CN106816600A - A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery - Google Patents

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

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Publication number
CN106816600A
CN106816600A CN201510863430.0A CN201510863430A CN106816600A CN 106816600 A CN106816600 A CN 106816600A CN 201510863430 A CN201510863430 A CN 201510863430A CN 106816600 A CN106816600 A CN 106816600A
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lithium
class material
manganese phosphate
active component
iron manganese
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CN106816600B (en
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徐茶清
陈靖华
游军飞
肖峰
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BYD Co Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery.The iron manganese phosphate for lithium class material includes thering is LiMnxFe1-x-yMyPO4The active component of/C-structure, wherein 0≤x≤1,0≤y≤1, M is one or more in Co, Ni, Mg, Zn, V and Ti；And the clad on the active component surface is wrapped in, the clad contains amorphous metal compound.The iron manganese phosphate for lithium class material is by with LiMnxFe1-x-yMyPO4The active component Surface coating of/C-structure contains the clad of the relatively low amorphous metal compound of water absorption rate, while the chemical property of iron manganese phosphate for lithium class material is kept, the water absorption rate of iron manganese phosphate for lithium class material is reduced, and then is conducive to improving memory capacity conservation rate at a high temperature of correspondingly lithium battery.

Description

A kind of iron manganese phosphate for lithium class material and preparation method thereof And cell size and positive pole and lithium battery
Technical field
The present invention relates to lithium battery preparation field, in particular it relates to a kind of iron manganese phosphate for lithium class Material and preparation method thereof, the invention further relates to a kind of battery including aforementioned phosphate ferromanganese lithium class material Slurry, the invention further relates to a kind of positive pole for including aforementioned phosphate ferromanganese lithium class material, and Lithium battery including aforementioned positive electrode.
Background technology
Lithium rechargeable battery is novel green high-power rechargeable battery, and it has, and voltage is high, energy is close The many merits such as degree is big, good cycle, small self discharge, memory-less effect, working range are wide, extensively It is general to be applied to mobile phone, notebook computer, portable power tool, electronic instrument, weaponry Deng, also had a good application prospect in electric automobile, countries in the world are turned at present and has competitively been studied The emphasis of exploitation.Positive electrode is a critically important part of lithium ion battery, in lithium-ion electric In the charge and discharge process of pond, reciprocal embedding/de- required lithium in positive and negative lithium intercalation compound is not only provided, And the lithium required for negative material surface forms SEI films is also provided, therefore, research and develop property high The positive electrode of energy is the key point of lithium ion battery development.
In anode material for lithium-ion batteries, iron manganese phosphate for lithium class material is showed most in combination property It is excellent, it is considered to be ideal lithium ion secondary power battery positive electrode.However, existing phosphorus , in nanoscale, its specific surface area is than larger for the particle diameter general control of sour ferromanganese lithium class material, once contact To malaria, moisture easily there is hydrophilic Li to be in contact with material surface, within a period of time Top layer lithium also can occur lithiation with water after (a few weeks) LiFePO4 contact malaria, cause phosphorus The moisture content of sour ferromanganese lithium class increases.And the of a relatively high iron manganese phosphate for lithium class material of this moisture content exists When being used as cell positive material, because moisture in materials is difficult in further battery dispensing pulling phase Removal, can be remained into battery always, and this memory capacity conservation rate for allowing for battery is showed mostly It is not good.In order to improve the memory capacity conservation rate of battery, research staff have studied kinds of schemes, for example, drop The water absorption rate of low iron manganese phosphate for lithium class material.
In the Chinese patent application of Application No. No.200910053346, a kind of raising phosphoric acid is disclosed The method of ferrous lithium anode material electric conductivity, the method is source of iron, lithium source and phosphate radical using raw material Source, synthetic method is solid phase method, is not required to any dopant activation, and ferrous phosphate is being synthesized according to a conventional method The gas that can be dehydrated of importing, vavuum pump draw water and five oxygen on the basis of lithium material, then during with high-temperature calcination Change the methods such as two phosphorus water suction and remove the moisture remained in ferrousphosphate lithium material, so as to be greatly improved material The electric conductivity of material.But the process of the method is complex, it is necessary to introduce various auxiliary materials, Moisture in removal material, and can not using the lithium iron phosphate cathode material prepared by the method Ensure water imbibition of the material in subsequent touch air.
In the Chinese patent application of Application No. No.200910044154, disclose a kind of surface and be modified Lithium ion battery anode material lithium cobaltate and its method of modifying, the patent presses Li: Co first Molal weight ratio weighs lithium salts and cobalt salt respectively for 1.038；Lithium salts is first added in ball mill, is added Cladding material calcium carbonate, is subsequently adding cobalt salt, is eventually adding industrial alcohol, carries out ball milling；After ball milling Material it is vacuum dried after, then burnt till first；Material after burning till is in broken, crushing Afterwards, washed with deionized water, twice firing；Decentralized processing is obtained final product in one layer of carbon of cobalt acid lithium Surface coating The positive electrode of sour calcium.This method of modifying has hydrophobic carbonic acid for one layer in cobalt acid lithium Surface coating Calcium, can intercept active material and contact with moisture, and the water imbibition of cobalt acid lithium is improved to a certain extent Can, but it introduces excessive impurity, causes active component to decline, and influences the electrochemistry of final material Energy.
As shown in the above, although proposing some in the prior art reduces iron manganese phosphate for lithium class material Expect the scheme of water imbibition, but its effect is unsatisfactory, and use the electricity as prepared by this material The high temperature storage capability retention of the battery of pole also tends to not good.
The content of the invention
Starched it is an object of the invention to provide a kind of iron manganese phosphate for lithium class material and preparation method thereof and battery Material and positive pole and lithium battery, to provide a kind of water absorption rate relatively low iron manganese phosphate for lithium class material, Jin Erti Capability retention under battery high-temperature storage high.
To achieve these goals, according to the first aspect of the invention, there is provided a kind of iron manganese phosphate for lithium Class material, the iron manganese phosphate for lithium class material includes thering is LiMnxFe1-x-yMyPO4The activearm of/C-structure Point, wherein 0≤x≤1,0≤y≤1, M be one kind in Co, Ni, Mg, Zn, V and Ti or It is various；And the active component surface coating layer is wrapped in, contain amorphous metal in the clad Compound.
According to the second aspect of the invention, there is provided a kind of preparation side of lithium ferric manganese phosphate class material Method, the preparation method is comprised the following steps：S1, offer have LiMnxFe1-x-yMyPO4/ C-structure Active component, wherein 0≤x≤1,0≤y≤1, M is in Co, Ni, Mg, Zn, V and Ti One or more；S2, with the active component as base material, the active component surface formed contain There is the clad of amorphous metal compound.
According to the third aspect of the present invention, there is provided iron manganese phosphate for lithium class material, the iron manganese phosphate for lithium Class material is prepared from by above-mentioned preparation method.
According to the fourth aspect of the present invention, there is provided a kind of cell size, the cell size includes phosphorus Sour ferromanganese lithium class material and solvent, wherein, the iron manganese phosphate for lithium class material is above-mentioned phosphoric acid of the invention Ferromanganese lithium class material.
