CN106340646B - A kind of spherical multiple phase calcium phosphate manganese iron lithium material and preparation method thereof - Google Patents
A kind of spherical multiple phase calcium phosphate manganese iron lithium material and preparation method thereof Download PDFInfo
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- CN106340646B CN106340646B CN201610843105.2A CN201610843105A CN106340646B CN 106340646 B CN106340646 B CN 106340646B CN 201610843105 A CN201610843105 A CN 201610843105A CN 106340646 B CN106340646 B CN 106340646B
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of spherical multiple phase calcium phosphate manganese iron lithium material and preparation method thereof, belongs to field of lithium ion battery anode.Spherical multiple phase calcium phosphate manganese iron lithium material is prepared using high temperature solid-state method.Source of iron, phosphorus source, lithium source, manganese source, dopant and dispersing agent are added to appropriate organic solvent, homogeneous slurry is made with twin-screw compounder, rotates evaporation drying, and low temperature presintering afterwards；It mixes and is sanded after pre-burning object and appropriate organic carbon source and CNT are added in aqueous solvent, then pelletizing by spraying, finally carry out sintering between 675-725 DEG C under an inert atmosphere and prepare required spherical multiple phase calcium phosphate manganese iron lithium material.The present invention utilizes control element adding proportion, forms (LiMn after pyroreactionxFe1‑x‑yMyPO4)·(Li4P2O7) z or (LiMnxFe1‑x‑ yMyPO4)·(Li3PO4) z composite diphase material, and contain CNT conductive network, Li can be improved+Migration rate, and be spheroidization material, tap density, and simple process, technology maturation can be improved, abundant raw material easily industrializes.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of spherical multiple phase calcium phosphate manganese iron lithium material and its preparation side
Method.
Background technique
Low-carbon economy, energy-saving and emission-reduction overall situation under, 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
Increasingly expansion with electric bicycle and new energy energy-storage system to lithium ion battery demand, lithium ion battery and its material city
Field space is huge.
The phosphate-based positive electrode of olivine-type structure security performance and in terms of be better than traditional layer
Shape structure positive electrode (such as cobalt acid lithium, lithium nickelate, ternary material), representative materials LiFePO4 (LiFePO4) learned
Art circle and industrial circle study confirmation extensively, and are widely used in the fields such as power and energy-storage battery.However, LiFePO4 3.4V
(vs.Li/Li+) current potential limits the promotion of battery energy density, therefore lithium iron phosphate dynamic battery market development is limited.With
LiFePO4 (LiFePO4) compare, iron manganese phosphate for lithium (LiMnFePO4) high potential with 4.0V or so and almost the same reason
By capacity, under conditions of equivalent capability plays, the energy density of iron manganese phosphate lithium battery will be improved than ferric phosphate lithium cell
20% or so.Therefore, iron manganese phosphate for lithium is classified as high-energy density power lithium-ion battery positive electrode of new generation in the world.But
It is iron manganese phosphate for lithium the problem of there is also conductivity and poor circulations etc. itself.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of spherical multiple phase calcium phosphate manganese iron lithium materials and preparation method thereof.
In order to improve electric conductivity, the present invention by introduced between particle and particle carbon nanotube (CNT) conductive carbon as electronics bridge with
And introduce lithium fast-ionic conductor and improve ionic conductivity, thus improve material property.
In order to solve the above technical problems, the invention provides the following technical scheme:
A kind of spherical multiple phase calcium phosphate manganese iron lithium material, the material be iron manganese phosphate for lithium main body substrate in be compounded with lithium fastly from
Sub- conductor and conductive network of carbon nanotubes.
