentration of 1L, the ferrum sulfuricum oxydatum solutum of the 0.2mol/l concentration of 1L and the 1mol/l concentration of 1L is added drop-wise in the reactor of 25 DEG C of circulating water heat insulations respectively simultaneously, control the PH of reaction solution with ascorbic acid is 6.5 simultaneously, dropping limit, limit is stirred, the sand milling that circulates is started when starting to occur precipitated product, within 2 hours, complete dropwise reaction, after filtration washing drying, obtain Mn 0.8fe 0.2pO 42H 2o precursor powder.
By the Mn of 0.6mol 0.8fe 0.2pO 42H 2o powder, 0.6mol lithium hydroxide, 14.13 grams of sucrose join in 1.2L deionized water respectively, by mixed solution sand milling 6 hours in sand mill, then solution after sand milling are carried out spraying dry.
Be placed in tube furnace by dried powder, under N2 protection, Isothermal sinter 10 hours at 720 DEG C, namely obtains bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0.8fe 0.2pO 4materials A 3.
2, battery S3 is prepared according to the method for embodiment 1.
embodiment 4
1, positive electrode active materials is prepared
The ammonium hydrogen phosphate solution of the manganese nitrate of the 0.1mol/l concentration of 1L, the iron nitrate solution of the 0.9mol/l concentration of 1L and the 1mol/l concentration of 1L is added drop-wise in the reactor of 60 DEG C of circulating water heat insulations respectively simultaneously, control the PH of reaction solution with ammoniacal liquor is 8 simultaneously, dropping limit, limit is stirred, the sand milling that circulates is started when starting to occur precipitated product, within 2 hours, complete dropwise reaction, after filtration washing drying, obtain Mn 0.1fe 0.9pO 42H 2o precursor powder.
By the Mn of 0.6mol 0.1fe 0.9pO 42H 2o powder, 0.6mol lithium hydroxide, 4.52 grams of phenolic resins join in 1.2L deionized water respectively, by mixed solution sand milling 6 hours in sand mill, then solution after sand milling are carried out spraying dry.
Be placed in tube furnace by dried powder, under N2 protection, Isothermal sinter 12 hours at 650 DEG C, namely obtains bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0.1fe 0.9pO 4materials A 4.
2, battery S4 is prepared according to the method for embodiment 1.
embodiment 5
1, positive electrode active materials is prepared
The phosphoric acid solution of the manganous bromide of the 0.9mol/l concentration of 1L, the ferric bromide solution of the 0.1mol/l concentration of 1L and the 1mol/l concentration of 1L is added drop-wise in the reactor of 50 DEG C of circulating water heat insulations respectively simultaneously, control the PH of reaction solution with ascorbic acid is 3 simultaneously, dropping limit, limit is stirred, the sand milling that circulates is started when starting to occur precipitated product, within 2 hours, complete dropwise reaction, after filtration washing drying, obtain Mn 0.9fe 0.1pO 42H 2o precursor powder.
By the Mn of 0.6mol 0.9fe 0.1pO 42H 2o powder, 0.6mol lithium hydroxide, 6.83 grams of starch join in 1.2L deionized water respectively, by mixed solution sand milling 6 hours in sand mill, then solution after sand milling are carried out spraying dry.
Be placed in tube furnace by dried powder, under N2 protection, Isothermal sinter 10 hours at 800 DEG C, namely obtains bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0.9fe 0.1pO 4materials A 5.
2, battery S5 is prepared according to the method for embodiment 1.
embodiment 6
1, positive electrode active materials is prepared
The phosphoric acid solution of the manganese chloride of the 0.6mol/l concentration of 1L, the ferric chloride solution of the 0.4mol/l concentration of 1L and the 1mol/l concentration of 1L is added drop-wise in the reactor of 100 DEG C of circulating water heat insulations respectively simultaneously, control the PH of reaction solution with ascorbic acid is 5.4 simultaneously, dropping limit, limit is stirred, within 2 hours, complete dropwise reaction, after filtration washing drying, obtain Mn 0.6fe 0.4pO 42H 2o precursor powder.
