CN106374105B - A kind of preparation method of ball shape ferric phosphate manganese lithium electrode material - Google Patents
A kind of preparation method of ball shape ferric phosphate manganese lithium electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 present invention provides a kind of ball shape ferric phosphate manganese lithium electrode material and preparation method, water-soluble lithium salts, manganese salt, molysite, phosphorus source are dissolved in deionized water respectively, it is emulsified in advance, lithium ferric manganese phosphate microballoon is flocculated into a liquid, pre-reaction spheric granules is further obtained by spray drying, then further calcining obtains ball shape ferric phosphate manganese lithium electrode material by pre-reaction spheric granules.The present invention offer above method overcomes prepares lithium ferric manganese phosphate presoma long preparation period in the prior art, product component is inhomogenous, particle size is uneven, cause final lithium ferric manganese phosphate performance unstable, and the lithium ferric manganese phosphate electrode material of the structure of preparation spherical shape needs to introduce template induction, it is more harsh to react preparation condition, the technical issues of being unsatisfactory for industrialization production requirements, present invention process is simple, short preparation period, the ball shape ferric phosphate manganese lithium electrode material homogeneity of acquisition is high, and electric conductivity, high and low temperature resistance are excellent.
Description
Technical field
The present invention relates to be a kind of lithium ion battery electrode material preparation field, and in particular to a kind of ball shape ferric phosphate manganese lithium
The preparation method of electrode material.
Background technology
The main composition material of lithium ion battery includes electrolyte, isolated material, positive and negative pole material etc., wherein positive electrode
Quality occupy larger proportion（The mass ratio of positive and negative pole material is 3-4:1）.Because the performance of positive electrode directly affects lithium
The performance of ion battery, cost also directly determines battery cost height, so anode material for lithium-ion batteries becomes research
It is popular.
Since the LiFePO4 of olivine-type structure was reported from 1997 with reversible removal lithium embedded characteristic, with its safety
Can it is good, cycle performance is excellent, environmental-friendly, raw material sources enrich, is at low cost the advantages that and as lithium ion battery it is main just
Pole material.However, when LiFePO4 is as anode material of lithium battery, however it remains defect is mainly manifested in the electricity of LiFePO4
Subconductivity poor performance, chargeable voltage are relatively low, low-temperature stability is poor, tap density is small, stored by unit volume battery
Electric energy it is less, Fe in the synthesis process2+It is oxidizable into Fe3+, single-phase LiFePO4 is difficult to obtain, purity is low, preparation process
Complexity, and long-time high-temperature calcination is needed, high energy consumption, period are long.Although the doping by lithium position, iron position improves ion and electricity
Subconductivity performance controls effective affecting acreage by the grain size and pattern that improve particle, is increased by adding in additional conductive agent
Electron conduction etc. is to improve the cryogenic property of LiFePO4, but the inherent characteristics of LiFePO 4 material, determines its low temperature properties
It can be inferior to other positive electrodes such as LiMn2O4.
However the LiMn2O4 of layer structure has many advantages, manganese as a kind of novel anode material for lithium-ion batteries
Resourceful, low in raw material price, it is smaller without heavy metal, environmental pollution, there is the up to theoretical capacity of 286mAh/g, electricity
Superior performance is applied in power vehicle field.In application process due to changing after de- lithium to spinel structure, crystal form
The variation repeatedly of structure easily causes volume expansion and contraction, and stable circulation performance is bad, and especially high temperature cyclic performance is poor, holds
Soluble loss, cycle life attenuation is very fast, bulging easily occurs, high-temperature behavior is poor, the service life is relatively short.
The defects of in order to make up LiFePO4 and stratiform manganese oxide lithium, technical staff attempt by the compound means of the two into
Row performance improvement.