According to the fifth aspect of the present invention, there is provided a kind of positive pole, the positive pole includes collector and sets The anode active material layer on the collector is put, the anode active material layer includes phosphorus of the present invention Sour ferromanganese lithium class material.
According to the sixth aspect of the invention, there is provided a kind of lithium battery, the lithium battery interior is equipped with Positive pole, the above-mentioned positive electrode just extremely of the invention.
Iron manganese phosphate for lithium class material provided by the present invention and preparation method thereof and cell size and positive pole With lithium battery, wherein iron manganese phosphate for lithium class material is by with LiMnxFe1-x-yMyPO4/ C-structure Active component Surface coating contains the clad of the relatively low amorphous metal compound of water absorption rate, is keeping While the chemical property of iron manganese phosphate for lithium class material, the water suction of iron manganese phosphate for lithium class material is reduced Rate, and then the water content of positive pole as prepared by it is reduced, and then be conducive to improving by the positive pole material Memory capacity conservation rate at a high temperature of the prepared lithium battery of material.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part It is bright.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, It is used to explain the present invention together with following specific embodiment, but does not constitute to limit of the invention System.In the accompanying drawings：
Fig. 1 shows 5 μm of the iron manganese phosphate for lithium class material P1 prepared by example produced according to the present invention 1 ESEM (SEM) collection of illustrative plates；
Fig. 2 shows 5 μm of the iron manganese phosphate for lithium class material DP1 according to prepared by comparative example of the present invention 1 ESEM (SEM) collection of illustrative plates.
Specific embodiment
Specific embodiment of the invention is described in detail below in conjunction with accompanying drawing.It should be understood that It is that specific embodiment described herein is merely to illustrate and explain the present invention, and is not limited to The present invention.
It is directed to pointed by background of invention part and " there is the storage appearance of battery in the prior art Amount conservation rate perform poor mostly " technical problem.The present inventor is in sides such as removal material moisture Face has carried out substantial amounts of work and research.And according to the first aspect of the invention, there is provided a kind of phosphoric acid Ferromanganese lithium class material, the iron manganese phosphate for lithium class material includes thering is LiMnxFe1-x-yMyPO4/ C-structure Active component, wherein 0≤x≤1,0≤y≤1, M is in Co, Ni, Mg, Zn, V and Ti One or more；And the clad on the active component surface is wrapped in, the clad contains amorphous State metallic compound.
" there is LiMn in the present inventionxFe1-x-yMyPO4The active component of/C-structure " refers to carbon bag Cover iron manganese phosphate for lithium class material (LiMnxFe1-x-yMyPO4) structure active component.
Iron manganese phosphate for lithium class material provided by the present invention, by with LiMnxFe1-x-yMyPO4/C The active component Surface coating of structure contains the clad of the relatively low amorphous metal compound of water absorption rate, While the chemical property of iron manganese phosphate for lithium class material is kept, iron manganese phosphate for lithium class material is reduced Water absorption rate, and then the water content of positive electrode as prepared by it is reduced, so as to be conducive to improving Memory capacity conservation rate at a high temperature of lithium battery as prepared by the positive electrode.
In iron manganese phosphate for lithium class material of the present invention, do not have particular/special requirement for material particle size, can be with With reference to the conventional selection of this area, such as particle diameter D50It can be 0.5-2.0 μm.The phosphoric acid of required preparation The particle diameter of ferromanganese lithium class material, the grain of active component in the iron manganese phosphate for lithium class material that can reasonably arrange Footpath and the thickness of clad, as long as the clad cladding in the present invention containing amorphous metal compound On the surface of active component.In the present invention preferably in the iron manganese phosphate for lithium class material, activity The particle diameter D of component50It is 0.5-1.0 μm, preferably 0.5-0.8 μm, amorphous metal compound clad Thickness be 1-5nm.Wherein particle diameter D in the present invention50It is volume average particle size, it is by that will treat Survey powder to be dispersed in water, then ultrasonic vibration 30 minutes, carry out testing graininess and obtain with laser particle analyzer .
In iron manganese phosphate for lithium class material of the present invention, for the amorphous metal compound in clad simultaneously There is no particular/special requirement, as long as its water absorption rate is less than active component.In the present invention preferably the amorphous State metallic compound be selected from amorphous state alundum (Al2O3), amorphous state lithium phosphate, amorphous state pyrophosphoric acid lithium, The oxidation of amorphous state ferric pyrophosphate, amorphous state ferrous pyrophosphate lithium, amorphous state manganese pyrophosphate lithium and amorphous state One or more mixing in silver.It was found by the inventors of the present invention that by these amorphous metal compound shapes Into clad compared with the clad that conventional amorphous metal compound is formed, its absorptivity is lower.Hair A person of good sense speculates, it may be possible to because this " amorphous metal compound " is typically regular random growth, and Its surface can form nonpolar bond, and these nonpolar bonds are difficult to be combined with the water of polarity, and this can just rise To the effect for stopping moisture infiltration, it is thus possible to preferably intercept active component and contact with moisture, Jin Ergai The water absorbing properties of kind iron manganese phosphate for lithium class material, while this inorganic amorphous metallic compound is formed Clad because of very thin thickness, therefore the electrification of prepared iron manganese phosphate for lithium class material can't be influenceed Performance is learned, and then causes that prepared iron manganese phosphate for lithium class material has preferable chemical property.
In the preferred embodiment of the present invention, above-mentioned iron manganese phosphate for lithium class material also includes cladding In the conductive carbon layer of the cover surface, by the cover surface containing amorphous metal compound Conductive carbon layer is further set to be conducive to further optimizing materials conductive performance.More preferably described conduction The thickness of layer of charcoal is 2-10nm.
In iron manganese phosphate for lithium class material of the present invention, for described with LiMnxFe1-x-yMyPO4/ C is tied Element proportioning in the active component of structure does not have particular/special requirement, its conventional element for being referred to this area Proportioning, as long as aforementioned structure can be formed.Preferably, Li and Mn, Fe and M sum are rubbed You are than being 0.98-1.02：1.It is preferred that the content of C element is activity in the active component The 0.5-3.5wt% of component weight.
The magnetic induction intensity for iron manganese phosphate for lithium class material does not have particular/special requirement in the present invention, can With reference to this area conventional selection.However, the electrification in order to optimize prepared iron manganese phosphate for lithium class material Performance is learned, the magnetic induction intensity of preferably described iron manganese phosphate for lithium class material is 750-1100ppm.Wherein phosphorus The magnetic induction intensity of sour ferromanganese lithium class material is surveyed using Mike's instrument magnetic analytical meter MA1040 Examination.Method of testing is, (height of specimen is during iron manganese phosphate for lithium class material powder is filled into specimen cup 12cm), the magnetic intensity for surveying 5 different directions is averaged.
According to the second aspect of the invention, a kind of lithium ferric manganese phosphate class material is additionally provided in the present invention The preparation method of material.The above-mentioned lithium ferric manganese phosphate class material of the present invention is referred to the conventional method of this area It is prepared, it is also possible to prepared by this preferred preparation method provided by the present invention.Institute of the present invention This preparation method for providing is comprised the following steps：S1, preparation have LiMnxFe1-x-yMyPO4/ C is tied The active component of structure, wherein 0≤x≤1,0≤y≤1, M is Co, Ni, Mg, Zn, V and Ti In one or more；S2, with the active component as base material, in the surface shape of the active component Into the clad containing amorphous metal compound.