A method of preparing spherical multiple phase calcium phosphate manganese iron lithium material, comprising the following steps:
(1) source of iron, lithium source, phosphorus source, manganese source, doped chemical M are pressed into (LiMnx Fe1-x-y My PO4)·(Li4 P2O7)zOr
Person (LiMnxFe1-x-yMyPO4)·(Li3PO4)zRecipe ratio mixing, wherein 0.6≤x≤0.9,0.01≤y≤0.02,0.01≤
Z≤0.03, and dispersing agent and organic solvent is added, grinding obtains slurry；Wherein, the doped chemical M is in Mg, Co, Ti, V
One or more kinds of mixtures, the organic solvent be ethyl alcohol, methanol, isopropanol, n-butanol, ether, in acetone
One or more kinds of mixtures, the dispersing agent be polyethylene glycol-1000, polyethylene glycol-1500, Polyethylene glycol-2000,
Polyethylene glycol-4000, polyethylene glycol-6000, mixture one or more kinds of in polyethylene glycol-20000；
(2) slurry in step (1) is dry, form small particles material；
(3) by step (2) small particles material 350-400 DEG C of pre-burning 6-8h under an inert atmosphere, pre-burning object is obtained；
(4) the carbon nanotube mixed grinding by pre-burning object, organic carbon source and diameter in step (3) no more than 10nm, then into
Row spray drying, is made spheroidization secondary agglomeration body material；
(5) the 675-725 DEG C of sintering in inert atmosphere roller kilns by the secondary agglomeration body material of spheroidization in step (4)
8h obtains spherical multiple phase calcium phosphate manganese iron lithium material (LiMnxFe1-x-yMyPO4)·(Li4P2O7)zOr (LiMnxFe1-x- yMyPO4)·(Li3PO4)z, the spherical multiple phase calcium phosphate manganese iron lithium material be iron manganese phosphate for lithium main body substrate in be compounded with lithium fastly from
Sub- conductor and conductive network of carbon nanotubes.
Further, in the step (1) dispersing agent additional amount be phosphorus source, source of iron and manganese source quality sum 3-5%, it is organic
Solvent adding amount is the 130-180% of phosphorus source, source of iron and manganese source quality sum.
Further, the partial size of step (2) the small particles material is less than 5mm.
Further, the carbon nanotube mixed grinding of pre-burning object, organic carbon source and diameter no more than 10nm in the step (3)
It is less than 200nm to average grain diameter D50, the diameter of spheroidization secondary agglomeration body material is between 10-25 μm.
Further, grinding includes being not more than pre-burning object, organic carbon source and diameter in step (3) in the step (4)
The carbon nanotube of 10nm is thrown roughly grind 1h in the Ball-stirring mill containing zirconia ball after, be transferred in sand mill fine grinding 3h to average grain diameter
D50 is less than 200nm.
Further, the lithium source in the step (1) be one or both of lithium carbonate, lithium acetate, lithium dihydrogen phosphate with
On mixture.
Further, the source of iron in the step (1) is one or both of ferrous acetate, ferrous oxalate, ironic citrate
Above mixture.
Further, the phosphorus source in the step (1) is one or more of lithium dihydrogen phosphate, ammonium dihydrogen phosphate
Mixture.
Further, the manganese source in the step (1) is one or more of manganese acetate, manganese oxalate, manganese carbonate
Mixture.
Further, inert atmosphere is one or more of nitrogen, argon gas, helium in the step (3) and (5)
Gaseous mixture.
Further, organic carbon source is one or more of sucrose, glucose, fructose, starch in the step (4)
Mixture.
The present invention has the following technical effect that
Lithium fast-ionic conductor ionic conductivity with higher, is capable of increasing the diffusion rate of lithium ion；Carbon nanotube is led
Multiple phase calcium phosphate manganese iron lithium material is connected with each other by power grid in inside, forms the electronics bridge of three-D space structure, and carbon nanotube
Conductive mesh intensity is high, reduces the feelings of conductive network rupture caused by multiple phase calcium phosphate manganese iron lithium material stretches in charge and discharge process
Condition, the Li of multiple phase calcium phosphate manganese iron lithium material+Migration rate and electric conductivity are greatly improved.Electrical property and head in half-cell
Secondary efficiency improves a lot compared to pure phase iron manganese phosphate lithium material.Multiple phase calcium phosphate manganese iron lithium material shape spherical in shape, can be improved vibration
Real density, processing performance have promotion.The process route simple process of the high temperature solid-state method used in the present invention, technology maturation are former
Material is abundant, easily industrializes.
Detailed description of the invention
Fig. 1 is preparation technology flow chart of the invention；
Fig. 2 is the spherical multiple phase calcium phosphate manganese iron lithium material containing fast-ionic conductor and conductive network of carbon nanotubes, and is free of
SEM microscopic comparison's piece of fast-ionic conductor and the pure phase iron manganese phosphate lithium material of conductive network of carbon nanotubes；
Fig. 3 is the XRD spectrum of spherical multiple phase calcium phosphate manganese iron lithium material prepared by embodiment 1.
Specific embodiment
In order to which the purpose of the present invention, technical solution and advantage is more clearly understood, below in conjunction with attached drawing and specifically
Embodiment, invention is further described in detail.Accompanying drawings and embodiments for explaining only the invention, are not used to limit this hair
It is bright.Those skilled in the art makes various modifications on the basis of the present invention, is regarded as protection model of the invention
It encloses.
