CN106816582B - A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and anode and lithium battery - Google Patents

A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and anode and lithium battery Download PDF

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CN106816582B
CN106816582B CN201510860701.7A CN201510860701A CN106816582B CN 106816582 B CN106816582 B CN 106816582B CN 201510860701 A CN201510860701 A CN 201510860701A CN 106816582 B CN106816582 B CN 106816582B
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manganese phosphate
iron manganese
lithium
iron
lithium material
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CN106816582A (en
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/36—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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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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Abstract

The invention discloses a kind of iron manganese phosphate for lithium class materials and preparation method thereof and anode and lithium battery.Wherein, which has LiMnxFe1‑x‑yMyPO4/ C-structure, wherein 0≤x≤1,0≤y≤1, M is the transition metal element in addition to Mn and Fe, the partial size D of the iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm, and cohesive force Cohesive≤1.5kPa of the iron manganese phosphate for lithium class material.Smaller (the partial size D of the partial size of this iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm), cohesive force is also smaller (Cohesive≤1.5kPa).Be conducive to improve the volume and capacity ratio of lithium battery by this iron manganese phosphate for lithium class material using the positive electrode prepared, and then improve the cruise duration of battery.

Description

A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and anode with Lithium battery
Technical field
The present invention relates to the preparation fields of positive electrode, in particular it relates to a kind of iron manganese phosphate for lithium class material, sheet Invention further relates to a kind of preparation method of iron manganese phosphate for lithium class material, and the present invention is further directed to a kind of include aforementioned phosphate manganese The cell size of iron lithium class material, the present invention are still further related to a kind of anode including aforementioned phosphate manganese iron lithium class material, And the lithium battery including the anode.
Background technique
Lithium ion secondary battery is novel green high-power rechargeable battery, high with voltage, energy density is big, cyclicity Can the good, many merits such as self discharge is small, memory-less effect, working range are wide, be widely used in mobile phone, laptop, Portable power tool, electronic instrument, weaponry etc., also have a good application prospect in electric car, have become at present The emphasis that countries in the world competitively research and develop.Positive electrode is a critically important component part of lithium ion battery, in lithium ion In battery charge and discharge process, reciprocal embedding/de- required lithium in positive and negative lithium intercalation compound is not only provided, but also also provide Negative electrode material surface forms lithium required for SEI film, and therefore, researching and developing high performance positive electrode is lithium ion battery hair The key point of exhibition.
In anode material for lithium-ion batteries, iron manganese phosphate for lithium class material shows optimal in comprehensive performance, it is considered to be Ideal lithium ion secondary power battery positive electrode.Currently, this phosphate material mainly uses high temperature solid-state method It is prepared, this high temperature solid-state method generally includes first to grind to form the slurry containing primary particle, then again to containing once The step of slurry of particle is dried, is sintered to form iron manganese phosphate for lithium class material.
In order to advanced optimize the quality of prepared phosphate material, research staff is also constantly to phosphate material Preparation method improve.For example, disclosing a kind of high-density spherical phosphoric acid in Chinese patent CN201210087676.X The preparation method of iron lithium, the specific steps are as follows: using lithium compound, iron compound, phosphate, doping metallic compound and carbon Black is raw material, and wet mixing in ball mill is added；Spray drying is placed on N2As carrying out pre-burning in the roaster of protective gas；So Binder polyvinyl alcohol is added afterwards and carries out wet mixing again, spray drying is placed on N2Roaster as protective gas carries out two Secondary roasting forms LiFePO4 class material with preparation.
Although providing the preparation method of a variety of this iron manganese phosphate for lithium class materials in the prior art, also gives and be based on Different preparation method a variety of iron manganese phosphate for lithium class materials obtained.However, in order to be adapted to social development for battery material Cruise duration or high temperature capacity retention ratio requirement, it is also necessary to further to this iron manganese phosphate for lithium class material and its system Preparation Method conducts further research.
Summary of the invention
The object of the present invention is to provide a kind of iron manganese phosphate for lithium class material and preparation method thereof and cell sizes and anode Material and lithium battery, it is smaller to provide a kind of partial size, and the lesser iron manganese phosphate for lithium class material of cohesive force, and then improve include by The volume and capacity ratio of the lithium battery of the positive electrode of this iron manganese phosphate lithium material production, and then improve the stand-by time of battery.
To achieve the goals above, according to the first aspect of the invention, a kind of iron manganese phosphate for lithium class material is provided, it should Iron manganese phosphate for lithium class material has LiMnxFe1-x-yMyPO4/ C-structure, wherein 0≤x≤1,0≤y≤1, M is in addition to Mn and Fe Transition metal element, the partial size D of the iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm, and the phosphorus Cohesive force Cohesive≤1.5kPa of sour manganese iron lithium class material.
According to the second aspect of the invention, a kind of preparation method of iron manganese phosphate for lithium class material, the preparation side are provided Method the following steps are included: by lithium source, optional manganese source, optional source of iron, and the optional source M, phosphorus source and carbon source in proportion into Row ground and mixed obtains the slurry containing primary particle；It is P1's that the slurry containing primary particle, which is passed sequentially through pressure, The second chamber that first chamber and pressure are P2, obtains refined pulp, wherein P1 >=4000Psi, and P1 is 3 times of P2 or more； The refined pulp is passed sequentially through into dry and sintering processes, obtains second particle, i.e., the described iron manganese phosphate for lithium class material.
According to the third aspect of the present invention, a kind of iron manganese phosphate for lithium class material is provided, the iron manganese phosphate for lithium class material It is to be prepared by above-mentioned preparation method.
According to the fourth aspect of the present invention, a kind of cell size is provided, which includes iron manganese phosphate for lithium class Material and solvent, the iron manganese phosphate for lithium class material are the above-mentioned iron manganese phosphate for lithium class material of the present invention.
According to the fifth aspect of the present invention, a kind of anode is provided, which includes collector and be arranged in the collection Anode active material layer on fluid, the anode active material layer include iron manganese phosphate for lithium class material of the present invention.
According to the sixth aspect of the invention, a kind of lithium battery is provided, the lithium battery interior is equipped with anode, the anode For the above-mentioned anode of the present invention.