The preparation method of this lithium ferric manganese phosphate class material provided by the present invention by by active component, And be coated on the clad on the surface of the active component and formed in different steps, be conducive to While ensureing the chemical property of lithium ferric manganese phosphate class material so that clad is more uniformly distributed, completely Be coated on active component surface, to intercept active component and contact with moisture, and then improve phosphoric acid The water absorbing properties of ferromanganese lithium.
In above-mentioned preparation method, S1 is provided has LiMnxFe1-x-yMyPO4The active component of/C-structure The step of in, with LiMnxFe1-x-yMyPO4The active component of/C-structure can be commercially available prod, also may be used Prepared with reference to conventional method in this area.In the present invention preferably through using high temperature solid-state legal system Standby, it is comprised the following steps：S11, by lithium source, optional source of iron, optional manganese source, optional M Source, phosphorus source and the first carbon source mix in proportion, and the first drying composite is obtained after drying；S12, by institute The first drying composite is stated at 600-800 DEG C, Isothermal sinter 5-30h forms the active component.
In the S11 of above-mentioned preparation method, each raw material can in proportion be mixed by the way of grinding, The mode that grinding can be used including but not limited to ball milling, sand milling or Ball-stirring mill etc..For the technique ground Condition is referred to the process conditions that this area routinely uses, such as in the speed of 1000-2000rpm Grinding 1-6h.Also include the step of adding lapping liquid, the lapping liquid bag in the step of ground and mixed Include but be not limited to deionized water and C1-C5One or more in alcohol.C1-C5The C that alcohol is preferably1-C5One First alcohol, it includes but is not limited to methyl alcohol, ethanol, normal propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, 2- Methyl isophthalic acid-propyl alcohol, 2- methyl-2-propanols, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanols, 2- One or more in methyl -2- butanol, 3- methyl -2- butanol and 2,2- dimethyl -1- propyl alcohol, preferably Ethanol.
In the S11 of above-mentioned preparation method, the mode of dried process includes but is not limited to vacuum drying, lazy Property gas shield heat drying, spray drying, freeze-drying or expansion drying etc., wherein be preferably spraying Mist is dried, and the condition for being spray-dried is referred to the process conditions of this area conventional selection, for example, enter Air temperature is 200-300 DEG C, and leaving air temp is 80-200 DEG C.
In the S12 of above-mentioned preparation method, the step of be sintered to first drying composite in can With with reference to the conventional mode of operation in this area, as long as the Isothermal sinter 5-30h at 600-800 DEG C. Preferably first drying composite is warming up to the speed of 0.1-2 DEG C/min in the present invention 600-800 DEG C, constant temperature treatment 5-30h.Shape is conducive to by the programming rate for adjusting the first drying composite Into well-developed crystallne phosphoric acid ferromanganese lithium class bulk material, it is ensured that material has of a relatively high electrochemistry Activity.
In the S11 of above-mentioned preparation method, preparing has LiMnxFe1-x-yMyPO4The activearm of/C-structure Point the step of in do not have particular/special requirement for the consumption of each raw material, according to envision formation LiMnxFe1-x-yMyPO4/ C-structure, reasonably selects the consumption of corresponding raw material.In the present invention It is preferred that in preparation raw material, lithium source in terms of Li with optional source of iron, optional manganese source, optional M sources Mol ratio is counted as 0.98-1.02 with Fe+Mn+M total amounts：1.Lithium source rubbing in terms of phosphorus with phosphorus source in terms of Li You are than being 0.98-1.02：1.Selection for each raw material in the present invention does not have particular/special requirement, can be with The conventional material employed in iron manganese phosphate for lithium class material is being prepared with reference to this area.Wherein：
The lithium source that can be used including but not limited to lithium hydroxide, lithium peroxide, lithia, lithium carbonate With one or more in lithium phosphate.
The phosphorus source that can be used including but not limited to phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid One or more in the ammonium of hydrogen two, ammonium phosphate, lithium phosphate, pyrophosphoric acid lithium.
The Fe sources that can be used including but not limited to ferrous oxide, ferroso-ferric oxide, di-iron trioxide, Ferric nitrate, ferrous nitrate, ferrous acetate, formic acid ferrous iron in one or more.
The Mn sources that can be used including but not limited to manganese dioxide, manganous oxide, mangano-manganic oxide, carbon Sour manganese manganese nitrate, Mn nitrate, acetic acid Asia manganese, formic acid Asia manganese in one or more
Optional M sources be containing Co, Ni, Mg, Zn, V and Ti in one or more of chemical combination Thing.Wherein it is possible to the compound containing Co for using including but not limited to cobaltosic oxide, cobalt nitrate, oxygen Change one or more in sub- cobalt, cobalt hydroxide, cobalt acetate and cobalt phosphate；Can use containing Niization Compound includes but is not limited to nickel protoxide, nickel oxide, nickel nitrate, nickel hydroxide, nickel acetate and nickel phosphate In one or more；The compound containing Mg that can be used including but not limited to magnesia, magnesium nitrate, One or more in magnesium hydroxide and magnesium acetate；The compound containing Zn that can be used is included but is not limited to One or more in zinc oxide, zinc nitrate, zinc hydroxide and zinc acetate；The chemical combination containing V that can be used Thing include but is not limited to vanadous oxide, vanadic anhydride, vanadium trioxide, nitric acid vanadium, vanadium hydroxide and One or more in acetic acid vanadium；The compound containing Ti that can be used including but not limited to titanium dioxide, One or more in titanium hydroxide, acetic acid titanium and the fourth fat of metatitanic acid four.
The carbon source that can be used including but not limited to glucose, sucrose, lactose, phenolic resin, graphite Alkene, CNT, graphite etc. have been carbonized or can be with the organic carbon source of high temperature cabonization or inorganic carbon sources. Preparing with LiMn in the present inventionxFe1-x-yMyPO4Added in the step of active component of/C-structure The purpose of carbon source is to improve material electronicses electric conductivity, and identical with this area conventional method, in the present invention The carbon source added, can be enriched to the surface of iron manganese phosphate for lithium class material during sintering processes, because This is formed has LiMnxFe1-x-yMyPO4The iron manganese phosphate for lithium class material of/C-structure, i.e. carbon coating structure. The inventory of added carbon source is referred to the conventional amount used of this area in the present invention, such as C sources Consumption is so that the content of C element is the 0.5-3.5wt% of active component gross weight in active component.
In the S2 of above-mentioned preparation method, the step of prepare amorphous metal compound clad in, it is right Do not have particular determination in the method for forming the clad containing amorphous metal compound, as long as institute's shape Into clad in material be as an amorphous form exist.It is preferred that the S2 is comprised the following steps： S21, by the active component with for forming the material source (in solvent, such as water) of metallic compound Mix, dry, obtain the second drying composite；S22, second drying composite is warming up to 300-500 DEG C does not carry out being incubated directly cooling, and the amorphous state is formed with the surface in the active component Metallic compound clad.