Multiple phase calcium phosphate manganese iron lithium material is spherical in shape, and be compounded in iron manganese phosphate for lithium main body substrate lithium fast-ionic conductor and
Conductive network of carbon nanotubes.
Embodiment 1
A kind of multiple phase calcium phosphate manganese iron lithium material, bulk composition are iron manganese phosphate for lithium, containing lithium phosphate or pyrophosphoric acid lithium this
Class lithium fast-ionic conductor, and have conductive network of carbon nanotubes.
Preparation method is as shown in Figure 1, I: raw and auxiliary material, and II: small particles material, III: pre-burning object, IV: spray drying is reunited
Body, V: finished product after sintering, preparation step are 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, polyethylene glycol-1000 additional amount are
The 3% of phosphorus source, source of iron and manganese source quality sum, alcohol solvent additional amount be phosphorus source, source of iron and manganese source quality sum 130% plus
Enter mixing, ball milling 2h, solid content in twin-screw compounder and be designed as 40%, forms uniform slurry, tire out in size distribution curve
D50=9 μm of equivalent diameter of the largest particles when product is distributed as 50%, when cumulative distribution is 100% in size distribution curve
D100=50 μm of the equivalent diameter of the largest particles；
2. gained slurry in step 1 to be transferred in rotary evaporator and is dried, heating water bath is to 90 DEG C, rotary evaporation
After 3h, slurry becomes the solid granulates that partial size is less than 5mm；
3. particulate matter in step 2 is taken to carry out 400 DEG C of pre-burning 6h in the batch-type furnace for having nitrogen protection, pre-burning object is obtained；
4. taking gained pre-burning object 1kg in step 3, the carbon nanotube water that arrange in pairs or groups 100g sucrose and 100g mass fraction are 5%
It is slurry, stirring corase grinding 1h in the Ball-stirring mill containing 1.8kg deionized water is added, D100 < 20 μm are transferred to containing 0.2mm oxygen
Change fine grinding 3h in the sand mill of zirconium ball, obtains the uniform sizing material of D50=197nm；
5. gained slurry in step 4 is spray-dried, control secondary agglomeration body material meso-position radius is 20 μm or so；
6. take the secondary agglomeration body material prepared in step 5 to be placed in the tunnel oven containing nitrogen atmosphere 675 DEG C of sintering 8h,
Required multiple phase calcium phosphate manganese iron lithium material can be obtained.
Embodiment 2
A kind of spherical multiple phase calcium phosphate manganese iron lithium material, bulk composition are iron manganese phosphate for lithium, contain lithium phosphate or pyrophosphoric acid
This kind of lithium fast-ionic conductor of lithium, and have conductive network of carbon nanotubes.
Steps are as follows for preparation method:
1. the raw materials such as ammonium di-hydrogen phosphate, manganese acetate, ironic 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, polyethylene glycol-1000 additional amount are phosphorus source, source of iron and manganese source
The 5% of quality sum, methanol solvate additional amount are 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, and D50=9.5 μm, D100=55 μm；
2. gained slurry in step 1 to be transferred in rotary evaporator and is dried, heating water bath is to 90 DEG C, rotary evaporation
After 3h, slurry becomes the solid granulates that partial size is less than 5mm；
3. particulate matter in step 2 is taken to carry out 350 DEG C of pre-burning 8h in the batch-type furnace for having nitrogen protection, pre-burning object is obtained；
4. taking gained pre-burning object 1kg in step 3, the carbon nanotube water system that arrange in pairs or groups 75g fructose and 100g mass fraction are 5%
Slurry is added stirring corase grinding 1h, D100 < 20 μm in the Ball-stirring mill containing 1.8kg deionized water and is transferred to and aoxidizes containing 0.2mm
Fine grinding 3h in the sand mill of zirconium ball, obtains the uniform sizing material of D50=199nm；
5. gained slurry in step 4 is spray-dried, control secondary agglomeration body material meso-position radius is 20 μm or so；
6. take the secondary agglomeration body material prepared in step 5 to be placed in the tunnel oven containing nitrogen atmosphere 700 DEG C of sintering 8h,
Required multiple phase calcium phosphate manganese iron lithium material can be obtained.
Embodiment 3
A kind of spherical multiple phase calcium phosphate manganese iron lithium material, bulk composition are iron manganese phosphate for lithium, contain lithium phosphate or pyrophosphoric acid
Lithium lithium fast-ionic conductor, and have conductive network of carbon nanotubes.