Chinese invention patent application number 201010527962.4 discloses a kind of lithium ion battery positive pole material phosphoric acid ferrimanganic
Lithium and preparation method thereof.Carbon source and metal salt are placed in container by the present invention, add in dispersant, in turning for 1000-2500r/min
The lower grinding distribution 1-3h of speed, pasty slurry is dried and is ground, then rises to 350-550 DEG C with the heating rate of 1-10 DEG C/min,
Constant temperature pre-burning 3-20h, cools to room temperature with the furnace, lithium ferric manganese phosphate is made, finally by lithium ferric manganese phosphate, carbon source, dispersant
Disperse 1-3h, after dry, rise to 600-850 DEG C with the heating rate of 1-10 DEG C/min, ferric phosphate is made in furnace cooling after heat preservation
Manganese lithium.However, the scheme of the invention prepare lithium ferric manganese phosphate due to being dried in pre-treatment using pasty slurry, the ferric phosphate of preparation
The particle size of manganese lithium is big, and for lithium ion transport mainly on surface, efficiency is low.
Chinese invention patent application number 201510480891.X discloses a kind of anode material of lithium battery lithium ferric manganese phosphate
Water-soluble manganese source, source of iron, phosphorus source and Li source compound and chelator acid citrate are dissolved and mixed in sequence by preparation method
Uniformly, higher-boiling compound DMSO is then added in, protection gas is passed through and is protected, product is obtained after heating.The scheme of the invention is led to
Addition higher boiling additive is crossed, reduces the potential barrier of hydro-thermal reaction, but the product of hydro-thermal reaction is inhomogenous, impurity is more, and purification is tired
Difficulty, the reaction time is long, the final properties of product for influencing lithium ferric manganese phosphate.
In order to improve the chemical property of lithium ferric manganese phosphate positive electrode and energy density, Chinese invention patent application number
201511015673.5 disclose a kind of ball shape ferric phosphate manganese lithium anode material and preparation method thereof.This method by lithium source, source of iron,
Manganese source, phosphorus source add in deionized water, then carbon-source cpd are added in mixed solution, add in CTAB templates thereto and stir
It mixes, adds EDTA, hydro-thermal reaction is carried out at 180 DEG C, lithium ferric manganese phosphate presoma is obtained by being filtered, washed, finally by phosphorus
Sour ferrimanganic lithium precursor powder, which is put into tube calciner, to be sintered, and is ground after cooling and is obtained carbon-coated ball shape ferric phosphate manganese lithium
Positive electrode.However, the addition for introducing template is needed to induce the formation of ball shape ferric phosphate manganese lithium in the forming process of product, it is somebody's turn to do
Invention is more demanding to template agent content and environment solution reaction condition, and synthesizes hydro-thermal method complex technical process and be not suitable for
For large-scale industrial production.
According to above-mentioned, the synthesis technology of lithium ferric manganese phosphate material is substantially at present first prepares phosphoric acid using the method for hydro-thermal
Ferrimanganic lithium presoma, and the hydro-thermal reaction time is long, hydro-thermal method product component is inhomogenous, needs multiple times of filtration and cleaning, and then leads
Cause final lithium ferric manganese phosphate performance unstable.In addition, the lithium ferric manganese phosphate electrode material of spherical structure is prepared in the prior art
It needs to introduce template induction, reaction preparation condition is more harsh, is unsatisfactory for industrial production demand.
Invention content
For in the synthesis technology of current lithium ferric manganese phosphate material, lithium ferric manganese phosphate presoma process is prepared using hydro-thermal method
Complexity, long preparation period, product component is inhomogenous, and particle size is uneven, causes final lithium ferric manganese phosphate performance unstable, with
And the lithium ferric manganese phosphate electrode material of the structure of preparation spherical shape needs to introduce template induction, reaction preparation condition is more harsh,
The technical issues of being unsatisfactory for industrialized production, the present invention propose a kind of preparation method of ball shape ferric phosphate manganese lithium electrode material, from
And realize the efficient preparation of uniform-spherical lithium ferric manganese phosphate electrode material, further push industrialized production.