Iron manganese phosphate for lithium class material provided by the present invention and preparation method thereof and cell size and positive electrode and lithium Battery, wherein smaller (the partial size D of the partial size of iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm), cohesive force Also smaller (Cohesive≤1.5kPa).Be conducive to improve lithium using the positive electrode prepared by this iron manganese phosphate for lithium class material The volume and capacity ratio of battery, and then improve the cruise duration of battery.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 show according to embodiments of the present invention 1 prepared by iron manganese phosphate for lithium class material 2.00 μm of scanning electron microscope (SEM) map；
Fig. 2 shows 2.00 μm of scanning electron microscope (SEM) figures of the iron manganese phosphate for lithium class material according to prepared by comparative example 1 Spectrum.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As pointed by background technology part, in order to be adapted to social demand, the volume for further increasing battery is also needed Specific capacity, and then extend battery standby time.For this purpose, the present inventor provides a kind of novel iron manganese phosphate for lithium class material Material, the iron manganese phosphate for lithium class material have LiMnxFe1-x-yMyPO4/ C-structure, wherein 0≤x≤1 (preferably 0.5≤x≤1), 0≤y ≤ 1 (preferably 0≤y≤0.5), for the transition metal element in addition to Mn and Fe, (preferably M is one in Co, Ni, Mg, Zn, V and Ti to M Kind is a variety of), the partial size D of the iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm, and the manganese phosphate Cohesive force Cohesive≤1.5kPa of iron lithium class material.
Above-mentioned iron manganese phosphate for lithium class material has LiMnxFe1-x-yMyPO4/ C-structure refers to carbon coating LiMnxFe1-x- yMyPO4The structure of particle.Smaller (the partial size D of partial size of the above-mentioned iron manganese phosphate for lithium class material of the present invention50It is 0.5-1.0 μm, D90For 1.0-5.0 μm), cohesive force is also smaller (Cohesive≤1.5kPa).Anode is prepared using by this iron manganese phosphate for lithium class material, Be conducive to improve the volume and capacity ratio of the lithium battery including the anode, and then improve the cruise duration of battery.
Wherein partial size D in the present invention50And D90For volume average particle size, be by the way that powder to be measured is dispersed in water, Then after ultrasonic vibration, testing graininess acquisition is carried out with laser particle analyzer.
In iron manganese phosphate for lithium class material of the present invention, for the specific surface area of iron manganese phosphate for lithium class material, compacted density with And there is no particular/special requirements for magnetic induction intensity, as long as the partial size D of iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90For 1.0- 5.0 μm, and cohesive force Cohesive≤1.5kPa of the iron manganese phosphate for lithium class material can correspondingly increase the body of lithium battery Product specific capacity.However, in order to advanced optimize the volume and capacity ratio or high temperature capacity retention ratio that improve lithium battery, the preferably described phosphorus Sour manganese iron lithium class material meets following require:
Preferably, the partial size D of the iron manganese phosphate for lithium class material50It is 0.5-0.8 μm, D90It is 1.0-3.0 μm, and described Cohesive force Cohesive≤1.2kPa of iron manganese phosphate for lithium class material.By the partial size and cohesive force of the iron manganese phosphate for lithium class material Optimization is conducive to improve in the range the compacted density of material.
Preferably, the specific surface area S of the iron manganese phosphate for lithium class material is 12m2/g≤S≤28m2/ g, preferably 15m2/g ≤S≤25m2/g.Be conducive to the specific surface area optimization of the iron manganese phosphate for lithium class material not influencing material within the above range In the case where expecting compaction capacity, material surface activity is promoted.
Preferably, the compacted density of the iron manganese phosphate for lithium class material is 2.0g/cm3-2.68g/cm3, preferably 2.2g/ cm3-2.55g/cm3.Be conducive to the compacted density optimization of the iron manganese phosphate for lithium class material to improve lithium battery in the range Volume energy density, it is ensured that the void density of application of electrode and lithium ion diffusion admittance it is smooth.
Preferably, the magnetic induction intensity of the iron manganese phosphate for lithium class material is 800-1100ppm, preferably 950- 1050ppm.Be conducive to the magnetic induction intensity optimization of the iron manganese phosphate for lithium class material to improve filling for lithium battery in the range Discharge capacity.Wherein the magnetic induction intensity of iron manganese phosphate for lithium class material is surveyed using Mike's instrument magnetic analytical meter MA1040 Examination.Test method is to be filled to iron manganese phosphate for lithium class material powder in specimen cup (height of specimen 12cm), surveys 5 not Tongfangs To magnetic intensity be averaged.
It is not special for the content of carbon in iron manganese phosphate for lithium class material in iron manganese phosphate for lithium class material of the present invention It is different to require, it is referred to the conventional amount used of carbon in this field.Such as the content of carbon is phosphoric acid in iron manganese phosphate for lithium class material The 0.1-5wt%, the preferably 0.5-3.5wt% of iron manganese phosphate for lithium class total amount of material of manganese iron lithium class total amount of material.By the phosphorus Carbon content optimization is conducive to that material is promoted to have relatively good electric conductivity within the above range in sour manganese iron lithium class material.
In the prior art there is no about prepare above-mentioned iron manganese phosphate for lithium class material provided by the present invention enlightenment and It is expected that directlying adopt conventional method in the prior art may also be difficult to prepare above-mentioned iron manganese phosphate for lithium provided by the present invention Class MATERIALS METHODS.This may be because are as follows:
Existing this high temperature solid-state method is during forming the slurry containing primary particle by grinding, due to grinding Mill mixes ineffective, and often the material granule of ball milling is larger, it is difficult to reach the present invention for material particle size requirement, it is more difficult to Reach requirement of the present invention for material cohesion
Although using wet mixing in Chinese patent CN201210087676.X, the step that centre is pre-sintered, rewetting is mixed, Hybrid mode used by this method cannot achieve raw material nano grade mixing, this just through first time wet mixing the successively grain arrived Being crushed for diameter is random, be easy to cause water chestnut more, and material surface is coarse and defect is more, and the cohesive force between particle is big, Jin Erzao At the relatively low problem of respective material bulk property difference and battery volume capacity.
For this purpose, being referred in the prior art for above-mentioned iron manganese phosphate for lithium class material provided by the present invention Conventional method prepared, but need to be formed by particle in strict control iron manganese phosphate for lithium class material preparation process Degree, and iron manganese phosphate for lithium class material prepared by rigorous screening, to obtain the above-mentioned iron manganese phosphate for lithium class material of the present invention.
However, also providing a kind of iron manganese phosphate in the present invention to simplify the preparation method of iron manganese phosphate for lithium class material The preparation method of lithium class material.The preparation method is the following steps are included: by lithium source, optional manganese source, optional source of iron, Yi Jiren The source M, phosphorus source and the carbon source of choosing carry out ground and mixed in proportion, obtain the slurry containing primary particle；It will be described containing once The slurry of grain passes sequentially through the first chamber that pressure is P1 and the second chamber that pressure is P2, obtains refined pulp, wherein and P1 >= 4000Psi, and P1 is 3 times of P2 or more, preferably P1 is 5 times of P2 or more, and preferably P1 is 5-10 times of P2；The refinement is starched Material passes sequentially through dry and sintering processes, obtains second particle, i.e., the described iron manganese phosphate for lithium class material.