By the Mn of 0.6mol 0.6fe 0.4pO 42H 2o powder, 0.6mol lithium hydroxide, 10.25 grams of lactose join in 1.2L deionized water respectively, by mixed solution sand milling 6 hours in sand mill, then solution after sand milling are carried out spraying dry.
Be placed in tube furnace by dried powder, under N2 protection, Isothermal sinter 15 hours at 600 DEG C, namely obtains bag carbon homogeneous phase LiMn after naturally cooling to room temperature 0.6fe 0.4pO 4materials A 6.
2, battery S6 is prepared according to the method for embodiment 1.
comparative example 1
1, positive electrode active materials is prepared
Under N2 protection; the glucose of 0.5mol lithium carbonate, 1mol ammonium dihydrogen phosphate, the sub-manganese of 0.65mol oxalic acid, 0.35mol ferrous oxalate and 23.55 grams is dispersed in 1L deionized water respectively; first with ball mill, ball milling is carried out 24 hours to mixed solution; mixed solution after ball milling is carried out spraying dry; dried powder is placed in tube furnace; under N2 protection, at 680 DEG C, sinter 24 hours, namely obtain the black LiMn having wrapped carbon 0.65fe 0.35pO 4material C A1.
Hitachi S4800 type scanning electron microscopy (SEM) is adopted to observe pattern and the LiMn of the phosphate presoma of above-mentioned preparation 0.65fe 0.35pO 4pattern, respectively as shown in Figure 3 and Figure 4.As shown in Figure 3, observe the presoma primary particle obtaining above-mentioned preparation comparatively large, and not of uniform size, there is obvious agglomeration.As shown in Figure 4, observe the iron manganese phosphate for lithium positive electrode active materials primary particle size obtaining above-mentioned preparation comparatively large, and between particle, size distribution scope is very wide.
Test adopts 40KV pipe pressure, electric current 200mA, step-length 1 °, test angle 10-90 ° of test LiMn 0.65fe 0.35pO 4xRD figure, the results are shown in Figure 6.As can be seen from Figure 6, prepared iron manganese phosphate for lithium has a small amount of without acromion, illustrates and has impurity to exist in iron manganese phosphate for lithium.
Fig. 8 is respectively the charging and discharging curve figure of prepared iron manganese phosphate for lithium.As can be seen from Figure 8, the discharge capacity that the discharge capacity of the iron manganese phosphate for lithium adopting the method to prepare than embodiment 1 is is low.
2, battery CS1 is prepared according to the method for embodiment 1.
comparative example 2
1, positive electrode active materials is prepared
Prepare lithium ferric manganese phosphate positive electrode active materials according to the method in CN101764203A embodiment 3, be designated as CA2.
2, battery CS2 is prepared according to the method for embodiment 1.
comparative example 3
1, positive electrode active materials is prepared
Prepare iron manganese phosphate for lithium active material according to the method in CN102249208A embodiment 4, be designated as CA3.
2, battery CS3 is prepared according to the method for embodiment 1.
performance test
1, average primary particle diameter test, the average primary particle diameter of positive electrode active materials A1-A6 and CA1-CA3 prepared by testing example 1-6 and comparative example 1-3, the results are shown in Table 1;
2, energy density test: carry out discharge and recharge under 0.1C multiplying power, carry out integration to electric discharge C-V curve, the area that discharge curve surrounds is the mass energy density of this material; The results are shown in Table 1;
3, charge/discharge capacity test: battery S1-S6 and CS1-CS3 prepared by embodiment 1-6 and comparative example 1-3 is placed on charge-discharge test instrument and carries out charge/discharge capacity test: at room temperature, 4.3V is charged under 0.1C multiplying power, cut-off current is 0.01C, then discharge into 2.5V under 0.1C multiplying power, the results are shown in Table 2;
4, high rate performance test: battery prepared by battery S1-S6 and CS1-CS3 prepared by embodiment 1-6 and comparative example 1-3 is placed on charge-discharge test instrument and carries out charge-discharge performance test, 4.3V is charged under 0.1C multiplying power, cut-off current is 0.01C, then under 1C, 2C, 5C and 10C multiplying power, 2.5V is discharged into respectively, the ratio of the discharge capacity of the discharge capacity under each multiplying power and 0.1C multiplying power, as the multiplying power efficiency under this multiplying power, the results are shown in Table 2;
Battery prepared by battery S1-S6 and CS1-CS3 prepared by 5, low-temperature test: embodiment 1-6 and comparative example 1-3 is under 0.2C after cycle charge-discharge twice, 4.3V is charged to 0.5C, battery is placed in-10 DEG C of environment 0.5C multiplying power dischargings to 2.5V, under the discharge capacity of-10 DEG C and room temperature, the ratio of the discharge capacity of 0.5C is the Efficiency at Low Temperature of this material-10 DEG C, the results are shown in Table 2.