The present invention provides a kind of preparation method of ball shape ferric phosphate manganese lithium electrode material, using water-soluble lithium salts, manganese salt,
Molysite, phosphorus source include the following steps as synthesis material：
（1）By water-soluble lithium salts, manganese salt, molysite, phosphorus source and emulsifier in molar ratio 3:(1-x):x:1:0.01 is claimed
It measures, wherein x=0.01-0.5, then manganese salt and molysite is codissolved in the solution of deionized water formation 0.5mol/L, by phosphorus source and lithium
Salt is dissolved in deionized water respectively, is respectively formed the phosphorus source solution of 0.5mol/L and the lithium salt solution of 1.5mol/L；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese salt and molysite:（0.01-0.05）Tartaric acid, formed tartaric acid
Mixed liquor, and constantly stir evenly, the phosphorus source solution isometric with the tartaric acid mixed liquor is then added to the winestone
In sour mixed liquor, mixed system is formed, and stir evenly, finally lithium salt solution is added in the mixed system, stirring is equal
It is even, precursor liquid is obtained, wherein, the lithium salt solution is equal with phosphorus source liquor capacity；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with organic solvent, emulsifier, setting spray drying
The reaction temperature of case is 160-200 DEG C, obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and organic solvent
It is 1:1-2；
（4）By the pre-reaction spheric granules further across calcination processing, ball shape ferric phosphate manganese lithium electrode material is obtained.
Preferably, the lithium salts use lithium hydroxide, lithium acetate, lithium sulfate and lithium nitrate it is therein it is any one or two kinds of with
On combination.
Preferably, the manganese salt is any in manganese oxalate, manganese acetate, manganese sulfate, manganese chloride, potassium permanganate, potassium manganate
Kind or two or more combinations, the molysite are any one of ferrous sulfate, ferrous nitrate, frerrous chloride soluble ferrite
Or two or more combination.
Preferably, phosphorus source is using any one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate or two kinds
Above combination.
Preferably, the emulsifier is fatty glyceride, methyl glycol fatty acid ester, dodecyl sodium sulfate, dodecane
Any one or more combinations of base benzene sulfonic acid sodium salt.
Preferably, the organic solvent for benzene,toluene,xylene, hexamethylene, cyclohexanone, toluene cyclohexanone, pentane, oneself
Any one or more combinations of alkane, octane.
Preferably, the calcine technology is the precalcining 2h at 230-300 DEG C, and it is 700-760 DEG C then to increase temperature, is risen
Warm speed is 10-30 DEG C/h, calcination time 1-2h.
A kind of ball shape ferric phosphate manganese lithium electrode material prepared by the present invention and common non-ball shape ferric phosphate manganese lithium electrode material
Performance is as shown in table 1.
Table 1：
| Performance indicator | Internal resistance（mΩ） | - 30 DEG C of specific capacities（mAh/g） | 80 DEG C of specific capacities（mAh/g） |
| The present invention | 1.2 | ≥ 242 | ≥ 256 |
| It is aspherical | 13 | ≥180 | ≥193 |
The present invention provides a kind of preparation method of ball shape ferric phosphate manganese lithium electrode material, compared with prior art, protrudes
The characteristics of and excellent effect be：
1st, then the present invention is obtained using the uniform raw slurry of emulsifying process prepared composition using the method for spray drying
Evengranular ball shape ferric phosphate manganese lithium particle, the ball shape ferric phosphate manganese lithium grain diameter and distributed components of preparation, is free of
Impurity component, electric conductivity, high and low temperature resistance are excellent.
2nd, then the present invention is obtained using the uniform raw slurry of emulsifying process prepared composition using the method for spray drying
Evengranular ball shape ferric phosphate manganese lithium particle, without the participation of template, preparation condition is easy to control, and is realized continuous, steady
Fixed, prepare with scale ball shape ferric phosphate manganese lithium particle, will further push extensive industrialized development.