The preparation method of the above-mentioned iron manganese phosphate for lithium class material of the present invention, by the way that ground and mixed is obtained containing once The slurry of grain passes sequentially through the biggish first chamber of differing pressure and second chamber, so that environmental pressure is from P1 bust to P2, with The unexpected release of this pressure energy, primary particle in second chamber narrow regions simultaneously by high speed shear, high frequency oscillation, sky The mechanical forces such as cave phenomenon and convection current shock, generate the strong cavitation of similar explosion effect.In such strong ground heddle Cooperation is used, and slides the water chestnut on primary particle surface by rounding, primary particle is also made to have obtained micronization processing.This When refined pulp obtained after high temperature sintering, the pattern of original particle can be kept substantially, only part material fusing is burnt Knot, so that surface is rounder and more smooth, this just greatly reduced the co-acting force between second particle, reduce prepared manganese phosphate The cohesive force of iron lithium class material.In addition, the partial size for significantly reducing primary particle is handled by micronization, so that particle is not It is easy to produce spot segregation again and generates impurity, and then is conducive to trace impurity contained in relative reduction finished-product material, improves The high temperature capacity storage rate of corresponding lithium battery.
In the preparation method of above-mentioned iron manganese phosphate for lithium class material provided by the present invention, as long as making containing primary particle Slurry pass sequentially through the first chamber (pressure P1) and second chamber (pressure P2) of pressure drop, and P1 >=4000Psi, P1 is 3 times of P2 or more.Pressure for first chamber and second chamber, the slurry containing primary particle are in first chamber With second chamber residence time (time difference until flowing out chamber since entering chamber in material), contain primary particle Slurry flow into the speed of second chamber without particular/special requirement from first chamber, can according to the actual conditions of selected device into Row adjustment appropriate.However, in order to advanced optimize the physical property of prepared iron manganese phosphate for lithium class material, preferably above-mentioned preparation side Each parameter further satisfaction requires as follows in method:
Preferably, P1 is 4000-28000Psi in above-mentioned preparation method；It is preferred that P1 is 10000-25000Psi；By P1, with And the difference DELTA P of P1 and P2 is set in above range, particularly preferably in range, advantageously forms strong cavitation.? In practical application, for the ease of choosing workable equipment, preferably P2 is 800-4000Psi, preferably 1000-4000Psi.
It is preferred that the above-mentioned slurry containing primary particle flows into second chamber from first chamber with 2-20m/s speed.It will contain The slurry of primary particle limits advantage within the above range with efficient process from the speed that first chamber flows into second chamber. The above-mentioned slurry containing primary particle from first chamber flow into second chamber speed can by adjusting be located at first chamber and The cross-sectional area (perpendicular to the cross-sectional area in the section of channel extending direction) in the channel between second chamber.
In the preferred embodiment of the present invention, the first chamber is high pressure homogenizer in the above preparation method Homogeneous chamber, the second chamber be the high pressure homogenizer emulsification chamber.The present invention can use existing in the prior art High pressure homogenizer containing homogeneous chamber and emulsification chamber simultaneously, can save equipment cost in this way.
It has been put forward for the first time in the preparation process of iron manganese phosphate for lithium class material in the present invention, using there is homogeneous chamber simultaneously With the homogenizer of emulsification chamber two chambers.And this homogenizer is selected in the present invention, it is that using it while there is homogeneous chamber With emulsification chamber two chambers, can be realized the present invention makes the slurry containing primary particle pass sequentially through differing pressure biggish first Chamber and second chamber can only achieve the purpose that refine primary particle partial size at normal temperature without carrying out at high temperature.
In the present invention by using this while there is homogeneous chamber and emulsify the homogenizer of chamber two chambers, containing once The slurry of particle is after being entered emulsification chamber by homogeneous chamber, this three of spool, valve seat and impact ring composition is narrow in emulsification chamber The strong cavitation of similar explosion effect is generated in region, simultaneous material is produced by the slit of spool and valve base chamber Raw shear action and the high-speed impact for hitting generation with impact ring act on, this allows for particle in refined pulp obtained Partial size is smaller, and the surface water chestnut of particle is ground rounder and more smooth, and then is more advantageous to and is reduced prepared iron manganese phosphate for lithium class material Impurity contained in material, and reduce the cohesive force of iron manganese phosphate for lithium class material.
In the preparation method of above-mentioned iron manganese phosphate for lithium class material provided by the present invention, for primary particle partial size simultaneously There is no particular/special requirement, is referred to the Particle size requirements of primary particle in conventional method in that art.One kind in the present invention is preferably In embodiment, the partial size D of primary particle50For 50-200nm, the D of the partial size of second particle50It is 0.5-1.0 μm, D90For 1.0- 5.0μm.The partial size of primary particle is limited within the above range, is conducive to promote the more uniform of particle mixing, and be conducive to Promote particle to react more abundant in subsequent high temperature, the partial size of second particle is limited within the above range, is conducive to improvement Intergranular agglomeration, and increase the compacted density of material.
In the preparation method of above-mentioned iron manganese phosphate for lithium class material provided by the present invention, for selected raw material and original For the proportion of material there is no particular/special requirement, being referred to be formed in conventional method in that art has LiMnxFe1-x-yMyPO4/ C-structure Raw material used by iron manganese phosphate lithium material and raw material proportioning, wherein 0≤x≤1 (preferably 0.5≤x≤1), 0≤y≤1 (preferably 0 ≤y≤0.5).In the preferred embodiment of the present invention, above-mentioned carbon source is according to final in the iron manganese phosphate for lithium class material Can remnants 0.5-3.5wt% amount addition.Identical as conventional method in that art, added carbon source, is being sintered in the present invention It can be enriched to the surface of iron manganese phosphate for lithium class material during processing, therefore formed with LiMnxFe1-x-yMyPO4/ C-structure, That is the iron manganese phosphate for lithium class material of carbon coating structure.Within the above range by the dosage control of carbon source, advantageously ensure that material is led Amount that is electrical and reducing non-active material.
In the preparation method of above-mentioned iron manganese phosphate for lithium class material provided by the present invention, by lithium source, transition metal source, phosphorus During source and carbon source carry out ground and mixed in proportion, lithium source in terms of lithium, manganese source and source of iron and the source M in terms of Mn+Fe+M total amount, The ratio that molar ratio of the phosphorus source in terms of phosphorus is (0.95-1.05): 1:1 mixes.