In the S21 of above-mentioned preparation method, for active component and the material for forming metallic compound The hybrid mode in source does not have particular/special requirement, as long as by both relatively uniform dispersions in a solvent, Can for example cause that both mix by way of stirring relatively uniform, mixing time is 15-50min.
In the S21 of above-mentioned preparation method, the mode of dried process can include but is not limited to vacuum and do Dry, inert gas shielding heat drying, spray drying, freeze-drying or expansion drying etc., wherein excellent Elect spray drying as, the condition for being spray-dried is referred to the process conditions of this area conventional selection, Will not be repeated here.
In the S22 of above-mentioned preparation method, the mode for heating does not have particular/special requirement, as long as Second drying composite is warming up into 300-500 DEG C does not carry out being incubated directly cooling, with the work Property component surface form the clad containing amorphous metal compound.It is excellent in the present invention Second drying composite is warming up to 300-500 DEG C by choosing with the speed of 30-80 DEG C/min.It is dry by second Dry mixture is warming up to 300-500 DEG C and is conducive to preferably in material surface with the speed of 30-80 DEG C/min Form the clad containing amorphous metal compound.
In the S2 of above-mentioned preparation method, mainly formed on the surface of active component and contain amorphous state gold Belong to the clad of compound, to reduce the water absorption rate and moisture content of iron manganese phosphate for lithium class material.In order to enter one Walk the water absorption rate and moisture content of the iron manganese phosphate for lithium class material prepared by reduction, institute in preferably described clad The amorphous metal compound for containing is selected from amorphous state alundum (Al2O3), amorphous state lithium phosphate, amorphous state Pyrophosphoric acid lithium, amorphous state ferric pyrophosphate, amorphous state ferrous pyrophosphate lithium, amorphous state manganese pyrophosphate lithium, One or more mixing in amorphous state silver oxide.
Preferably, material source including but not limited to alundum (Al2O3), the acetic acid of alundum (Al2O3) can be formed Aluminium, aluminum nitrate or aluminium hydroxide.The material source that lithium phosphate can be formed includes lithium source and phosphorus source or phosphorus lithium Source, wherein lithium source include but is not limited to lithium hydroxide or lithium carbonate, and phosphorus source includes but is not limited to phosphoric acid, phosphorus Lithium source includes but is not limited to lithium dihydrogen phosphate or lithium phosphate.The material source that pyrophosphoric acid lithium can be formed includes lithium Source and phosphorus source or phosphorus lithium source, wherein lithium source include but is not limited to lithium hydroxide or lithium carbonate, phosphorus source include but Phosphoric acid is not limited to, phosphorus lithium source includes but is not limited to lithium dihydrogen phosphate or lithium phosphate or pyrophosphoric acid lithium.Can be with shape Material source into ferric pyrophosphate includes source of iron and phosphorus source, or ferrophosphorus source.Wherein source of iron is included but is not limited to Di-iron trioxide or ferric acetate, phosphorus source include but is not limited to phosphoric acid, and ferrophosphorus source includes but is not limited to phosphoric acid Iron.The material source that ferrous pyrophosphate lithium can be formed includes lithium source, source of iron and phosphorus source, and wherein lithium source includes But it is not limited to lithium hydroxide, lithium carbonate, lithium dihydrogen phosphate, lithium phosphate；Source of iron includes but is not limited to three oxygen Change two iron, ferric acetate or ferric phosphate, phosphorus source includes but is not limited to phosphoric acid, lithium dihydrogen phosphate, lithium phosphate. The material source that manganese pyrophosphate lithium can be formed includes lithium source, manganese source and phosphorus source.Wherein lithium source includes but does not limit In lithium hydroxide, lithium carbonate, lithium dihydrogen phosphate or lithium phosphate；Manganese source include but is not limited to manganese dioxide, Manganese carbonate, manganese acetate or mangano-manganic oxide；Phosphorus source includes but is not limited to monophosphate monophosphate dihydro lithium or lithium phosphate. Material source including but not limited to silver oxide, silver acetate, silver nitrate or the hydroxide of silver oxide can be formed Silver.
In a kind of preferred embodiment in the present invention, above-mentioned preparation method is further comprising the steps of：S3 The intermediate product obtained with S2 forms conductive carbon layer as base material on the surface of the intermediate product.Shape The step of into conductive carbon layer, is referred to according to this area conventional method and Conventional process parameters.In this hair The preferred S3 is comprised the following steps in bright：The intermediate product that will be obtained in S2 is with second carbon source (molten In agent, such as water) mixing, it is dried to obtain the 3rd drying composite；By the 3rd drying composite liter After warm to 600-750 DEG C, insulation 3-10h forms the conductive carbon layer with the surface in the active component.
In the S3 of above-mentioned preparation method, do not have with the hybrid mode of second carbon source for intermediate product Particular/special requirement, as long as by both relatively uniform dispersions in a solvent, for example can be by stirring It is relatively uniform that mode causes that both mix, and mixing time is 15-50min.
In the S3 of above-mentioned preparation method, the mode of dried process can include but is not limited to vacuum and do Dry, inert gas shielding heat drying, spray drying, freeze-drying or expansion drying etc., wherein excellent Elect spray drying as, the condition for being spray-dried is referred to the process conditions of this area conventional selection, Will not be repeated here.
In the S3 of above-mentioned preparation method, the mode for heating does not have particular/special requirement, as long as 3rd drying composite is warming up to 600-750 DEG C of insulation 3-10h.It is preferred in the present invention 3rd drying composite is warming up to 300-500 DEG C with the speed of 2-10 DEG C/min.Second is dried Mixture is warming up to 300-500 DEG C and is conducive to preferably forming amorphous on surface with the speed of 2-10 DEG C/min State clad.
In above-mentioned preparation method of the invention, preferably S1 and S2 whole process is entered in the presence of an inert gas OK.(preparing has noncrystal gold to carry out S1 (preparation active component) and S2 in the presence of an inert gas Belong to the internal coating of compound structure) be conducive to avoiding the introducing of impurity, the prepared iron manganese phosphate of optimization The chemical property of lithium class material.The inert gas that can wherein use includes but is not limited to nitrogen, argon One or more in gas, helium of mixing.
Meanwhile, according to the third aspect of the present invention, a kind of iron manganese phosphate for lithium class material is additionally provided, should Iron manganese phosphate for lithium class material is prepared from by above-mentioned preparation method of the invention.The iron manganese phosphate for lithium class material bag Include with LiMnxFe1-x-yMyPO4The active component of/C-structure, wherein 0≤x≤1,0≤y≤1, M One or more in for Co, Ni, Mg, Zn, V and Ti；And it is wrapped in the active component table The clad containing amorphous metal compound in face.Preferably, the particle diameter D of the active component50For 0.5-1.0 μm, the thickness of the inorganic amorphous material clad is 1-5nm.
Preferably, amorphous metal compound is selected from amorphous state alundum (Al2O3), amorphous in the clad It is state lithium phosphate, amorphous state pyrophosphoric acid lithium, amorphous state ferric pyrophosphate, amorphous state ferrous pyrophosphate lithium, non- One or more mixing in crystalline state manganese pyrophosphate lithium, amorphous state silver oxide
Preferably, the iron manganese phosphate for lithium class material is also coated on the conductive carbon of the cover surface Layer；Preferably, the thickness of the conductive carbon layer is 2-10nm.