3rd, with short production cycle, at low cost, non-environmental-pollution of the invention, has significant market application value.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By lithium hydroxide, manganese oxalate, ferrous sulfate, phosphoric acid and fatty glyceride in molar ratio 3:0.5:0.5:1:
0.01 is weighed, and manganese oxalate and ferrous sulfate then are codissolved in the solution that deionized water forms 0.5mol/L, by phosphoric acid and
Lithium hydroxide is dissolved in deionized water respectively, be respectively formed 0.5mol/L phosphoric acid solution and 1.5mol/L lithium hydroxide it is molten
Liquid；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese oxalate and ferrous sulfate:0.01 tartaric acid forms tartaric acid
Mixed liquor, and constantly stir evenly, the phosphoric acid solution isometric with the tartaric acid mixed liquor is then added to the winestone
In sour mixed liquor, mixed system is formed, and stir evenly, finally lithium hydroxide solution is added in the mixed system, is stirred
It mixes uniformly, obtains precursor liquid, wherein, the lithium hydroxide solution is equal with the phosphoric acid solution volume；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with toluene, the reaction temperature of setting spray drying case
It is 160 DEG C to spend, and obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and toluene is 1:1；
（4）By the pre-reaction spheric granules further across calcination processing, calcine technology is the precalcining at 230 DEG C
0.5h, it is 700 DEG C then to increase temperature, and heating rate is 10 DEG C/h, calcination time 1h, obtains ball shape ferric phosphate manganese lithium electrode
Material.
It is used as cell positive material by the ball shape ferric phosphate manganese lithium that method in embodiment 1 is prepared, by performance test
It is as shown in table 2 to obtain parameter.
Embodiment 2
（1）By lithium hydroxide, manganese acetate, ferrous nitrate, ammonium dihydrogen phosphate and methyl glycol fatty acid ester in molar ratio 3:
0.6:0.4:1:0.01 is weighed, and manganese acetate and ferrous nitrate then are codissolved in deionized water forms the molten of 0.5mol/L
Ammonium dihydrogen phosphate and lithium hydroxide are dissolved in deionized water by liquid respectively, are respectively formed the ammonium dihydrogen phosphate of 0.5mol/L
With the lithium hydroxide solution of 1.5mol/L；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese acetate and ferrous nitrate:0.03 tartaric acid forms tartaric acid
Mixed liquor, and constantly stir evenly, the ammonium dihydrogen phosphate isometric with the tartaric acid mixed liquor is then added to institute
It states in tartaric acid mixed liquor, forms mixed system, and stir evenly, lithium hydroxide solution is finally added to the mixed system
In, it stirs evenly, obtains precursor liquid, wherein, the lithium hydroxide solution is equal with the ammonium dihydrogen phosphate volume；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with hexamethylene, the reaction of setting spray drying case
Temperature is 180 DEG C, obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and hexamethylene is 1:1.1；
（4）By the pre-reaction spheric granules further across calcination processing, calcine technology is the precalcining at 250 DEG C
0.5h, it is 720 DEG C then to increase temperature, and heating rate is 15 DEG C/h, calcination time 1.5h, obtains ball shape ferric phosphate manganese lithium electricity
Pole material.
It is used as cell positive material by the ball shape ferric phosphate manganese lithium that method in embodiment 2 is prepared, by performance test
It is as shown in table 2 to obtain parameter.