Steps are as follows for preparation method:
1. the raw materials such as ammonium di-hydrogen phosphate, manganese carbonate, ferrous oxalate, 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, polyethylene glycol-1000 additional amount are phosphorus
Source, source of iron and manganese source quality sum 4%, alcohol solvent additional amount is the 150% of phosphorus source, source of iron and manganese source quality sum to be added
Mixing, ball milling 2h in twin-screw compounder, solid content is designed as 40%, forms uniform slurry, and D50=10 μm, D100=61 μ
m；
2. gained slurry in step 1 to be transferred in rotary evaporator and is dried, heating water bath is to 90 DEG C, rotary evaporation
After 3h, slurry becomes the solid granulates that partial size is less than 5mm；
3. particulate matter in step 2 is taken to carry out 375 DEG C of pre-burning 6h in the batch-type furnace for having nitrogen protection, pre-burning object is obtained；
4. taking gained pre-burning object 1kg in step 3, the carbon nanotube that arrange in pairs or groups 100g glucose and 100g mass fraction are 5%
Stirring corase grinding 1h in the Ball-stirring mill containing 1.8kg deionized water is added in aqueous slurry, and D100 < 20 μm are transferred to containing 0.2mm
Fine grinding 3h in the sand mill of zirconia ball, obtains the uniform sizing material of D50=189nm；
5. gained slurry in step 4 is spray-dried, control secondary agglomeration body material meso-position radius is 20 μm or so；
6. take the secondary agglomeration body material prepared in step 5 to be placed in the tunnel oven containing nitrogen atmosphere 725 DEG C of sintering 8h,
Required multiple phase calcium phosphate manganese iron lithium material can be obtained.
Embodiment 4
A kind of spherical multiple phase calcium phosphate manganese iron lithium material, bulk composition are iron manganese phosphate for lithium, contain lithium phosphate or pyrophosphoric acid
Lithium lithium fast-ionic conductor, and have conductive network of carbon nanotubes.
Steps are as follows for preparation method:
1. by originals such as lithium dihydrogen phosphate, manganese carbonate, ironic citrate, vanadic anhydride, magnesium acetate, isopropyl titanate, lithium carbonates
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
- 1000 additional amount of glycol is the 5% of phosphorus source, source of iron and manganese source quality sum, and alcohol solvent additional amount is phosphorus source, source of iron and manganese source
The 180% of quality sum is added mixing, ball milling 2h, solid content in twin-screw compounder and is designed as 40%, forms uniform slurry,
D50=9 μm, D100=48 μm；
2. gained slurry in step 1 to be transferred in rotary evaporator and is dried, heating water bath is to 90 DEG C, rotary evaporation
After 3h, slurry becomes the solid granulates that partial size is less than 5mm；
3. particulate matter in step 2 is taken to carry out 400 DEG C of pre-burning 6h in the batch-type furnace for having nitrogen protection, pre-burning object is obtained；
4. taking gained pre-burning object 1kg in step 3, the carbon nanotube water that arrange in pairs or groups 100g sucrose and 100g mass fraction are 5%
It is slurry, stirring corase grinding 1h in the Ball-stirring mill containing 1.8kg deionized water is added, D100 < 20 μm are transferred to containing 0.2mm oxygen
Change fine grinding 3h in the sand mill of zirconium ball, obtains the uniform sizing material of D50=191nm；
5. gained slurry in step 4 is spray-dried, control secondary agglomeration body material meso-position radius is 20 μm or so；
6. take the secondary agglomeration body material prepared in step 5 to be placed in the tunnel oven containing nitrogen atmosphere 725 DEG C of sintering 8h,
Required multiple phase calcium phosphate manganese iron lithium material can be obtained.
Embodiment 5
A kind of spherical multiple phase calcium phosphate manganese iron lithium material containing lithium fast-ionic conductor, bulk composition are iron manganese phosphate for lithium, are contained
There are lithium phosphate or this kind of lithium fast-ionic conductor of pyrophosphoric acid lithium, but carbon-free nanoscale pipe conductive network.