Preferably, it is described with LiMnxFe1-x-yMyPO4In the active component of/C-structure, Li and Mn, The mol ratio of Fe and M sums is 0.98-1.02：1；Preferably, C element in the active component Content is the 0.5-3.5wt% of active component gross weight.
In addition, according to the fourth aspect of the present invention, a kind of cell size is additionally provided, the cell size Including iron manganese phosphate for lithium class material and solvent, the iron manganese phosphate for lithium class material is above-mentioned manganese phosphate of the invention Iron lithium class material.The solvent that can be used in above-mentioned cell size including but not limited to water, N- methyl One kind in pyrrolidones.
Do not have special wanting for the solid content of cell size during above-mentioned cell size is prepared Ask, appropriate selection can be carried out according to the use requirement of cell size.Usually, above-mentioned battery slurry Solid content is 30-60wt%, more preferably preferably 40-50wt%, 45-50wt% in material.
Also include solvent, binding agent and conductive agent in the above-mentioned cell size of the present invention.Wherein binding agent, lead The raw material and consumption of electric agent and solvent are referred to this area conventional selection, and such as binding agent can be poly- Vinylidene, 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 binding agent is 80:10:10.The solvent that can be used in above-mentioned cell size includes But it is not limited to one or more in water, ethanol and methyl alcohol.
According to the fifth aspect of the present invention, a kind of positive pole is still further provides, the positive pole includes afflux Body and the anode active material layer being arranged on the collector, the anode active material layer include this Invention iron manganese phosphate for lithium class material.This positive pole provided by the present invention, by using containing of the invention The cell size of iron manganese phosphate for lithium class material is prepared from, in view of iron manganese phosphate for lithium class material of the present invention Water absorption rate is relatively low, and the water absorption rate of the positive pole is relatively low.Preferably, above-mentioned collector is referred to ability The conventional use of conductive metallic material in domain, for example including but not limited to platinum (Pt) paper tinsel, palladium (Pd) paper tinsel, Aluminium (Al) paper tinsel etc..
A kind of lithium battery is still further provides in the present invention, the lithium battery interior is equipped with positive pole, and this is just Extremely above-mentioned positive pole.This lithium battery provided by the present invention, is contained by using provided by the present invention The relatively low positive electrode of water rate so that the moisture remained in battery pole piece is relatively low, particularly exists Under high-temperature storage, reduce moisture and the possibility that irreversible side reaction produces HF compositions occurs with electrolyte Property, it is to avoid the dissolved deterioration consequence of electrode material, improve battery storage at high operating temperatures Capability retention.
Iron manganese phosphate for lithium class material of the present invention is further illustrated below with reference to specific embodiment and comparative example And preparation method thereof with positive pole and lithium battery, and its advantage.
In following preparation example, prepare comparative example, embodiment and comparative example in involved test event and Method of testing is as follows：
In following preparation example and contrast preparation example, using inductively coupled plasma emission spectrography (ICP) To determine the composition of iron manganese phosphate for lithium class material of the present invention；This is observed using transmission electron microscope (TEM) collection of illustrative plates The pattern and particle diameter of invention iron manganese phosphate for lithium class material.
In following preparation example and contrast preparation example, using limited commercially available from the new powder test equipment of Chengdu essence The laser particle analyzer of company come determine iron manganese phosphate for lithium class material of the present invention average grain diameter (volume put down Equal particle diameter).Using front and rear particle diameter method of comparison, and transmission electron microscope (TEM) collection of illustrative plates speculates and observes The thickness of the middle clad of iron manganese phosphate for lithium class material of the present invention.
In following preparation example and contrast preparation example, identical process conditions, bag are used the step of spray drying It is 200-300 DEG C to include EAT, and leaving air temp is 80-200 DEG C.
First, preparation example and contrast preparation example
Preparation example 1
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous state in clad Metallic compound is amorphous state alundum (Al2O3))
(1) weigh 3.69 grams of lithium carbonates, 11.50 grams of ammonium dihydrogen phosphates, 7.98 grams of di-iron trioxides and 1.42 grams of sucrose, add sand mill, and rotating speed is that 2000rpm grinds 3h, and spray drying is protected in nitrogen Under shield, slowly heated up 680 DEG C with the heating rate of 0.1 DEG C/min, constant temperature 5h is naturally cold, is had There is LiFePO4The active component of/C-structure, the particle diameter D of the active component50It is 0.58 μm；
(2) weigh 0.58 gram of nine water aluminum nitrate, add 1L water and 15.75 grams it is above-mentioned with LiFePO4 The active component of structure, stirs 30min, spray drying, under nitrogen protection, with the liter of 30 DEG C/min Warm speed is slowly heated up 500 DEG C, and directly cooling is not incubated, and the oxygen of amorphous state three is formed on active component surface Change two aluminium clads, obtain intermediate product, the wherein thickness of clad is 3.9nm；
(3) 1.16 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying under nitrogen protection, is slowly heated up 700 DEG C with the heating rate of 5 DEG C/min, Constant temperature 3h, cooling obtains final product P1 in intermediate product Surface coating conductive carbon layer, wherein conductive The thickness of carbon-coating is 8.2nm.
(4) using JEOL JEM-2010 (HR) type transmission electron microscope tester to above-mentioned Final product P1 is detected.Test condition：It is 200KV in accelerating potential, vacuum is less than 2×10-5Pa.Method of testing：Final product P1 is scattered in ethanol solution, ultrasonic disperse 30min, It is added dropwise on copper mesh, is vacuum dried 2h.
Test result：The granule-morphology TEM collection of illustrative plates of P1 prepared by preparation example 1 is as shown in figure 1, Fig. 1 In substantially it can be seen that there is two-layer clad on the surface of active component, internal layer is amorphous metal chemical combination Thing clad (water absorption rate is relatively low), outer layer is conductive carbon layer (electric conductivity is preferable), this two-layer clad There are beneficial to promoting prepared iron manganese phosphate lithium material while with relatively low water absorption rate, have Preferable electric conductivity.
