CN106340646A - Spherical multiphase LiMnFePO4 material and preparation method thereof - Google Patents

Spherical multiphase LiMnFePO4 material and preparation method thereof Download PDF

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CN106340646A
CN106340646A CN201610843105.2A CN201610843105A CN106340646A CN 106340646 A CN106340646 A CN 106340646A CN 201610843105 A CN201610843105 A CN 201610843105A CN 106340646 A CN106340646 A CN 106340646A
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lithium
calcium phosphate
multiple phase
phase calcium
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CN106340646B (en
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计佳佳
汪志全
齐美洲
陈勇
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a spherical multiphase LiMnFePO4 material and a preparation method of the spherical multiphase LiMnFePO4 material, and belongs to the field of anode materials for lithium ion cells. The spherical multiphase LiMnFePO4 material is prepared by using a high-temperature solid phase method. An iron source, a phosphorus source, a lithium source, a manganese source, a dopant and a dispersant are added to a proper amount of organic solvents, and prepared into homogeneous slurries by using a double-screw mixer, and then subjected to rotary evaporation and dried, and further presintered at low temperature; presintering materials and a proper amount of organic carbon sources and CNT are added to a water solvent, and mixed and ground, and then subjected to spray pelletization, finally sintered between the temperature of 675 to 725 DEG C under inert atmosphere to prepare the required spherical multiphase LiMnFePO4 material. According to the invention, the adding proportions of control elements are controlled, so that (LiMnxFe1-X-YMyPO4). (Li4P2O7)z or (LiMnxFe1-X-YMyPO4).(Li3PO4)z multiphase material is formed after the high-temperature reaction, and the spherical multiphase LiMnFePO4 material further contains a CNT conductive network, so that the Li<+> migration rate can be improved, and the tap density for the spherical material can be further improved; furthermore, the spherical multiphase LiMnFePO4 material is simple in process, mature in technology, rich in raw materiasl and easy in industrialization.

Description

A kind of spherical multiple phase calcium phosphate ferromanganese lithium material and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery is and in particular to a kind of spherical multiple phase calcium phosphate ferromanganese lithium material and its preparation side Method.
Background technology
Under low-carbon economy, the overall situation of energy-saving and emission-reduction, new-energy automobile represents the developing direction of future automobile industry, It is the ground zero that Chinese Automobile Industry ' catches up with and surpasses World Auto Industry.Lithium ion battery is one of new-energy automobile major impetus, newly Energy automobile industrialization will directly drive lithium ion battery market rapid growth, along with traditional consumer electronics, electric tool With the day by day expansion to lithium ion battery demand of electric bicycle and new forms of energy energy-storage system, lithium ion battery and its material city Field space is huge.
The phosphate-based positive electrode of olivine-type structure is better than traditional layer at the aspect such as security performance and cycle life Shape structure positive electrode (as cobalt acid lithium, lithium nickelate, ternary material), its representative materials LiFePO4 (lifepo4) learned Art circle and the widely studied confirmation of industrial circle, and it is widely used in the fields such as power and energy-storage battery.However, LiFePO4 3.4v (vs.li/li+) current potential limits the lifting of battery energy density, therefore limited by lithium iron phosphate dynamic battery market development.With LiFePO4 (lifepo4) compare, iron manganese phosphate for lithium (limnfepo4) have 4.0v about high potential and almost identical reason By capacity, under conditions of equivalent capability plays, the energy density of iron manganese phosphate lithium battery will improve than ferric phosphate lithium cell 20% about.Therefore, in the world iron manganese phosphate for lithium is classified as high-energy-density power lithium-ion battery positive electrode of new generation.But It is that iron manganese phosphate for lithium there is also the problem of itself such as electrical conductivity and cycle performance difference.
Content of the invention
The present invention is directed to the deficiencies in the prior art, provides a kind of spherical multiple phase calcium phosphate ferromanganese lithium material and preparation method thereof. In order to improve electric conductivity, the present invention by between particle and particle introduce CNT (cnt) conductive carbon be used as electronics bridge with And introduce lithium fast-ionic conductor raising ionic conductivity, thus to improve material property.
For solving above-mentioned technical problem, the present invention following technical scheme of offer:
A kind of spherical multiple phase calcium phosphate ferromanganese lithium material, described material be iron manganese phosphate for lithium main body base material in be compounded with lithium soon from Sub- conductor and CNT cnt conductive network.