Embodiment 3
（1）By lithium sulfate, manganese chloride, frerrous chloride, ammonium phosphate and dodecyl sodium sulfate in molar ratio 3:0.7:0.3:
1:0.01 is weighed, and then manganese chloride and frerrous chloride is codissolved in the solution of deionized water formation 0.5mol/L, by phosphoric acid
Ammonium and lithium sulfate are dissolved in deionized water respectively, be respectively formed 0.5mol/L ammonium phosphate solution and 1.5mol/L lithium sulfate it is molten
Liquid；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese chloride and frerrous chloride:0.03 tartaric acid forms tartaric acid
Mixed liquor, and constantly stir evenly, the ammonium phosphate solution isometric with the tartaric acid mixed liquor is then added to the wine
In stone acid mixed liquor, mixed system is formed, and stir evenly, finally lithium sulfate solution is added in the mixed system, is stirred
It mixes uniformly, obtains precursor liquid, wherein, the lithium sulfate solution is equal with the ammonium phosphate solution volume；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with pentane, the reaction temperature of setting spray drying case
It is 185 DEG C to spend, and obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and pentane is 1:1.5；
（4）By the pre-reaction spheric granules further across calcination processing, calcine technology is the precalcining at 280 DEG C
2h, it is 740 DEG C then to increase temperature, and heating rate is 18 DEG C/h, calcination time 2h, obtains ball shape ferric phosphate manganese lithium electrode material
Material.
It is used as cell positive material by the ball shape ferric phosphate manganese lithium that method in embodiment 3 is prepared, by performance test
It is as shown in table 2 to obtain parameter.
Embodiment 4
（1）By lithium nitrate, manganese sulfate, frerrous chloride, ammonium dihydrogen phosphate and neopelex in molar ratio 3:
0.7:0.3:1:0.01 is weighed, and manganese sulfate and frerrous chloride then are codissolved in deionized water forms the molten of 0.5mol/L
Ammonium dihydrogen phosphate and lithium nitrate are dissolved in deionized water by liquid respectively, be respectively formed 0.5mol/L ammonium dihydrogen phosphate and
The lithium nitrate solution of 1.5mol/L；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese sulfate and frerrous chloride:0.04 tartaric acid forms tartaric acid
Mixed liquor, and constantly stir evenly, the ammonium dihydrogen phosphate isometric with the tartaric acid mixed liquor is then added to institute
It states in tartaric acid mixed liquor, forms mixed system, and stir evenly, lithium nitrate solution is finally added to the mixed system
In, it stirs evenly, obtains precursor liquid, wherein, the lithium nitrate solution is equal with the ammonium dihydrogen phosphate volume；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with octane solvent, setting is spray-dried the anti-of case
It is 190 DEG C to answer temperature, obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and octane solvent is 1:1.6；
（4）By the pre-reaction spheric granules further across calcination processing, calcine technology is the precalcining at 300 DEG C
0.5h, it is 760 DEG C then to increase temperature, and heating rate is 30 DEG C/h, calcination time 1h, obtains ball shape ferric phosphate manganese lithium electrode
Material.
It is used as cell positive material by the ball shape ferric phosphate manganese lithium that method in embodiment 4 is prepared, by performance test
Obtain parameter as shown in Table 2.
Embodiment 5
（1）By lithium acetate, potassium manganate, ferrous sulfate, phosphoric acid and methyl glycol fatty acid ester in molar ratio 3:0.99:0.01:
1:0.01 is weighed, and then potassium manganate and ferrous sulfate is codissolved in the solution of deionized water formation 0.5mol/L, by phosphoric acid
It is dissolved in deionized water respectively with lithium acetate, is respectively formed the phosphoric acid solution of 0.5mol/L and the lithium acetate solution of 1.5mol/L；
（2）It is 1 that volume ratio is added in into the mixed liquor of potassium manganate and ferrous sulfate:0.05 tartaric acid forms tartaric acid
Mixed liquor, and constantly stir evenly, the phosphoric acid solution isometric with the tartaric acid mixed liquor is then added to the winestone
In sour mixed liquor, mixed system is formed, and stir evenly, finally lithium acetate solution is added in the mixed system, stirred
Uniformly, precursor liquid is obtained, wherein, the lithium acetate solution is equal with the phosphoric acid solution volume；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with toluene cyclohexanone solvent, setting spray drying
The reaction temperature of case is 200 DEG C, obtains pre-reaction spheric granules, wherein, the volume of the precursor liquid and toluene cyclohexanone solvent
Than being 1:2；
（4）By the pre-reaction spheric granules further across calcination processing, calcine technology is the precalcining at 300 DEG C
2h, it is 760 DEG C then to increase temperature, and heating rate is 30 DEG C/h, calcination time 2h, obtains ball shape ferric phosphate manganese lithium electrode material
Material.