For the selection of each raw material, there is no particular/special requirements in the present invention, are referred to this field and are preparing iron manganese phosphate Conventional material employed in lithium class material.Wherein:
The lithium source that can be used includes but is not limited to lithium hydroxide, lithium peroxide, lithia, lithium formate, lithium nitrate, carbonic acid One of lithium and iron manganese phosphate for lithium are a variety of.
The phosphorus source that can be used includes but is not limited to phosphoric acid, iron manganese phosphate for lithium, one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, corresponding One or more of transition metal phosphate.
The source of iron that can be used include but is not limited to one of ferrous oxide, iron oxide, ferric oxalate and ferrous acetate or It is a variety of.
The manganese source that can be used includes but is not limited to one of manganese carbonate, manganese phosphate, manganese nitrate and manganese oxide or a variety of.
Contain one of Co, Ni, Mg, Zn, V and Ti or a variety of compounds in the above-mentioned source M.Wherein it is possible to which what is used contains Co compound includes but is not limited to one of cobaltosic oxide, cobalt nitrate, cobalt protoxide, cobalt acetate and cobalt phosphate or a variety of； The compound containing Ni that can be used includes but is not limited to one of nickel protoxide, nickel oxide, nickel nitrate, nickel acetate and nickel phosphate Or it is a variety of；The compound containing Mg that can be used includes but is not limited to one of magnesia, magnesium nitrate and magnesium acetate or a variety of；It can It with the compound containing Zn used include but is not limited to one of zinc oxide, zinc nitrate and zinc acetate or a variety of；It can be used Compound containing V include but is not limited to one of vanadous oxide, vanadic anhydride, vanadium trioxide, nitric acid vanadium and acetic acid vanadium or It is a variety of；The compound containing Ti that can be used includes but is not limited to one of four fourth rouge of titanium dioxide, acetic acid titanium and metatitanic acid or more Kind.
The carbon source that can be used includes but is not limited to that benzene naphthalene phenanthrene terpolymer, benzene phenanthrene bipolymer, benzene anthracene binary are total Polymers gathers to benzene, soluble starch, polyvinyl alcohol, sucrose, glucose, phenolic resin, furfural resin, artificial graphite, natural stone One or more of ink, superconduction acetylene black, acetylene black, carbon black and mesocarbon bead, or inert atmosphere heat can be passed through Handle only one of organic matter of residual carbon or a variety of.
The process employed in the preparation method of above-mentioned iron manganese phosphate for lithium class material provided by the present invention is not There is particular/special requirement, as long as can be realized corresponding technique purpose.Wherein,
The mode that the step of ground and mixed can be used includes but is not limited to ball milling, sand milling or Ball-stirring mill etc., is preferably ground Time consuming is 1-6h.It further include that lapping liquid is added in order to obtain the slurry containing primary particle in the ground and mixed the step of Step, the lapping liquid include but is not limited to one of deionized water, ethyl alcohol or formaldehyde or a variety of.
The mode that the withering step of refined pulp can be used includes but is not limited to vacuum drying, indifferent gas Body protects heat drying, spray drying, freeze-drying or expansion drying etc., wherein being preferably spray-dried, the item of spray drying Part is 200-300 DEG C of inlet temperature, 95-120 DEG C of discharge port temperature.
To in the step of being sintered through the dry precursor powder generated, the condition of sintering is referred in existing method Common process condition, the condition of preferred sintering processes is included in Isothermal sinter 2-20h at 650-780 DEG C in the present invention.It will The term restriction of sintering processes help to obtain the more complete crystal form of development within the above range.
Preferably, the present invention also provides a kind of iron manganese phosphate for lithium class materials being prepared by above-mentioned preparation method.It should Iron manganese phosphate for lithium class material has LiMnxFe1-x-yMyPO4/ C-structure, wherein 0≤x≤1,0≤y≤1, M is in addition to Mn and Fe Transition metal element, the partial size D of the iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm, and the phosphorus Cohesive force Cohesive≤1.5kPa of sour manganese iron lithium class material.
Preferably, the partial size D of above-mentioned iron manganese phosphate for lithium class material50It is 0.5-0.8 μm, D90It is 1.0-3.0 μm, and described Cohesive force Cohesive≤1.2kPa of iron manganese phosphate for lithium class material.
Preferably, the specific surface area S of above-mentioned iron manganese phosphate for lithium class iron manganese phosphate lithium material is 12m2/g≤S≤28m2/ g, it is excellent It is selected as 15m2/g≤S≤25m2/g。
Preferably, the compacted density of above-mentioned iron manganese phosphate for lithium class material is 2.0g/cm3-2.68g/cm3, preferably 2.2g/ cm3-2.55g/cm3。
Preferably, the magnetic induction intensity of above-mentioned iron manganese phosphate for lithium class material is 800-1100ppm, preferably 950- 1050ppm。
Preferably, in above-mentioned iron manganese phosphate for lithium class material carbon content be iron manganese phosphate for lithium class total amount of material 0.5- 3.5wt%.
Preferably, M is one of Co, Ni, Mg, Zn, V and Ti or a variety of in above-mentioned iron manganese phosphate for lithium class material.
This iron manganese phosphate for lithium class material provided by the present invention is prepared by the above method, by being obtained ground and mixed The slurry containing primary particle pass sequentially through the biggish first chamber of differing pressure and second chamber so that environmental pressure from P1 bust to P2, make primary particle in second chamber narrow regions simultaneously by high speed shear, high frequency oscillation, cavitation and The mechanical forces such as convection current shock generate the strong cavitation of similar explosion effect.This just not only makes prepared phosphorus Sour manganese iron lithium class material surface is rounder and more smooth, greatly reduced the co-acting force between second particle, reduces prepared phosphorus The cohesive force of sour manganese iron lithium class material.And also reduce the content of impurity in finished-product material.
Meanwhile additionally provide a kind of cell size in the present invention, the cell size include iron manganese phosphate for lithium class material and Solvent, the iron manganese phosphate for lithium class material are the above-mentioned iron manganese phosphate for lithium class material of the present invention.It preferably can in above-mentioned cell size It with the solvent used include but is not limited to one of water, ethyl alcohol and methanol or a variety of.Also contain in the above-mentioned cell size of the present invention There are binder and conductive agent, wherein the raw material and dosage of binder and conductive agent are referred to this field conventional selection, such as Binder can be Kynoar, conductive agent can be acetylene black, iron manganese phosphate for lithium class material (positive electrode active materials) with lead The weight ratio of electric agent and binder is 80:10:10.
For the solid content of cell size, there is no particular/special requirements during preparing above-mentioned cell size, can basis The requirement of cell size makes appropriate choice.Generally, solid content is 30-60wt% in above-mentioned cell size, preferably For 40-50wt%, more preferably 45-50wt%.