A kind of method preparing spherical multiple phase calcium phosphate ferromanganese lithium material, comprises the following steps:
(1) source of iron, lithium source, phosphorus source, manganese source, doped chemical are pressed (limnxfe1-x-ymypo4)·(li4p2o7) z or (limnxfe1-x-ymypo4)·(li3po4) z recipe ratio mixing, wherein 0.6≤x≤0.9,0.01≤y≤0.02,0.01≤z ≤ 0.03, and add dispersant and organic solvent, grind and obtain slurry；
(2) by slurry drying in step (1), form small particles material；
(3) by step (2) small particles material 350-400 DEG C of pre-burning 6-8h under an inert atmosphere, obtain pre-burning thing；
(4) pre-burning thing, organic carbon source and diameter in step (3) are not more than the cnt mixed grinding of 10nm, then are sprayed It is dried, make spheroidization secondary agglomeration body material；
(5) the secondary agglomeration body material of spheroidization in step (4) is sintered for 675-725 DEG C in inert atmosphere roller kilns 8h, obtains spherical multiple phase calcium phosphate ferromanganese lithium material.
Further, in described step (1), dispersant addition is the 3-5% of phosphorus source, source of iron and manganese source quality sum, organic Solvent adding amount is the 130-180% of phosphorus source, source of iron and manganese source quality sum.
Further, the particle diameter of described step (2) small particles material is less than 5mm.
Further, in described step (3), pre-burning thing, the organic carbon source and diameter no more than cnt mixed grinding of 10nm is extremely flat All particle diameter d50 is less than 200nm, and the diameter of spheroidization secondary agglomeration body material is between 10-25 μm.
Further, grind in described step (4) and include being not more than pre-burning thing, organic carbon source and diameter in step (3) After the cnt of 10nm throws corase grind 1h in the Ball-stirring mill containing zirconia ball, proceed to fine grinding 3h in sand mill little to mean diameter d50 In 200nm.
Further, the lithium source in described step (1) be one of lithium carbonate, Quilonorm (SKB), lithium dihydrogen phosphate or two kinds with On mixture.
Further, the source of iron in described step (1) is one of ferrous acetate, Ferrox., ferric citrate or two kinds Above mixture.
Further, the phosphorus source in described step (1) is one of lithium dihydrogen phosphate, ammonium dihydrogen phosphate or two or more Mixture.
Further, the manganese source in described step (1) is one of manganese acetate, manganese oxalate, manganese carbonate or two or more Mixture.
Further, doped chemical m in described step (1) is one of mg, co, ti, v or two or more mixing Thing.
Further, the organic solvent in described step (1) be ethanol, methanol, isopropanol, n-butyl alcohol, ether, in acetone One or more mixture.
Further, the dispersant in described step (1) be PEG-6000, PEG-4000, Polyethylene Glycol- 2000th, PEG-4000, PEG-4000, one or more mixture in PEG-400.
Further, in described step (3) and (5), inert atmosphere is one of nitrogen, argon, helium or two or more Gaseous mixture.
Further, in described step (4), organic carbon source is one of sucrose, glucose, Fructose, starch or two or more Mixture.
The present invention has the following technical effect that
Lithium fast-ionic conductor has higher ionic conductivity, can increase the diffusion rate of lithium ion；Cnt conductive mesh will Multiple phase calcium phosphate ferromanganese lithium material is internally connected with each other, and forms the electronics bridge of three-D space structure, and cnt conductive mesh intensity Height, reduces the situation of multiple phase calcium phosphate ferromanganese lithium material flexible conductive network rupture leading in charge and discharge process, multiple phase calcium phosphate The li of ferromanganese lithium material+Migration rate and electric conductivity are all greatly improved.Electrical property in half-cell is compared with efficiency first Improve a lot in pure phase iron manganese phosphate lithium material.Multiple phase calcium phosphate ferromanganese lithium material shape spherical in shape, can improve tap density, processing Performance has lifting.The process route process is simple of the high temperature solid-state method adopting in the present invention, technology maturation, abundant raw material, Yi Gong Industry.
Brief description
Fig. 1 is the preparation technology flow chart of the present invention；
Fig. 2 is the spherical multiple phase calcium phosphate ferromanganese lithium material containing fast-ionic conductor and cnt conductive network, and without fast ion Sem microscopic comparison's piece of the pure phase iron manganese phosphate lithium material of conductor and cnt conductive network；
Fig. 3 is the xrd collection of illustrative plates of the spherical multiple phase calcium phosphate ferromanganese lithium material of embodiment 1 preparation.