It is used as cell positive material by the ball shape ferric phosphate manganese lithium that method in embodiment 5 is prepared, by performance test
It is as shown in table 2 to obtain parameter.
Table 2
| Performance indicator | Internal resistance（mΩ） | - 30 DEG C of specific capacities（mAh/g） | 80 DEG C of specific capacities（mAh/g） |
| Embodiment 1 | 2.3 | 255 | 265 |
| Embodiment 2 | 1.6 | 251 | 268 |
| Embodiment 3 | 1.2 | 268 | 273 |
| Embodiment 4 | 3.9 | 267 | 276 |
| Embodiment 5 | 1.6 | 242 | 256 |
Claims (7)
1. a kind of preparation method of ball shape ferric phosphate manganese lithium electrode material, which is characterized in that the method uses water-soluble lithium
Salt, manganese salt, molysite, phosphorus source include the following steps as synthesis material：
（1）By water-soluble lithium salts, manganese salt, molysite, phosphorus source and emulsifier in molar ratio 3:(1-x):x:1:0.01 is weighed,
Then manganese salt and molysite are codissolved in the solution of deionized water formation 0.5mol/L by middle x=0.01-0.5, by phosphorus source and lithium salts point
It is not dissolved in deionized water, is respectively formed the phosphorus source solution of 0.5mol/L and the lithium salt solution of 1.5mol/L；
（2）It is 1 that volume ratio is added in into the mixed liquor of manganese salt and molysite:（0.01-0.05）Tartaric acid, formed tartaric acid mixing
Liquid, and constantly stir evenly, the phosphorus source solution isometric with the tartaric acid mixed liquor then is added to the tartaric acid mixes
It closes in liquid, forms mixed system, and stir evenly, finally lithium salt solution is added in the mixed system, is stirred evenly, is obtained
To precursor liquid, wherein, the lithium salt solution is equal with phosphorus source liquor capacity；
（3）It is sprayed from spray drying case after the precursor liquid is mixed with organic solvent, emulsifier, setting spray drying case
Reaction temperature is 160-200 DEG C, obtains pre-reaction spheric granules, wherein, the volume ratio of the precursor liquid and organic solvent is 1:
1-2；
（4）By the pre-reaction spheric granules further across calcination processing, ball shape ferric phosphate manganese lithium electrode material is obtained.
2. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Lithium salts uses lithium hydroxide, lithium acetate, lithium sulfate and lithium nitrate any one or more combination therein.
3. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Manganese salt is manganese oxalate, manganese acetate, manganese sulfate, manganese chloride, potassium permanganate, any one of potassium manganate or two or more combinations,
The molysite is any one of ferrous sulfate, ferrous nitrate, frerrous chloride soluble ferrite or two or more combinations.
4. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Phosphorus source is using any one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate or two or more combinations.
5. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Emulsifier is fatty glyceride, methyl glycol fatty acid ester, dodecyl sodium sulfate, neopelex any or
Two or more combinations.
6. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Organic solvent is benzene,toluene,xylene, hexamethylene, cyclohexanone, toluene cyclohexanone, pentane, hexane, octane any or two
Kind or more combination.
7. the preparation method of a kind of ball shape ferric phosphate manganese lithium electrode material according to claim 1, which is characterized in that described
Calcine technology is the precalcining 0.5-2h at 230-300 DEG C, and it is 700-760 DEG C then to increase temperature, heating rate 10-30
DEG C/h, calcination time 1-2h.
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