Preparation example 2
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state lithium phosphate)
(1) weigh 3.69 grams of lithium carbonates, 11.50 grams of ammonium dihydrogen phosphates, 7.98 grams of di-iron trioxides and 1.42 grams of sucrose, add sand mill, and rotating speed is that 2000rpm grinds 3h, and spray drying is protected in nitrogen Under shield, slowly heated up 800 DEG C with the heating rate of 2 DEG C/min, constant temperature 20h is naturally cold, is had There is LiFePO4The active component of/C-structure, the particle diameter D of the active component50It is 0.61 μm；
(2) 0.16 gram of phosphoric acid (content 85wt%) and 0.17 gram of Lithium hydroxide monohydrate are weighed, is added 1L water and 15.78 grams of above-mentioned active components, stir 30min, are spray-dried, under nitrogen protection, with The heating rate of 80 DEG C/min slowly heats up 300 DEG C, directly cooling is not incubated, in active component surface shape Into amorphous state lithium phosphate clad, intermediate product, the thickness of clad in the intermediate product for being obtained are obtained It is 3.5nm to spend；
(3) 1.16 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 600 DEG C, 10h is incubated, cooling obtains final product P2, and the wherein thickness of conductive carbon layer is 8.2 nm。
Preparation example 3
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state pyrophosphoric acid lithium)
(1) 3.69 grams of lithium carbonates, 18.68 grams of phosphate dihydrate iron and 1.42 grams of sucrose are weighed, sand is added Grinding machine, rotating speed is that 1000rpm grinds 3h, spray drying, under nitrogen protection, with 0.1 DEG C/min's Heating rate slowly heats up 800 DEG C, constant temperature 5h, and naturally cold, obtaining has LiFePO4The work of/C-structure Property component, the particle diameter D of the active component50It is 0.75 μm；
(2) 0.31 gram of phosphoric acid (content 85wt%) and 0.34 gram of lithium hydroxide are weighed, 1L water is added With 15.75 grams of above-mentioned active components, 30min, spray drying, under nitrogen protection, with 30 DEG C are stirred The heating rate of/min slowly heats up 500 DEG C, directly cooling is not incubated and forms amorphous on active component surface State pyrophosphoric acid lithium clad, obtains intermediate product, and the thickness of wherein amorphous state pyrophosphoric acid lithium clad is 2.4nm；
(3) 1.0 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 750 DEG C, constant temperature 6h, cooling obtains final product P3 in intermediate product Surface coating conductive carbon layer, Wherein the thickness of conductive carbon layer is 7.1nm.
Preparation example 4
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferric pyrophosphate)
(1) with step (1) in preparation example 3, obtaining has LiFePO4The active component of/C-structure, The particle diameter D of the active component50It is 0.74 μm；
(2) 0.24 gram of phosphate dihydrate iron is weighed, 1L water and 15.75 grams of above-mentioned active components are added, is stirred 30min is mixed, is spray-dried, under nitrogen protection, slowly heated up with the heating rate of 30 DEG C/min , directly cooling is not incubated and forms amorphous state ferric pyrophosphate clad on active component surface, obtain by 700 DEG C The thickness of intermediate product, wherein clad is 2.1nm；
(3) 1.16 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 700 DEG C, constant temperature 10h, cooling obtains final product P4 in intermediate product Surface coating conductive carbon layer, Wherein the thickness of conductive carbon layer is 7.0nm.
Preparation example 5
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferrous pyrophosphate lithium)
(1) with step (1) in preparation example 3, obtaining has LiFePO4The active component of/C-structure, The particle diameter D of the active component50It is 0.74 μm；
(2) 0.10 gram of phosphate dihydrate iron, 0.08 gram of phosphoric acid (content 85wt%) and 0.02 gram of carbon are weighed Sour lithium, adds 1L water and 15.75 grams of above-mentioned active components, stirs 30min, spray drying, in nitrogen Under protection, slowly heated up 500 DEG C with the heating rate of 30 DEG C/min, directly cooling is not incubated in activearm Divide surface to form amorphous state ferrous pyrophosphate lithium clad, obtain intermediate product, the wherein thickness of clad It is 1.4nm to spend；
(3) 0.50 gram of sucrose is weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 700 DEG C, constant temperature 10h, cooling obtains final product P5 in intermediate product Surface coating conductive carbon layer, Wherein the thickness of conductive carbon layer is 3.5nm.
Preparation example 6
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state manganese pyrophosphate lithium)
(1) with step (1) in preparation example 3, obtaining has LiFePO4The active component of/C-structure, The particle diameter D of the active component50It is 0.75 μm；
(2) 0.12 gram of manganese carbonate, 0.12 gram of phosphoric acid (content 85wt%) and 0.07 gram of lithium carbonate are weighed, 1L water and 15.75 grams of above-mentioned active components are added, 30min, spray drying, in nitrogen protection is stirred Under, slowly heated up 500 DEG C with the heating rate of 30 DEG C/min, directly cooling is not incubated in active component table Face forms amorphous state manganese pyrophosphate lithium clad, obtains intermediate product, and the thickness of wherein clad is 1.4nm；
(3) 1.00 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 700 DEG C, constant temperature 10h, cooling obtains final product P6 in intermediate product Surface coating conductive carbon layer, Wherein the thickness of conductive carbon layer is 7.1nm.
Preparation example 7
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state silver oxide)
(1) with step (1) in preparation example 3, obtaining has LiFePO4The active component of/C-structure, The particle diameter D of the active component50It is 0.75 μm；
(2) 0.08 gram of silver oxide is weighed, 1L water and 15.78 grams of above-mentioned active components, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 30 DEG C/min 500 DEG C, directly cooling is not incubated and forms amorphous state oxidation silver coating on active component surface, in acquisition Between product, wherein the thickness of clad be 1.2nm；
(3) 1.0 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned intermediate products, stirring are added 30min, spray drying, under nitrogen protection, is slowly heated up with the heating rate of 10 DEG C/min 700 DEG C, constant temperature 10h, cooling obtains final product P7 in intermediate product Surface coating conductive carbon layer, Wherein the thickness of conductive carbon layer is 6.0nm.
Preparation example 8
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferric pyrophosphate)
The preparation method of iron manganese phosphate for lithium class material：With reference to preparation example 3, difference is：
(1) 3.69 grams of lithium carbonates, 4.60 grams of manganese carbonates, 9.34 grams of ferric phosphates, 1.19 grams of carbonic acid are weighed Cobalt and 1.42 grams of sucrose, add sand mill, and rotating speed is that 1000rpm grinds 3h, spray drying, in nitrogen Under gas shielded, slowly heated up 750 DEG C with the heating rate of 0.1 DEG C/min, constant temperature 5h is naturally cold, obtains There must be LiMn0.4Fe0.5Co0.1PO4The active component of structure, the particle diameter D of the active component50For 0.76μm；Final product is obtained by the method and is designated as P8.
Preparation example 9
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferric pyrophosphate)
The preparation method of iron manganese phosphate for lithium class material：With reference to preparation example 3, difference is：
In step (1), slowly heated up 800 DEG C with the heating rate of 3 DEG C/min, constant temperature 5h is natural Cold, obtaining has LiFePO4The active component of/C-structure, the particle diameter D of the active component50For 0.77μm.Final product is obtained by the method and is designated as P9.
Preparation example 10-11
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferric pyrophosphate)
The preparation method of iron manganese phosphate for lithium class material：With reference to preparation example 3, difference is：
In step (2), slowly heated up 500 DEG C with the heating rate of 20 and 100 DEG C/min respectively, no Directly cooling forms amorphous state pyrophosphoric acid lithium clad on active component surface for insulation, obtains intermediate product, The thickness of wherein amorphous state pyrophosphoric acid lithium clad is respectively 2.2nm and 2.9nm.Obtained by the method Final product is designated as P10 and P11.