Specific embodiment
In order that the purpose of the present invention, technical scheme and advantage become more apparent, below in conjunction with accompanying drawing and specifically Embodiment, is described in further detail to the present invention.Drawings and Examples are only used for explaining the present invention, are not used to limit this Bright.Those skilled in the art makes various modifications on the basis of the present invention, is regarded as the protection model of the present invention Enclose.
Multiple phase calcium phosphate ferromanganese lithium material is spherical in shape, and be compounded with iron manganese phosphate for lithium main body base material lithium fast-ionic conductor and CNT cnt conductive network.
Embodiment 1
A kind of multiple phase calcium phosphate ferromanganese lithium material, its bulk composition is iron manganese phosphate for lithium, containing lithium phosphate or pyrophosphoric acid lithium this Class lithium fast-ionic conductor, and have cnt conductive network.
Preparation method as shown in figure 1: raw and auxiliary material: small particles material: pre-burning thing: be spray-dried reunite Body: finished product after sintering, preparation process is as follows:
1. the raw materials such as ammonium dihydrogen phosphate, manganese acetate, ferrous acetate, magnesium acetate, isopropyl titanate, lithium carbonate are pressed li:mn: The molar ratio ingredient of fe:co:mg:ti:p=1.04:0.7:0.28:0.01:0.01:1.02, PEG-6000 addition is The 3% of phosphorus source, source of iron and manganese source quality sum, alcohol solvent addition is phosphorus source, source of iron and manganese source quality sum 130% plus Enter mixing, ball milling 2h in twin-screw compounder, solid content is designed as 40%, forms uniform slurry, tired in size distribution curve D50=9 μm of the equivalent diameter of the long-pending the largest particles being distributed as when 50%, in size distribution curve, cumulative distribution is when 100% D100=50 μm of the equivalent diameter of the largest particles；
2. gained slurry in step 1 is transferred in rotary evaporator and is dried, heating in water bath to 90 DEG C, rotary evaporation After 3h, slurry becomes the solid granulates that particle diameter is less than 5mm；
3. take particulate matter in step 2 to carry out 400 DEG C of pre-burning 6h in the batch-type furnace having nitrogen protection, obtain pre-burning thing；
4. take gained pre-burning thing 1kg in step 3, collocation 100g sucrose and the cnt water system slurry that 100g mass fraction is 5% Material, adds stirring corase grind 1h in the Ball-stirring mill containing 1.8kg deionized water, d100 < 20 μm, is transferred to containing 0.2mm zirconium oxide Fine grinding 3h in the sand mill of ball, obtains the uniform sizing material of d50=197nm；
5. gained slurry in step 4 is spray-dried, controls secondary agglomeration body material meso-position radius to be 20 μm about；
6. the secondary agglomeration body material taking preparation in step 5 is placed in the tunnel cave containing nitrogen atmosphere 675 DEG C of sintering 8h, Can get required multiple phase calcium phosphate ferromanganese lithium material.
Embodiment 2
A kind of spherical multiple phase calcium phosphate ferromanganese lithium material, its bulk composition is iron manganese phosphate for lithium, containing lithium phosphate or pyrophosphoric acid This kind of lithium fast-ionic conductor of lithium, and have cnt conductive network.
Preparation method step is as follows:
1. the raw materials such as ammonium di-hydrogen phosphate, manganese acetate, ferric citrate, butyl titanate, lithium carbonate are pressed li:mn:fe:ti:p The molar ratio ingredient of=1.08:0.8:0.175:0.025:1.04, PEG-6000 addition is phosphorus source, source of iron and manganese source The 5% of quality sum, methanol solvate addition is 180% addition twin-screw compounder of phosphorus source, source of iron and manganese source quality sum Middle mixing, ball milling 2h, solid content is designed as 40%, forms uniform slurry, d50=9.5 μm, d100=55 μm；
2. gained slurry in step 1 is transferred in rotary evaporator and is dried, heating in water bath to 90 DEG C, rotary evaporation After 3h, slurry becomes the solid granulates that particle diameter is less than 5mm；
3. take particulate matter in step 2 to carry out 350 DEG C of pre-burning 8h in the batch-type furnace having nitrogen protection, obtain pre-burning thing；
4. take gained pre-burning thing 1kg in step 3, collocation 75g Fructose and the cnt aqueous slurry that 100g mass fraction is 5%, Add stirring corase grind 1h in the Ball-stirring mill containing 1.8kg deionized water, d100 < 20 μm, be transferred to containing 0.2mm zirconia ball Fine grinding 3h in sand mill, obtains the uniform sizing material of d50=199nm；
5. gained slurry in step 4 is spray-dried, controls secondary agglomeration body material meso-position radius to be 20 μm about；
6. the secondary agglomeration body material taking preparation in step 5 is placed in the tunnel cave containing nitrogen atmosphere 700 DEG C of sintering 8h, Can get required multiple phase calcium phosphate ferromanganese lithium material.