In addition, still further providing a kind of anode in the present invention, which includes collector and is arranged in the afflux Anode active material layer on body, the anode active material layer include iron manganese phosphate for lithium class material of the present invention.The present invention is mentioned This positive electrode supplied is prepared, because of manganese phosphate by using the cell size containing above-mentioned iron manganese phosphate for lithium class material The cohesive force of iron lithium class material is relatively small, is conducive to the compacted density for improving positive electrode.
Preferably, above-mentioned collector is referred to current collector material commonly used in the art, for example including but be not limited to Silver-colored platinum (Pt), palladium (Pd), aluminium (Al) foil etc..
In addition, still further providing a kind of lithium battery in the present invention, the lithium battery interior is equipped with anode, the positive electrode For above-mentioned anode.This lithium battery provided by the present invention is starched by using the battery containing above-mentioned iron manganese phosphate for lithium class material Anode is prepared in material, and volume energy density is opposite to be improved.
Below with reference to specific embodiment and comparative example further illustrate carbon coating iron manganese phosphate lithium material of the present invention and its Preparation method and cell size and lithium battery and its advantages.
The high pressure homogenizer involved in following examples and comparative example is Germany APV high pressure homogenizer APV2000.
The test item involved in following examples and comparative example and test method are as follows:
Cohesive force: the multi-functional powder tester of FT4 of (Freeman Technology company) production is praised using big Chang Hua It is tested, test condition is to pre-process three times, applying pressure 9KPa, the 18 °/min of rotation speed of agitating paddle
Partial size: using the particle size analyzer of Jinan micro-nano, doing dispersing agent with deionized water, and ultrasonic disperse 10 minutes.
Specific surface area: using being tested in Jin Aipu V-Sorb2800 equipment, using static method, by iron manganese phosphate for lithium class material Sample pre-processes drying 2h at 150 DEG C.
Compacted density: 80 parts by weight iron manganese phosphate for lithium class material sample of the present invention: 10 parts by weight acetylene blacks (are commercially available from The Termical company trade mark is the product of SuperP): 10 parts by weight PVDF (are commercially available from A Kema (Changshu) fluorine Chemical Co., Ltd. The trade mark be PVDF HSV900 product) configuration 80 DEG C of cell size drying 2 hours after, after grinding cross 400 mesh screens, claim 0.3 gram Tabletting is carried out under 2Mpa pressure, Thickness Measurement by Microwave according to THICKNESS CALCULATION volume, and calculates compacted density according to this.
Magnetic induction intensity: it is tested using Mike's instrument magnetic analytical meter MA1040.Test method is, by iron manganese phosphate Lithium class material powder is filled in specimen cup (height of specimen 12cm), and the magnetic intensity for surveying 5 different directions is averaged.
Embodiment 1-12
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof.
Embodiment 1
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method:
The phosphoric acid (concentration 85wt%) for weighing 0.5mol, is dissolved in 1L deionized water, weigh 57.47 grams of manganese carbonates, 75.41 grams of ferric phosphates and 19.3 grams of glucose (finally can remnants 2.5wt%), respectively delay manganese carbonate, ferric phosphate and glucose It is slow that phosphoric acid solution is added, obtain solution A；41.9 grams of Lithium hydroxide monohydrates are weighed again, and are dissolved in 1L deionized water.By hydrogen-oxygen Change and be added in above-mentioned solution A under lithium aqueous solution stirring condition, obtains mixed solution B.
Mixed solution B is added to ball mill, 2h is ground with 300rpm revolving speed, is obtained containing primary particle (partial size 2.8 μm) slurry C.Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, Pressure is 15000Psi in middle homogeneous chamber, and flows into emulsification chamber with 10m/s speed, and emulsification cavity pressure is 2000Psi, is refined Slurry D；Refined pulp D is spray-dried, 700 DEG C, and constant temperature 10h are then heated in nitrogen atmosphere, is subsequently cooled to room Temperature can be obtained carbon-coated iron manganese phosphate lithium material.
(2) the electron-microscope scanning map of iron manganese phosphate for lithium class material
As shown in FIG. 1, FIG. 1 is aforementioned prepared iron manganese phosphate lithium materials in 2.00 μm of lower scanning electron microscope (SEM) maps, It can be seen that size distribution is comparatively uniform by the figure, and particle water chestnut is smaller, sphericity is relatively preferable.
(3) iron manganese phosphate for lithium class material properties test result
The partial size D of the iron manganese phosphate lithium material50For 0.65 μm, partial size D90For 1.8 μm, specific surface area 21.5m2/ g, pressure Real density is 2.53g/cm3；Cohesive force Cohesive is 0.84kPa, magnetic induction intensity 980ppm.
Embodiment 2
(1) iron manganese phosphate for lithium class (LiMn0.5Fe0.5PO4/ C) material preparation method: referring to embodiment 1, difference is:
Mixed solution B is added to ball mill, 1.5h is ground with 300rpm revolving speed, obtains that (partial size is containing primary particle 3.2 μm) slurry C.Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, Wherein pressure is 10000Psi in homogeneous chamber, and slurry C flows into emulsification chamber with 7m/s speed, and emulsification cavity pressure is 1000Psi, is obtained Refined pulp D；Refined pulp D is spray-dried, 780 DEG C, and constant temperature 5h are heated in nitrogen atmosphere, is then cooled to room temperature, It can be obtained iron manganese phosphate lithium material.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.78 μm, partial size D90For 2.1 μm, specific surface area 20.7m2/ g, pressure Real density is 2.52g/cm3；Cohesive force Cohesive is 0.92kPa, magnetic induction intensity 1010ppm.
Embodiment 3
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Mixed solution B is added to ball mill, 2.5h is ground with 300rmp revolving speed, obtains that (partial size is containing primary particle 2.5 μm) slurry C.Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, Wherein pressure is 25000Psi in homogeneous chamber, and slurry C flows into emulsification chamber with 14m/s speed, and emulsification cavity pressure is 3000Psi, is obtained Obtain refined pulp D；Refined pulp D is spray-dried, 650 DEG C, and constant temperature 20h are heated in nitrogen atmosphere, is subsequently cooled to room Temperature can be obtained iron manganese phosphate lithium material.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 0.58 μm, partial size D90For 1.4 μm, specific surface area 22.6m2/ g, pressure Real density is 2.51g/cm3；Cohesive force Cohesive is 0.74kPa, magnetic induction intensity 956ppm.