Preparation example 12
For illustrating iron manganese phosphate for lithium class material of the present invention and preparation method thereof (wherein amorphous metal chemical combination Thing is amorphous state ferric pyrophosphate)
The preparation method of iron manganese phosphate for lithium class material：With reference to preparation example 3, difference is：
In step (3), slowly heated up 750 DEG C with the heating rate of 15 DEG C/min, constant temperature 6h, cooling In intermediate product Surface coating conductive carbon layer, final product P12 is obtained, the thickness of wherein conductive carbon layer is 6.8nm.Final product is obtained by the method and is designated as P12.
Contrast preparation example 1
For comparative illustration iron manganese phosphate for lithium class material of the present invention and preparation method thereof
(1) with step (1) in embodiment 1, obtaining has LiFePO4The active component of structure；
(2) 1.16 grams of sucrose are weighed, 100mL water and 15.75 grams of above-mentioned active components, stirring are added 30min, spray drying under nitrogen protection, is slowly heated up 700 DEG C with the heating rate of 5 DEG C/min, Constant temperature 3h, cooling obtains final product DP1.
(3) using JEOL JEM-2010 (HR) type transmission electron microscope tester to above-mentioned Final product P1 is detected.Test condition：It is 200KV in accelerating potential, vacuum is less than 2×10-5Pa.Method of testing：Final product DP1 is scattered in ethanol solution, ultrasonic disperse 30min, It is added dropwise on copper mesh, is vacuum dried 2h.
Test result：Contrast preparation example 1 prepare DP1 granule-morphology TEM collection of illustrative plates as shown in Fig. 2 Substantially can see in fig. 2 has one layer of conductive carbon layer clad on the surface of active component, wherein simultaneously In the absence of amorphous metal compound clad.Iron manganese phosphate lithium material with this structure is although increase The thickness of conductive carbon layer, but do not exist amorphous metal compound clad wherein, when it is contacted with water, Moisture is still readily permeable to be combined through carbon-coating with the Li of material internal.
Contrast preparation example 2
With reference to prepared by method in the Chinese patent application embodiment 1 of Application No. 200910053346 Iron manganese phosphate for lithium class material, is designated as DP2.
Contrast preparation example 3
With reference to prepared by method in embodiment 1 in the Chinese patent application of Application No. 200910044154 Iron manganese phosphate for lithium class material, be designated as DP3.
2nd, embodiment 1-12 and comparative example 1-3
For illustrating positive pole of the present invention and preparation method thereof.
Preparation method：Iron manganese phosphate for lithium class material, acetylene black, Kynoar (are celebrated purchased from Dongguan City Rich plastic material Co., Ltd, the trade mark is FR900) by weight it is 80:10:10 are dissolved in N- methyl pyrroles It is the cell size of 50wt% that solid content is formed in pyrrolidone, and the slurry obtained after stirring is applied Apply on the aluminium foil that thickness is 25 μm, and toasted at 110 DEG C ± 5 DEG C, it is 20 μm to form thickness Material layer, obtains positive electrode.Prepared positive pole and iron manganese phosphate for lithium class material contained therein Contrast relationship it is as shown in table 1.
Table 1.
Positive electrode Iron manganese phosphate for lithium class material Positive electrode Iron manganese phosphate for lithium class material
S1 P1 S2 P2
S3 P3 S4 P4
S5 P5 S6 P6
S7 P7 S8 P8
S9 P9 S10 P10
S11 P11 S12 P12
DS1 DP1 DS2 DP2
DS3 DP3
Test：
Iron manganese phosphate for lithium class material prepared by difference preparation example 1-12 of the present invention and contrast preparation example 1-3 P1-P12 and DP1-DP3, and to the positive pole prepared by embodiment of the present invention 1-12 and comparative example 1-3 S1-S12 and DS1-DS12 carries out performance test.
(1) moisture content of iron manganese phosphate for lithium class material：According to preparation example 1 to 12 and contrast preparation example 1 Method prepares iron manganese phosphate for lithium class material, and the directly test iron manganese phosphate for lithium class after sintering is come out of the stove into 3 The moisture content of material.
Method of testing includes：First blank testing bottle moisture M0, then sample 0.2g is weighed, in air Under conditions of flow velocity degree 40ml/min, with the heating rate of 15 DEG C/min, 200 DEG C are warmed up to, obtained Total moisture content M1, then, and the moisture content M2=M1-M0 of iron manganese phosphate for lithium class material.
Test result：As shown in table 2：
Table 2
Embodiment Moisture content (ppm) Embodiment Moisture content (ppm)
P1 980.4 P2 863.7
P3 250.3 P4 525.2
P5 343.3 P6 344.6
P7 350.0 P8 258.3
P9 325.6 P10 550.0
P11 725.0 P12 601.2
DP1 3860 DP2 2068.3
DP3 2845.2
(2) moisture content (equivalent to the water absorption rate of iron manganese phosphate for lithium class material) of positive pole：By preparation example 1 Prepared iron manganese phosphate for lithium class material is within the identical time cycle into 12 and contrast preparation example 1 to 3 Within be prepared into after positive pole the moisture content for measuring positive pole S1-S12 and DS1-DS3.
Method of testing includes：First blank testing bottle moisture N0, then sample 0.2g is weighed, in air Under conditions of flow velocity degree 40ml/min, with the heating rate of 15 DEG C/min, 200 DEG C are warmed up to, obtained Total moisture content N1, then the water absorption rate N2=N1-N0-M2 of iron manganese phosphate for lithium class material, wherein M2 It is the moisture content of iron manganese phosphate for lithium class material.
Test result：As shown in table 3：
Table 3.
Embodiment Moisture content (%) Embodiment Moisture content (%)
S1 876.5 S2 1106.4
S3 412.7 S4 875.4
S5 572.1 S6 574.3
S7 583.3 S8 418.7
S9 1041.7 S10 916.7
S11 1208.3 S12 1002.3
DS1 2880.2 DS2 2106.4
DS3 3670.4
Be can be seen that by data in table 2 and table 3：By the embodiment 1 to 12 of method produced according to the present invention All than relatively low, it is substantially better than by contrasting the moisture content and water absorption rate of prepared iron manganese phosphate for lithium class material The moisture content and water absorption rate of the iron manganese phosphate for lithium class material prepared by example 1-3 are all.
3rd, implementation of an application example 1-12 and contrast application examples 1-3
For illustrating lithium battery of the present invention and preparation method thereof.
Preparation method：Positive pole S1-S12 prepared by implementation of an application example 1-12 and comparative example 1-3 and DS1-DS3 makes lithium ion monolithic battery T1-T12 and DT1-DT3, negative pole material in made battery Expect to be graphite, diaphragm material is that (Kynoar is fluorinated work to PVDF commercially available from A Kema (Changshu) Co., Ltd's trade mark is the product of PVDF HSV900), electrolyte is 1mol/LLiPF6/ (EC+DMC) (wherein LiPF6 is lithium hexafluoro phosphate, and EC is ethylene carbonate, and DMC is carbonic acid Dimethyl ester, the volume ratio of EC and DMC is 1:1).
Prepared lithium battery and the contrast relationship of positive electrode contained therein are as shown in table 4.
Table 4.