Embodiment 3
A kind of spherical multiple phase calcium phosphate ferromanganese lithium material, its bulk composition is iron manganese phosphate for lithium, containing lithium phosphate or pyrophosphoric acid Lithium lithium fast-ionic conductor, and have cnt conductive network.
Preparation method step is as follows:
1. the raw materials such as ammonium di-hydrogen phosphate, manganese carbonate, Ferrox., magnesium acetate, butyl titanate, lithium carbonate are pressed li:mn: The molar ratio ingredient of fe:mg:ti:p=1.1:0.8:0.18:0.01:0.01:1.05, PEG-6000 addition is phosphorus The 4% of source, source of iron and manganese source quality sum, alcohol solvent addition is 150% addition of phosphorus source, source of iron and manganese source quality sum Mixing, ball milling 2h in twin-screw compounder, solid content is designed as 40%, forms uniform slurry, d50=10 μm, d100=61 μ m；
2. gained slurry in step 1 is transferred in rotary evaporator and is dried, heating in water bath to 90 DEG C, rotary evaporation After 3h, slurry becomes the solid granulates that particle diameter is less than 5mm；
3. take particulate matter in step 2 to carry out 375 DEG C of pre-burning 6h in the batch-type furnace having nitrogen protection, obtain pre-burning thing；
4. take gained pre-burning thing 1kg in step 3, collocation 100g glucose and the cnt water system slurry that 100g mass fraction is 5% Material, adds stirring corase grind 1h in the Ball-stirring mill containing 1.8kg deionized water, d100 < 20 μm, is transferred to containing 0.2mm zirconium oxide Fine grinding 3h in the sand mill of ball, obtains the uniform sizing material of d50=189nm；
5. gained slurry in step 4 is spray-dried, controls secondary agglomeration body material meso-position radius to be 20 μm about；
6. the secondary agglomeration body material taking preparation in step 5 is placed in the tunnel cave containing nitrogen atmosphere 725 DEG C of sintering 8h, Can get required multiple phase calcium phosphate ferromanganese lithium material.
Embodiment 4
A kind of spherical multiple phase calcium phosphate ferromanganese lithium material, its bulk composition is iron manganese phosphate for lithium, containing lithium phosphate or pyrophosphoric acid Lithium lithium fast-ionic conductor, and have cnt conductive network.
Preparation method step is as follows:
1. will be former to lithium dihydrogen phosphate, manganese carbonate, ferric citrate, vanadic anhydride, magnesium acetate, isopropyl titanate, lithium carbonate etc. Material presses the molar ratio ingredient of li:mn:fe:v:mg:ti:p=1.06:0.7:0.28:0.003:0.008:0.009:1.02, poly- second Glycol -1000 addition is the 5% of phosphorus source, source of iron and manganese source quality sum, and alcohol solvent addition is phosphorus source, source of iron and manganese source Mixing, ball milling 2h in 180% addition twin-screw compounder of quality sum, solid content is designed as 40%, forms uniform slurry, D50=9 μm, d100=48 μm；
2. gained slurry in step 1 is transferred in rotary evaporator and is dried, heating in water bath to 90 DEG C, rotary evaporation After 3h, slurry becomes the solid granulates that particle diameter is less than 5mm；
3. take particulate matter in step 2 to carry out 400 DEG C of pre-burning 6h in the batch-type furnace having nitrogen protection, obtain pre-burning thing；
4. take gained pre-burning thing 1kg in step 3, collocation 100g sucrose and the cnt water system slurry that 100g mass fraction is 5% Material, adds stirring corase grind 1h in the Ball-stirring mill containing 1.8kg deionized water, d100 < 20 μm, is transferred to containing 0.2mm zirconium oxide Fine grinding 3h in the sand mill of ball, obtains the uniform sizing material of d50=191nm；
5. gained slurry in step 4 is spray-dried, controls secondary agglomeration body material meso-position radius to be 20 μm about；
6. the secondary agglomeration body material taking preparation in step 5 is placed in the tunnel cave containing nitrogen atmosphere 725 DEG C of sintering 8h, Can get required multiple phase calcium phosphate ferromanganese lithium material.