Embodiment 4
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Mixed solution B is added to ball mill, 3.5h is ground with 200 turns of min revolving speeds, obtains containing primary particle (partial size For the slurry C of 2.6um).Slurry C is added in high pressure homogenizer, homogeneous chamber and the emulsification in high pressure homogenizer are passed sequentially through Chamber, wherein pressure limit is 20000Psi in homogeneous chamber, and slurry C flows into emulsification chamber with 14m/s speed, and emulsification cavity pressure range is 4000Psi obtains refined pulp D；Refined pulp D is spray-dried, 680 DEG C, and constant temperature 12h are heated in nitrogen atmosphere, so After be cooled to room temperature, can be obtained iron manganese phosphate lithium material.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.53 μm, partial size D90For 1.3 μm, specific surface area 24.3m2/ g, pressure Real density is 2.54g/cm3；Cohesive force Cohesive is 0.65kPa, magnetic induction intensity 915ppm.
Embodiment 5
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is: Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer is passed sequentially through, is wherein pressed in homogeneous chamber Power is 8000Psi, and slurry C flows into emulsification chamber with 6m/s speed, and emulsification cavity pressure is 800Psi, obtains refined pulp D.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 0.82 μm, partial size D90For 2.5 μm, specific surface area 16.3m2/ g, pressure Real density is 2.42g/cm3；Cohesive force Cohesive is 1.12kPa, magnetic induction intensity 1050ppm.
Embodiment 6
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, wherein Pressure limit is 4000Psi in matter chamber, and slurry C flows into emulsification chamber with 3m/s speed, and emulsification cavity pressure range is 800Psi, is obtained Refined pulp D.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.96 μm, partial size D90For 2.9 μm, specific surface area 12.9m2/ g, pressure Real density is 2.41g/cm3；Cohesive force Cohesive is 1.47kPa, magnetic induction intensity 1098ppm.
Embodiment 7
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, wherein Pressure limit is 28000Psi in matter chamber, and slurry C flows into emulsification chamber with 20m/s speed, and emulsification cavity pressure range is 2800Psi, Obtain refined pulp D.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.59 μm, partial size D90For 1.2 μm, specific surface area 26.4m2/ g, pressure Real density is 2.62g/cm3；Cohesive force Cohesive is 0.58kPa, magnetic induction intensity 842ppm.
Embodiment 8
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, wherein Pressure limit is 28000Psi in matter chamber, and slurry C flows into emulsification chamber with 20m/s speed, and emulsification cavity pressure range is 4000Psi, Obtain refined pulp D.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.52 μm, partial size D90For 1.1 μm, specific surface area 27.6m2/ g, pressure Real density is 2.67g/cm3；Cohesive force Cohesive is 0.51kPa, magnetic induction intensity 815ppm.
Embodiment 9
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, wherein Pressure limit is 15000Psi in matter chamber, and slurry C flows into emulsification chamber with 11m/s speed, and emulsification cavity pressure range is 5000Psi, Obtain refined pulp D；Refined pulp D is spray-dried, 700 DEG C, and constant temperature 10h are heated in nitrogen atmosphere, is subsequently cooled to Room temperature can be obtained iron manganese phosphate lithium material.
(2) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 0.51 μm, partial size D90For 0.99 μm, specific surface area 29.6m2/ g, pressure Real density is 2.43g/cm3；Cohesive force Cohesive is 0.56kPa, magnetic induction intensity 792ppm.
Comparative example 1
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Mixed solution B is added to ball mill, 2h is ground with 300rmp revolving speed, obtains partial size D50Slurry less than 2.8 μm C.Slurry C is spray-dried, 700 DEG C, and constant temperature 10h are heated in nitrogen atmosphere, then cools to room temperature, can be obtained phosphoric acid Manganese iron lithium material.
(2) the electron-microscope scanning map of iron manganese phosphate for lithium class material
As shown in Fig. 2, Fig. 2 is scanning electron microscope (SEM) figure of aforementioned prepared iron manganese phosphate lithium material under 2.00 μm Spectrum, can be seen that the granularity of prepared iron manganese phosphate lithium material is very big by the figure, water chestnut is clearly demarcated.
(3) character of iron manganese phosphate for lithium class material and performance test and result
The partial size D of the iron manganese phosphate lithium material50For 2.5 μm, partial size D90For 8.5 μm, specific surface area 12.3m2/ g, compacting Density is 1.88g/cm3；Cohesive force Cohesive is 14.3kPa, magnetic induction intensity 4250ppm.
Comparative example 2
(1) iron manganese phosphate for lithium class material (LiMn0.5Fe0.5PO4/ C) preparation method: referring to embodiment 1, difference is:
Mixed solution B is added to ball mill, 2h is ground with 400rmp revolving speed, is obtained containing primary particle (partial size D50For 1.8 μm) slurry C.Slurry C is added in high pressure homogenizer, the homogeneous chamber and emulsification chamber in high pressure homogenizer are passed sequentially through, Wherein pressure limit is 2000Psi in homogeneous chamber, and slurry C flows into emulsification chamber with 1m/s speed, and emulsification cavity pressure range is 200Psi obtains refined pulp D；Refined pulp D is spray-dried, 700 DEG C, and constant temperature are then heated in nitrogen atmosphere 10h is then cooled to room temperature, and can be obtained iron manganese phosphate lithium material.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 1.5 μm, partial size D90For 4.2 μm, specific surface area 13.8m2/ g, compacting Density is 1.99g/cm3；Cohesive force Cohesive is 12.1kPa, magnetic induction intensity 3560ppm.
Embodiment 10
(1) iron manganese phosphate for lithium class material (LiMn0.3Fe0.7PO4/ C) preparation method: referring to embodiment 1, difference is,
The phosphoric acid (concentration 85wt%) for weighing 0.3mol, is dissolved in 1L deionized water, weigh 34.5 grams of manganese carbonates, 105.6 grams of ferric phosphates and 22.7 grams of glucose, are slowly added to phosphoric acid solution for manganese carbonate, ferric phosphate and glucose respectively, obtain Solution A；41.9 grams of Lithium hydroxide monohydrates are weighed again, and are dissolved in 1L deionized water.By lithium hydroxide aqueous solution stirring condition It is lower to be added in above-mentioned solution A, obtain mixed solution B.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size of the iron manganese phosphate lithium material is 0.68 μm, partial size D90For 1.7 μm, specific surface area 20.5g/cm3, compacting Density is 2.55g/cm3, cohesive force Cohesive be 0.82kPa, magnetic induction intensity 845ppm.
Comparative example 3
(1) iron manganese phosphate for lithium class material (LiMn0.3Fe0.7PO4/ C) preparation method: referring to embodiment 10, difference is:
Mixed solution B is added to ball mill, 2h is ground with 300rmp revolving speed, obtains slurry C of the partial size less than 2.9 μm. Slurry C is spray-dried, 700 DEG C, and constant temperature 10h are heated in nitrogen atmosphere, then cools to room temperature, can be obtained manganese phosphate Iron lithium material.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 2.5 μm, partial size D90For 9.28 μm, specific surface area 14.5m2/ g, pressure Real density is 2.1g/cm3；Cohesive force Cohesive is 19.4kPa, magnetic induction intensity 2890ppm.