Positive electrode Iron manganese phosphate for lithium class material Positive electrode Iron manganese phosphate for lithium class material
T1 S1 T2 S2
T3 S3 T4 S4
T5 S5 T6 S6
T7 S7 T8 S8
T9 S9 T10 S10
T11 S11 T12 S12
DT1 DS1 DT2 DS2
DT3 DS3
Test：
Respectively to the lithium battery T1-T12 prepared by implementation of an application example 1-12 and contrast application examples 1-3 and DT1-DT3 carries out performance test.
(1) test event and method：
1., specific discharge capacity：Lithium ion battery obtained above is individually placed in test cabinet, first with 0.1C carries out constant-current constant-voltage charging, and chargeable range is 2.5-4.35V, and the electric discharge first for recording battery is held Amount, records the discharge capacity of battery again, and calculates the specific discharge capacity of battery according to the following equation.
Specific discharge capacity=battery discharge capacity (MAH)/positive electrode weight (gram) first.
2., 25 days capability retentions of (60 DEG C) storages of the high temperature of lithium battery：First by battery in 0.1C electricity Flow down discharge and recharge one week, record discharge capacity C0；Again by battery under the 0.1C it is fully charged after in 65 DEG C of bakings After case high temperature is stored 7 days, after taking out battery cooling, discharge into by voltage 2.5V, record is remaining to be held C1 is measured, then high temperature capability retention=(C0/C1) * 100%.
(3) test result：As shown in table 5：
Table 5.
Be can be seen that as the electricity according to prepared by implementation of an application example 1 to 12 of the present invention as data in table 5 The initial capacity of pond T1-T3 produces harmful effect (referring to specific discharge capacity data), and with excellent High temperature capability retention；And the battery DT1-DT3's according to prepared by contrast application examples 1 to 3 is initial Capacity have received obvious influence, and high temperature capability retention is not also relatively good.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention is not It is limited to the detail in above-mentioned implementation method, in range of the technology design of the invention, can be to this The technical scheme of invention carries out various simple variants, and these simple variants belong to protection model of the invention Enclose.
It is further to note that each particular technique described in above-mentioned specific embodiment is special Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid not Necessary repetition, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as , without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention for it.

Claims (19)

1. a kind of iron manganese phosphate for lithium class material, it is characterised in that the iron manganese phosphate for lithium class material includes With LiMnxFe1-x-yMyPO4The active component of/C-structure, wherein 0≤x≤1,0≤y≤1, M is One or more in Co, Ni, Mg, Zn, V and Ti；And it is wrapped in the active component surface Clad, the clad contains amorphous metal compound.
2. iron manganese phosphate for lithium class material according to claim 1, wherein, the active component Particle diameter D50It it is 0.5-1.0 μm, the thickness of the clad is 1-5nm.
3. iron manganese phosphate for lithium class material according to claim 1, wherein, the amorphous metal Compound is selected from amorphous state alundum (Al2O3), amorphous state lithium phosphate, amorphous state pyrophosphoric acid lithium, amorphous state In ferric pyrophosphate, amorphous state ferrous pyrophosphate lithium, amorphous state manganese pyrophosphate lithium and amorphous state silver oxide One or more mixing.
4. iron manganese phosphate for lithium class material according to claim 1 and 2, wherein, the manganese phosphate Iron lithium class material is also coated on the conductive carbon layer of the cover surface.
5. iron manganese phosphate for lithium class material according to claim 4, wherein, the conductive carbon layer Thickness is 2-10nm.
6. iron manganese phosphate for lithium class material according to claim 1, wherein, it is described to have LiMnxFe1-x-yMyPO4In the active component of/C-structure, the mol ratio of Li and Mn, Fe and M sum It is 0.98-1.02：1；
It is preferred that the content of C element is the 0.5-3.5wt% of active component gross weight in the active component.
7. a kind of preparation method of lithium ferric manganese phosphate class material, it is characterised in that the preparation method bag Include following steps：
S1, offer have LiMnxFe1-x-yMyPO4The active component of/C-structure, wherein 0≤x≤1,0 ≤ y≤1, M is one or more in Co, Ni, Mg, Zn, V and Ti；
S2, with the active component as base material, the active component surface formed contain amorphous state The clad of metallic compound.
8. preparation method according to claim 7, wherein, the preparation of active component in the S1 Method is comprised the following steps：
S11, by lithium source, optional source of iron, optional manganese source, optional M sources, phosphorus source and the first carbon Source mixes in proportion, and the first drying composite is obtained after drying；
S12, by first drying composite at 600-800 DEG C, Isothermal sinter 5-30h forms described Active component.
9. preparation method according to claim 8, wherein, it is dry by described first in the S12 Dry mixture is warming up to 600-800 DEG C with the speed of 0.1-2 DEG C/min.
10. preparation method according to claim 8, wherein, in the S11, lithium source is with Li Count and be with optional source of iron, optional manganese source, optional M sources mol ratio in terms of Fe+Mn+M total amounts 0.98-1.02：1；
It is preferred that the consumption in the C sources is so that the content of C element is active component gross weight in active component The 0.5-3.5wt% of amount.
11. preparation methods according to claim 7, wherein, the S2 is comprised the following steps：
S21, the active component is mixed with the material source for forming the amorphous metal compound, Dry, obtain the second drying composite；
S22, second drying composite is warming up to 300-500 DEG C does not carry out being incubated directly cooling, with The clad containing amorphous metal compound is formed on the surface of the active component.
12. preparation methods according to claim 11, wherein, by described second in the S22 Drying composite is warming up to 300-500 DEG C with the speed of 30-80 DEG C/min.
13. preparation methods according to claim 11, wherein, the clad that the S2 is formed In, the amorphous metal compound is selected from amorphous state alundum (Al2O3), amorphous state lithium phosphate, amorphous state Pyrophosphoric acid lithium, amorphous state ferric pyrophosphate, amorphous state ferrous pyrophosphate lithium, amorphous state manganese pyrophosphate lithium, One or more mixing in amorphous state silver oxide.
14. preparation methods according to claim 7, wherein, the preparation method also includes following Step：
S3, the intermediate product that will be obtained in S2 mix with second carbon source, are dried to obtain the 3rd dry mixed Thing, after the 3rd drying composite is warming up into 600-750 DEG C, 3-10h is with the centre for insulation The surface of product forms conductive carbon layer.
15. preparation methods according to claim 14, wherein, the drying is mixed in the S3 Compound is warming up to 600-750 DEG C with the speed of 2-10 DEG C/min.
A kind of 16. iron manganese phosphate for lithium class materials, it is characterised in that the iron manganese phosphate for lithium class material by Preparation method in claim 7 to 15 described in any one is prepared from.
A kind of 17. cell sizes, the cell size includes iron manganese phosphate for lithium class material and solvent, its It is characterised by, the iron manganese phosphate for lithium class material is any one institute in claim 1 to 6 and 16 The iron manganese phosphate for lithium class material stated.
A kind of 18. positive poles, the positive pole includes that collector and the positive pole being arranged on the collector are lived Property material layer, it is characterised in that the anode active material layer include claim 1 to 6 and 16 Iron manganese phosphate for lithium class material described in middle any one.
A kind of 19. lithium batteries, the lithium battery interior is equipped with positive pole, it is characterised in that the positive pole Material includes the positive pole described in claim 18.
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