Embodiment 5
A kind of spherical multiple phase calcium phosphate ferromanganese lithium material containing lithium fast-ionic conductor, its bulk composition is iron manganese phosphate for lithium, contains There are lithium phosphate or this kind of lithium fast-ionic conductor of pyrophosphoric acid lithium, but no cnt conductive network.
Preparation method step is as follows:
1. will be former to lithium dihydrogen phosphate, manganese carbonate, ferric citrate, vanadic anhydride, magnesium acetate, isopropyl titanate, lithium carbonate etc. Material presses the molar ratio ingredient of li:mn:fe:v:mg:ti:p=1.06:0.7:0.28:0.003:0.008:0.009:1.02, poly- second Glycol -1000 addition is the 5% of phosphorus source, source of iron and manganese source quality sum, and alcohol solvent addition is phosphorus source, source of iron and manganese source Mixing, ball milling 2h in 180% addition twin-screw compounder of quality sum, solid content is designed as 40%, forms uniform slurry, D50=9 μm, d100=48 μm；
2. gained slurry in step 1 is transferred in rotary evaporator and is dried, heating in water bath to 90 DEG C, rotary evaporation After 3h, slurry becomes the solid granulates that particle diameter is less than 5mm；
3. take particulate matter in step 2 to carry out 400 DEG C of pre-burning 6h in the batch-type furnace having nitrogen protection, obtain pre-burning thing；
4. take gained pre-burning thing 1kg in step 3,100g sucrose of arranging in pairs or groups, add in the Ball-stirring mill containing 1.8kg deionized water Stirring corase grind 1h, is transferred to fine grinding 3h in the sand mill containing 0.2mm zirconia ball, obtains d50=191nm's by d100 < 20 μm Uniform sizing material；
5. gained slurry in step 4 is spray-dried, controls secondary agglomeration body material sphere diameter to be less than 20 μm；
6. the secondary agglomeration body material taking preparation in step 5 is placed in the tunnel cave containing nitrogen atmosphere 725 DEG C of sintering 8h, Can get required multiple phase calcium phosphate ferromanganese lithium material.
Table 1 be embodiment 1,4,5 in preparation the spherical multiple phase calcium phosphate ferromanganese lithium material sample containing lithium fast-ionic conductor with Pure phase iron manganese phosphate for lithium materials control sample electrical property correction data in half-cell.
Table 1
0.2c d 1c d Efficiency first Remarks
sample 1 147mah/g 140mah/g 95.3% Embodiment 1 sample
sample 4 145mah/g 140mah/g 95.6% Embodiment 4 sample
sample 5 138mah/g 130mah/g 94.3% Embodiment 5 sample
sample 0 131mah/g 123mah/g 90.1% Control sample
Result in table 1 show electrical property in half-cell for the embodiment 1,4 and 5 and first efficiency be superior to control sample Product.
Fig. 2 is the spherical multiple phase calcium phosphate ferromanganese lithium material containing fast-ionic conductor and cnt conductive network, and without fast ion Sem microscopic comparison's piece of the pure phase iron manganese phosphate lithium material of conductor and cnt conductive network.Sample0 is all without fast ion The sem electron microscope of the pure phase iron manganese phosphate lithium material of conductor and cnt conductive network；Sample3-1 is containing of embodiment 3 preparation Sem electron microscope under high power lenses for the multiple phase calcium phosphate ferromanganese lithium material of fast-ionic conductor and cnt conductive network；Sample3-2 is Sem electricity under low power lens for the multiple phase calcium phosphate ferromanganese lithium material containing fast-ionic conductor and cnt conductive network of embodiment 3 preparation Mirror figure.
Fig. 3 is the xrd collection of illustrative plates of the spherical multiple phase calcium phosphate ferromanganese lithium material of embodiment 1 preparation, can be seen that ball from collection of illustrative plates There is li in shape multiple phase calcium phosphate ferromanganese lithium material3po4Lithium fast-ionic conductor.

Claims (16)

1. a kind of spherical multiple phase calcium phosphate ferromanganese lithium material is it is characterised in that described material is multiple in iron manganese phosphate for lithium main body base material Conjunction has lithium fast-ionic conductor and CNT cnt conductive network.