Embodiment 11
(1) iron manganese phosphate for lithium class material (LiFePO4/ C) preparation method: referring to embodiment 1, difference is,
150.8 grams of ferric phosphates and 27.6 grams of glucose are weighed, ferric phosphate and glucose are slowly added to phosphoric acid solution respectively, Obtain solution A；41.9 grams of Lithium hydroxide monohydrates are weighed again, and are dissolved in 1L deionized water.Lithium hydroxide aqueous solution is stirred Under the conditions of be added in above-mentioned solution A, obtain mixed solution B.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size of the iron manganese phosphate lithium material is 0.67 μm, partial size D90For 1.6 μm, specific surface area 20.8g/cm3, compacting Density is 2.51g/cm3, cohesive force Cohesive be 0.79kPa, magnetic induction intensity 809ppm.
Comparative example 4
(1) iron manganese phosphate for lithium class material (LiFePO4/ C) preparation method: referring to embodiment 11, difference is:
Mixed solution B is added to ball mill, 2h is ground with 300rmp revolving speed, obtains slurry C of the partial size less than 2.9 μm. Slurry C is spray-dried, 700 DEG C, and constant temperature 10h are heated in nitrogen atmosphere, then cools to room temperature, can be obtained manganese phosphate Iron lithium material.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 2.4 μm, partial size D90For 5.9 μm, specific surface area 11.2m2/ g, compacting Density is 2.0g/cm3；Cohesive force Cohesive is 2.8kPa, magnetic induction intensity 926.7ppm.
Embodiment 12
(1) iron manganese phosphate for lithium class material (LiMn0.4Fe0.5Co0.1PO4/ C) preparation method: referring to embodiment 1, difference exists In:
The phosphoric acid (concentration 85wt%) for weighing 0.5mol, is dissolved in 1L deionized water, weigh 46.0 grams of manganese carbonates, 75.4 grams of ferric phosphates, 11.9 grams of cobalt carbonate and 13.4 grams of sucrose (finally can remnants 1.6wt%), respectively by manganese carbonate, phosphoric acid Iron, cobalt carbonate and sucrose are slowly added to phosphoric acid solution, obtain solution A；41.9 grams of Lithium hydroxide monohydrates are weighed again, and are dissolved in 1L In deionized water.It will be added in above-mentioned solution A under lithium hydroxide aqueous solution stirring condition, obtain mixed solution B.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size of the iron manganese phosphate lithium material is 0.75 μm, partial size D90For 1.9 μm, specific surface area 21.6g/cm3, compacting Density is 2.55g/cm3, cohesive force Cohesive be 0.75kPa, magnetic induction intensity 913ppm.
Comparative example 5
(1) iron manganese phosphate for lithium class material (LiMn0.4Fe0.5Co0.1PO4/ C) preparation method: referring to embodiment 12, difference It is:
Mixed solution B is added to ball mill, 2h is ground with 300rmp revolving speed, obtains slurry C of the partial size less than 2.9 μm. Slurry C is spray-dried, 700 DEG C, and constant temperature 10h are heated in nitrogen atmosphere, then cools to room temperature, can be obtained manganese phosphate Iron lithium material.
(2) the performance test results of iron manganese phosphate for lithium class material
The partial size D of the iron manganese phosphate lithium material50For 2.6 μm, partial size D90For 6.7 μm, specific surface area 11.7m2/ g, compacting Density is 2.2g/cm3；Cohesive force Cohesive is 18.9kPa, magnetic induction intensity 9850ppm.
Test
(1) it positive preparation: is positive respectively with iron manganese phosphate for lithium class material prepared by embodiment 1-12 and comparative example 1-5 The positive electrode active materials and acetylene black, Kynoar (are celebrated the rich limited public affairs of plastic material purchased from Dongguan City by pole active material Department, trade mark FR900) by weight being that 80:10:10 is dissolved in N-Methyl pyrrolidone (NMP) and is mixed to form solid content and is The cell size of 50wt%, and the slurry obtained after mixing evenly is coated on collector (aluminium foil with a thickness of 16 μm), and It is toasted at 100 DEG C ± 5 DEG C, forms the material layer with a thickness of 70 μm, obtain positive electrode S1-S12 and D1-D5.
(2) preparation of lithium ion monolithic battery: respectively using by LiFePO 4 material in embodiment 1-12 and comparative example 1-5 Prepared positive S1-S12 and D1-D5 makes lithium ion monolithic battery, and negative electrode material is graphite, diaphragm in made battery Material is that (PVDF is commercially available from the production that A Kema (Changshu) the fluorine Chemical Co., Ltd. trade mark is PVDF HSV900 to Kynoar Product), electrolyte 1mol/LLiPF6(wherein LiPF6 is lithium hexafluoro phosphate to/(EC+DMC), and EC is ethylene carbonate, and DMC is carbon The volume ratio of dimethyl phthalate, EC and DMC are 1:1), made battery is denoted as T1-T12 and P1-P5 respectively.
(3) battery performance test
1., battery is denoted as T1-T12 respectively respectively and P1-P5 is placed in test cabinet, constant current constant voltage is first carried out with 0.1C and is filled Electricity, chargeable range 2.5-4.35V, and the discharge capacity for the first time of battery is recorded, and record the discharge capacity for the first time of battery, and press The specific discharge capacity and volume and capacity ratio of battery are calculated according to following formula；
Specific discharge capacity=battery discharge capacity (milliampere hour)/positive electrode weight (gram) for the first time
Volume and capacity ratio=battery discharge capacity (milliampere hour)/positive electrode volume (cm for the first time3)
2., first by battery charge and discharge one week (7 days) under 0.1C electric current, record discharge capacity C0；Again by battery in 0.1C Under it is fully charged after after 65 DEG C of baking oven high temperatures store 7 days, take out battery it is cooling after, discharge by voltage 2.5V, record is surplus Covolume amount C1,65 DEG C of 7 days capacity retention ratios of battery are (C0/C1) * 100%.
(2) test result: as shown in table 1.