Steps are as follows for preparation method:
1. by originals such as lithium dihydrogen phosphate, manganese carbonate, ironic citrate, vanadic anhydride, magnesium acetate, isopropyl titanate, lithium carbonates
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
- 1000 additional amount of glycol is the 5% of phosphorus source, source of iron and manganese source quality sum, and alcohol solvent additional amount is phosphorus source, source of iron and manganese source
The 180% of quality sum is added mixing, ball milling 2h, solid content in twin-screw compounder and is designed as 40%, forms uniform slurry,
D50=9 μm, D100=48 μm；
2. gained slurry in step 1 to be transferred in rotary evaporator and is dried, heating water bath is to 90 DEG C, rotary evaporation
After 3h, slurry becomes the solid granulates that partial size is less than 5mm；
3. particulate matter in step 2 is taken to carry out 400 DEG C of pre-burning 6h in the batch-type furnace for having nitrogen protection, pre-burning object is obtained；
4. taking gained pre-burning object 1kg in step 3,100g sucrose of arranging in pairs or groups is added in the Ball-stirring mill containing 1.8kg deionized water
Stirring corase grinding 1h, D100 < 20 μm are transferred to fine grinding 3h in the sand mill containing 0.2mm zirconia ball, obtain D50=191nm's
Uniform sizing material；
5. gained slurry in step 4 is spray-dried, secondary agglomeration body material sphere diameter is controlled less than 20 μm；
6. take the secondary agglomeration body material prepared in step 5 to be placed in the tunnel oven containing nitrogen atmosphere 725 DEG C of sintering 8h,
Required multiple phase calcium phosphate manganese iron lithium material can be obtained.
Table 1 be the spherical multiple phase calcium phosphate manganese iron lithium material sample containing lithium fast-ionic conductor that is prepared in embodiment 1,4,5 with
Pure phase iron manganese phosphate lithium material control sample electrical property correlation data in half-cell.
Table 1
| 0.2C D | 1C D | First charge discharge efficiency | Remarks | |
| Sample 1 | 147mAh/g | 140mAh/g | 95.3% | 1 sample of embodiment |
| Sample 4 | 145mAh/g | 140mAh/g | 95.6% | 4 sample of embodiment |
| Sample 5 | 138mAh/g | 130mAh/g | 94.3% | 5 sample of embodiment |
| Sample 0 | 131mAh/g | 123mAh/g | 90.1% | Control sample |
Electrical property and first charge discharge efficiency of the embodiment as the result is shown 1,4 and 5 in half-cell in table 1 is superior to control sample
Product.
Fig. 2 is the spherical multiple phase calcium phosphate manganese iron lithium material containing fast-ionic conductor and conductive network of carbon nanotubes, and is free of
SEM microscopic comparison's piece of fast-ionic conductor and the pure phase iron manganese phosphate lithium material of conductive network of carbon nanotubes.Sample0 is equal
The SEM electron microscope of pure phase iron manganese phosphate lithium material without fast-ionic conductor and conductive network of carbon nanotubes；Sample3-1 is real
The multiple phase calcium phosphate manganese iron lithium material containing fast-ionic conductor and conductive network of carbon nanotubes of the preparation of example 3 is applied under high power lens
SEM electron microscope；Sample3-2 is the multiple phase calcium phosphate containing fast-ionic conductor and conductive network of carbon nanotubes prepared by embodiment 3
SEM electron microscope of the manganese iron lithium material under low power lens.
Fig. 3 is the XRD spectrum of spherical multiple phase calcium phosphate manganese iron lithium material prepared by embodiment 1, as can be seen that ball from map
There is Li in shape multiple phase calcium phosphate manganese iron lithium material3PO4Lithium fast-ionic conductor.
Claims (12)
1. a kind of method for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which comprises the following steps:
(1) source of iron, lithium source, phosphorus source, manganese source, doped chemical M are pressed into (LiMnxFe1-x-yMyPO4)·(Li4P2O7)zOr
(LiMnxFe1-x-yMyPO4)·(Li3PO4)zRecipe ratio mixing, wherein 0.6≤x≤0.9,0.01≤y≤0.02,0.01≤z
≤ 0.03, and dispersing agent and organic solvent is added, grinding obtains slurry；Wherein, the doped chemical M is in Mg, Co, Ti, V
One or more kinds of mixtures, the organic solvent are ethyl alcohol, methanol, isopropanol, n-butanol, ether, one in acetone
Kind or two or more mixtures, the dispersing agent are polyethylene glycol-1000, polyethylene glycol-1500, Polyethylene glycol-2000, gather
Ethylene glycol -4000, polyethylene glycol-6000, mixture one or more kinds of in polyethylene glycol-20000；
(2) slurry in step (1) is dry, form small particles material；
(3) by step (2) small particles material 350-400 DEG C of pre-burning 6-8h under an inert atmosphere, pre-burning object is obtained；
(4) pre-burning object, organic carbon source and diameter in step (3) are not more than to the carbon nanotube mixed grinding of 10 nm, then sprayed
Mist is dry, and spheroidization secondary agglomeration body material is made；
(5) by the secondary agglomeration body material of spheroidization in step (4) in inert atmosphere roller kilns 675-725 DEG C of sintering 8h, obtain
To spherical multiple phase calcium phosphate manganese iron lithium material (LiMnxFe1-x-yMyPO4)•(Li4P2O7)zOr (LiMnxFe1-x-yMyPO4)•
(Li3PO4)z, the spherical multiple phase calcium phosphate manganese iron lithium material be iron manganese phosphate for lithium main body substrate in be compounded with lithium fast-ionic conductor and
Conductive network of carbon nanotubes.
2. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(1) in dispersing agent additional amount be phosphorus source, source of iron and manganese source quality sum 3-5 %, organic solvent additional amount be phosphorus source, source of iron with
The 130-180 % of manganese source quality sum.
3. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(2) partial size of small particles material is less than 5 mm.
4. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(3) the carbon nanotube mixed grinding of pre-burning object, organic carbon source and diameter no more than 10 nm is less than to average grain diameter D50 in
200nm, the diameter of spheroidization secondary agglomeration body material is between 10-25 μm.
5. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(4) between organic carbon source and the mass ratio 5-12% of pre-burning object, the mass ratio of carbon nanotube and pre-burning object is 0 .2-0 .5 %.
6. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(4) grinding includes throwing pre-burning object, organic carbon source and diameter in step (3) in containing aerobic no more than the carbon nanotube of 10 nm in
Change after roughly grinding 1h in the Ball-stirring mill of zirconium ball, is transferred to fine grinding 3h to average grain diameter D50 in sand mill and is less than 200nm.
7. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(1) lithium source in is the mixture of one or more of lithium carbonate, lithium acetate, lithium dihydrogen phosphate.
8. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(1) source of iron in is the mixture of one or more of ferrous acetate, ferrous oxalate, ironic citrate.
9. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
(1) phosphorus source in is the mixture of one or more of lithium dihydrogen phosphate, ammonium dihydrogen phosphate.
10. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
Suddenly the manganese source in (1) is the mixture of one or more of manganese acetate, manganese oxalate, manganese carbonate.
11. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
Suddenly in (3) and (5) inert atmosphere be one or more of nitrogen, argon gas, helium gaseous mixture.
12. the method according to claim 1 for preparing spherical multiple phase calcium phosphate manganese iron lithium material, which is characterized in that the step
Suddenly in (4) organic carbon source be one or more of sucrose, glucose, fructose, starch mixture.
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| CN106785173B (en) * | 2017-02-16 | 2019-03-22 | 盐城工学院 | A kind of regeneration tertiary cathode material and preparation method thereof |
| 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 |
| CN114620703B (en) * | 2022-03-31 | 2023-04-07 | 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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| WO2011038233A1 (en) * | 2009-09-25 | 2011-03-31 | Lawrence Livermore National Security, Llc | High-performance rechargeable batteries with fast solid-state ion conductors |
| CN103094567A (en) * | 2013-01-24 | 2013-05-08 | 浙江正电新能源有限公司 | Anode material of lithium fast ionic conductor compounded lithium battery and preparation method of anode material |
| CN103337606A (en) * | 2013-07-02 | 2013-10-02 | 山东润峰集团新能源科技有限公司 | Method for improving performance of lithium power battery |
| CN103456951A (en) * | 2013-07-24 | 2013-12-18 | 湖南大学 | High-magnification nano lithium iron phosphate positive material cross-linked and covered by carbon nano tube and preparation method of material |
| CN103441269B (en) * | 2013-08-05 | 2016-08-17 | 北大先行科技产业有限公司 | A kind of pyrophosphoric acid lithium/carbon-coated lithium iron phosphate composite and preparation method thereof |
| CN103730657B (en) * | 2014-01-09 | 2016-05-18 | 北大先行科技产业有限公司 | A kind of preparation method of lithium phosphate/carbon-coated lithium iron phosphate composite |
| CN104393234A (en) * | 2014-11-21 | 2015-03-04 | 海宁美达瑞新材料科技有限公司 | Modified lithium ion battery composite positive pole material and preparation method thereof |
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