2. a kind of method preparing spherical multiple phase calcium phosphate ferromanganese lithium material is it is characterised in that comprise the following steps:
(1) source of iron, lithium source, phosphorus source, manganese source, doped chemical are pressed (limnxfe1-x-ymypo4)·(li4p2o7) z or (limnxfe1-x-ymypo4)·(li3po4) z recipe ratio mixing, wherein 0.6≤x≤0.9,0.01≤y≤0.02,0.01≤z ≤ 0.03, and add dispersant and organic solvent, grind and obtain slurry；
(2) by slurry drying in step (1), form small particles material；
(3) by step (2) small particles material 350-400 DEG C of pre-burning 6-8 h under an inert atmosphere, obtain pre-burning thing；
(4) pre-burning thing, organic carbon source and diameter in step (3) are not more than the cnt mixed grinding of 10 nm, then carry out spray dried Dry, make spheroidization secondary agglomeration body material；
(5) the secondary agglomeration body material of spheroidization in step (4) is sintered 8 h for 675-725 DEG C in inert atmosphere roller kilns, Obtain spherical multiple phase calcium phosphate ferromanganese lithium material.
3. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (1) in dispersant addition be phosphorus source, source of iron and manganese source quality sum 3-5 %, organic solvent addition be phosphorus source, source of iron with The 130-180 % of manganese source quality sum.
4. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (2) particle diameter of small particles material is less than 5 mm.
5. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (3) in, pre-burning thing, the organic carbon source and diameter no more than cnt mixed grinding of 10 nm is less than 200 nm, ball to mean diameter d50 The diameter of shape secondary agglomeration body material is between 10-25 μm.
6. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (4) in, between 5-12 %, cnt is 0.2-0.5 % with the mass ratio of pre-burning thing to the mass ratio of organic carbon source and pre-burning thing.
7. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (4) grind the cnt including that pre-burning thing, organic carbon source and diameter in step (3) are not more than 10 nm in and throw in containing zirconia ball Ball-stirring mill in roughly grind 1 h after, proceed in sand mill fine grinding 3 h and be less than 200 nm to mean diameter d50.
8. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (1) lithium source in is one of lithium carbonate, Quilonorm (SKB), lithium dihydrogen phosphate or two or more mixture.
9. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step (1) source of iron in is one of ferrous acetate, Ferrox., ferric citrate or two or more mixture.
10. the method preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 is it is characterised in that described step Suddenly the phosphorus source in (1) is one of lithium dihydrogen phosphate, ammonium dihydrogen phosphate or two or more mixture.
11. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly the manganese source in (1) is one of manganese acetate, manganese oxalate, manganese carbonate or two or more mixture.
12. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly doped chemical m in (1) is one of mg, co, ti, v or two or more mixture.
13. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly the organic solvent in (1) is one of ethanol, methanol, isopropanol, n-butyl alcohol, ether, acetone or two or more mixing Thing.
14. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly the dispersant in (1) is PEG-6000, PEG-4000, Polyethylene glycol-2000, PEG-4000, poly- second One or more mixture in glycol -6000, PEG-400.
15. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly in (3) and (5), inert atmosphere is one of nitrogen, argon, helium or two or more gaseous mixtures.
16. methods preparing spherical multiple phase calcium phosphate ferromanganese lithium material according to claim 2 are it is characterised in that described step Suddenly in (4), organic carbon source is one of sucrose, glucose, Fructose, starch or two or more mixture.
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CN106785173A (en) * 2017-02-16 2017-05-31 盐城工学院 One kind regeneration tertiary cathode material and preparation method thereof
CN106785173B (en) * 2017-02-16 2019-03-22 盐城工学院 A kind of regeneration tertiary cathode material and preparation method thereof
CN110323434A (en) * 2019-07-11 2019-10-11 江苏力泰锂能科技有限公司 Prepare iron manganese phosphate for lithium-carbon composite method and iron manganese phosphate for lithium-carbon composite
CN110323434B (en) * 2019-07-11 2022-07-22 江苏力泰锂能科技有限公司 Method for preparing lithium iron manganese phosphate-carbon composite material and lithium iron manganese phosphate-carbon composite material
CN114068889A (en) * 2020-08-06 2022-02-18 东莞新能安科技有限公司 Cathode material, electrochemical device and electronic device containing the same
CN114082346A (en) * 2021-12-07 2022-02-25 广东派勒智能纳米科技股份有限公司 Production process of lithium ion battery anode material
CN114620703A (en) * 2022-03-31 2022-06-14 重庆长安新能源汽车科技有限公司 Carbon-coated lithium manganese iron phosphate composite material and preparation method thereof
CN115180608A (en) * 2022-07-26 2022-10-14 江西赣锋锂电科技股份有限公司 Preparation method of spherical lithium iron manganese phosphate with high tap density

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