Table 1
Test item T1 T2 T3 T4 T5 T6
Specific discharge capacity (milliampere/gram) 165.3 162.6 163.3 158.3 157.2 151.0
Volume and capacity ratio (milliampere/cm3) 418.2 409.8 410.0 402.2 380.4 363.9
65 DEG C of 7 days capacity retention ratios (%) 98.5% 98.0% 98.3% 97.2% 97.2% 96.8%
Test item T7 T8 T9 T10 T11 T12
Specific discharge capacity (milliampere/gram) 146.8 145.9 161.3 162.5 159.8 161.7
Volume and capacity ratio (milliampere/cm3) 384.6 389.6 391.8 414.4 401.1 412.3
65 DEG C of 7 days capacity retention ratios (%) 97.3% 97.4% 97.4% 97.3% 97.4% 97.2%
Test item P1 P2 P3 P4 P5
Specific discharge capacity (milliampere/gram) 135.2 150.2 143.8 132.6 110.8
Volume and capacity ratio (milliampere/cm3) 254.2 298.9 302.0 265.2 243.8
65 degree of 7 days capacity retention ratios (%) 90.5% 91.9% 93.2% 87.4% 79.3%
In conjunction with data in table 1 and Fig. 1 and Fig. 2 it is found that compared with the iron manganese phosphate lithium material prepared by the comparative example 1, according to Iron manganese phosphate lithium material prepared by the embodiment 1-12 of the method for the present invention, size distribution is comparatively uniform, and particle Water chestnut is smaller, and sphericity is relatively preferable, and the partial size of the iron manganese phosphate lithium material is smaller, and cohesive force is lower, and by rationally setting Relatively high compacted density can also be accessed by setting, and being includes that the battery of anode prepared by the iron manganese phosphate lithium material is having While having higher specific discharge capacity, also there is relatively high volume and capacity ratio, be conducive to extend the stand-by time of battery. Meanwhile iron manganese phosphate lithium material prepared by embodiment 1-12 according to the method for the present invention, grain diameter is smaller, and the table of particle Face water chestnut is ground rounder and more smooth, and then is more advantageous to impurity contained in the iron manganese phosphate for lithium class material prepared by reducing, into And be conducive to improve battery high-temperature (65 DEG C 7 days) capacity retention ratio.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (21)

1. a kind of iron manganese phosphate lithium material, which is characterized in that the iron manganese phosphate lithium material has LiMnxFe1-x-yMyPO4/ C knot Structure, wherein 0 < x < 1,0≤y < 1, M are the transition metal element in addition to Mn and Fe, the partial size D of the iron manganese phosphate lithium material50 It is 0.5-1.0 μm, D90It is 1.0-5.0 μm, and cohesive force Cohesive≤1.5kPa of the iron manganese phosphate lithium material；
The iron manganese phosphate lithium material is prepared by following methods:
Lithium source, manganese source, source of iron and the optional source M, phosphorus source and carbon source are subjected to ground and mixed in proportion, obtained containing once The slurry of particle；
The slurry containing primary particle is passed sequentially through into the first chamber that pressure is P1 and the second chamber that pressure is P2, is obtained To refined pulp, wherein P1 >=4000Psi, and P1 is 3 times of P2 or more；
The refined pulp is passed sequentially through into dry and sintering processes, obtains second particle, i.e., the described iron manganese phosphate lithium material.
2. iron manganese phosphate lithium material according to claim 1, wherein the partial size D of the iron manganese phosphate lithium material50For 0.5- 0.8 μm, D90It is 1.0-3.0 μm, and cohesive force Cohesive≤1.2kPa of the iron manganese phosphate lithium material.
3. iron manganese phosphate lithium material according to claim 1 or 2, wherein the specific surface area S of the iron manganese phosphate lithium material For 12m2/g≤S≤28m2/g。
4. iron manganese phosphate lithium material according to claim 1 or 2, wherein the specific surface area S of the iron manganese phosphate lithium material For 15m2/g≤S≤25m2/g。
5. iron manganese phosphate lithium material according to claim 1 or 2, wherein the compacted density of the iron manganese phosphate lithium material For 2.0 g/cm3-2.68 g/cm3。
6. iron manganese phosphate lithium material according to claim 1 or 2, wherein the compacted density of the iron manganese phosphate lithium material For 2.2g/cm3-2.55g/cm3。
7. iron manganese phosphate lithium material according to claim 1 or 2, wherein carbon in the iron manganese phosphate lithium material Content is the 0.5-3.5wt% of iron manganese phosphate for lithium total amount of material.
8. iron manganese phosphate lithium material according to claim 1 or 2, wherein the M is in Co, Ni, Mg, Zn, V and Ti It is one or more.
9. the preparation method of iron manganese phosphate lithium material described in a kind of any one of claim 1 to 8, which is characterized in that institute State preparation method the following steps are included:
Lithium source, manganese source, source of iron and the optional source M, phosphorus source and carbon source are subjected to ground and mixed in proportion, obtained containing once The slurry of particle；
The slurry containing primary particle is passed sequentially through into the first chamber that pressure is P1 and the second chamber that pressure is P2, is obtained To refined pulp, wherein P1 >=4000Psi, and P1 is 3 times of P2 or more；
The refined pulp is passed sequentially through into dry and sintering processes, obtains second particle, i.e., the described iron manganese phosphate material.
10. preparation method according to claim 9, wherein the P1 is 4000-28000Psi.
11. preparation method according to claim 10, wherein the P1 is 10000-25000Psi.
12. preparation method according to claim 11, wherein P1 is 5 times of P2 or more.
13. preparation method according to claim 12, wherein P2 1000-4000Psi.
14. preparation method according to claim 10, wherein the slurry containing primary particle is with 2-20m/s speed Second chamber is flowed into from first chamber.
15. the preparation method according to any one of claim 9 to 14, wherein the first chamber is high-pressure homogeneous The homogeneous chamber of machine, the second chamber are the emulsification chamber of the high pressure homogenizer.
16. the preparation method according to any one of claim 9 to 14, wherein the partial size of the primary particle is 50- 200nm, the partial size of the second particle are 2-10 μm.
17. the preparation method according to any one of claim 9 to 14, wherein the carbon source is according to prepared phosphorus The content of the carbon of final residual is that the 0.5-3.5wt% of iron manganese phosphate lithium material total weight is added in sour manganese iron lithium material.
18. the preparation method according to any one of claim 9 to 14, wherein the condition of the sintering processes includes The Isothermal sinter 2-20h at 650-780 DEG C.
19. a kind of cell size, the cell size includes iron manganese phosphate lithium material and solvent, which is characterized in that the phosphoric acid Manganese iron lithium material is iron manganese phosphate lithium material described in any one of claim 1 to 8.
20. a kind of anode, the anode includes collector and the anode active material layer being arranged on the collector, feature It is, the anode active material layer includes iron manganese phosphate lithium material described in any one of claim 1 to 8.
21. a kind of lithium battery, the lithium battery interior is equipped with anode, which is characterized in that the anode includes claim 20 institute The anode stated.
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