Table 1
。
Table 2
。
The positive electrode active materials domain size distribution prepared of the present invention is homogeneous as can be seen from Table 1 and Table 2, and pattern is perfect, soilless sticking, and grain diameter is little, be conducive to the electric conductivity improving 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 stablized, and good cycle, for the development of excellent positive electrode active materials provides the foundation, is conducive to the application of this kind of material and the development of battery.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (14)

1. a LiMn xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the method comprises the steps:
S1, phosphorous to solubility manganic salting liquid, solubility ferric salt solution and solubility acid group substance solution is mixed to form mixed liquor, and to add pH value regulator adjust ph be 3-14, reaction generates Mn xfe 1-xpO 42H 2o presoma;
S2, under an inert atmosphere, Mn prepared by step S1 xfe 1-xpO 42H 2o presoma mixes with lithium source and water, drying, and then roasting obtains LiMn under an inert atmosphere xfe 1-xpO 4;
Wherein, 0 < X < 1.
2. LiMn according to claim 1 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, starts to disperse mixed liquor in described step S1 while forming mixed liquor.
3. LiMn according to claim 1 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the method for described dispersion is circulation sand milling.
4. LiMn according to claim 1 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, at Mn in described step S2 xfe 1-xpO 42H 2o presoma adds carbon source when mixing with lithium source and water.
5. the LiMn according to claim 1-4 any one xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, in described step S1, described trivalent iron salt is with Fe 3+meter, described manganic salt is with Mn 3+meter, the phosphorous acid group material of described solubility is with PO 4 3-meter, the mol ratio of described trivalent iron salt, described manganic salt and the phosphorous acid group material of described solubility is 0-1:0-1:1-1.2; And the mole of described trivalent iron salt and described manganic salt is not 0.
6. LiMn according to claim 5 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the mol ratio of described trivalent iron salt, described manganic salt and the phosphorous acid group material of described solubility is 0.2-0.5:0.5-0.8:1.
7. LiMn according to claim 6 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the integral molar quantity of described trivalent iron salt and described manganic salt equals the mole of the phosphorous acid group material of described solubility.
8. LiMn according to claim 7 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, 0.5≤X≤0.8.
9. the LiMn stated according to Claim 8 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the pH of described step S1 is 6-8.
10. according to the LiMn that claim 9 is stated xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the reaction temperature in described step S1 is 0-100 DEG C.
11. LiMn according to claim 1 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, the temperature of described roasting is 600-800 DEG C.
12. LiMn according to claim 4 xfe 1-xpO 4the preparation method of positive electrode active materials, is characterized in that, described solubility manganic salt is at least one in manganese chloride, manganous bromide, manganese nitrate, manganese sulfate and manganese acetate; Described solubility trivalent iron salt is at least one in iron chloride, ferric bromide, ferric nitrate, ferric sulfate and ferric acetate; Described lithium source is at least one in lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chloride, lithium fluoride, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate and lithium tartrate; The phosphorous acid group material of described solubility is at least one in phosphoric acid, lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate and potassium phosphate; Described carbon source is at least one in glucose sugar, sucrose, maltose, lactose, graphite, carbon nano-tube, Graphene, phenolic resins and starch; Described pH value regulator is at least one in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, ammoniacal liquor, NaOH, lithium hydroxide and potassium hydroxide.
13. 1 kinds of LiMn xfe 1-xpO 4positive electrode active materials, is characterized in that, this positive electrode active materials is prepared by the method described in claim 1-12 any one.
14. LiMn according to claim 13 xfe 1-xpO 4positive electrode active materials, is characterized in that, described LiMn xfe 1-xpO 4average 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
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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
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