CN104124453A - Lithium iron manganese phosphate composite positive electrode material and preparation method, positive electrode and lithium battery - Google Patents
Lithium iron manganese phosphate composite positive electrode material and preparation method, positive electrode and lithium battery Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- 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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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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Abstract
The invention discloses a lithium iron manganese phosphate composite positive electrode material and a preparation method thereof, a lithium battery positive electrode and a lithium battery. The size of the lithium iron manganese phosphate composite positive electrode material is nano-scale, graphdiyne is compounded in a lithium iron manganese phosphate base material, and the mass of the graphdiyne is 0.1-10% that of the lithium iron manganese phosphate base material. The preparation method comprises the steps of dissolving nano-scale lithium source, manganese source, iron source and phosphorus source in a solvent according to the molar ratio of the elements of lithium iron manganese phosphate to form a solution, sequentially adding a complexing agent and a graphdiyne solution into the solution, then drying, grinding, sintering and annealing. Both the lithium battery positive electrode and the lithium battery contain the lithium iron manganese phosphate composite positive electrode material. According to the lithium iron manganese phosphate composite positive electrode material, the migration paths of Li<+> and electrons are shortened by reducing the primary particle size, so that the electric conductivity of the material is improved. According to the preparation method, the performance stability of the lithium iron manganese phosphate composite positive electrode material can be ensured. The discharge gram volume and circulating volume retention rate of the lithium battery is high.
Description
Technical field
The invention belongs to battery technology field, be specifically related to a kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof, lithium battery anode and lithium battery.
Background technology
In the last few years, anode material for lithium-ion batteries LiFePO
4because thering are raw material wide material sources, low price, thermal stability is excellent, good cycle, the advantages such as safety non-toxic receive much concern, and are considered to desirable anode material for lithium-ion batteries of new generation, however LiFePO
4lower discharge voltage plateau (about 3.4V) is can metric density lower has limited its development and application.
With LiFePO
4the LiMnPO with same structure
4with respect to Li
+the electrode potential of/Li is 4.1V, far above LiFePO
4voltage platform, and be positioned at the electrochemical stability window of existing electrolyte system, following application prospect is extensive, therefore receives much concern.Yet, due to LiMnPO
4conductivity extreme difference, be considered to insulator, cause the synthetic LiMnPO that can reversiblely discharge and recharge
4very difficult, limited its development and application.
Iron manganese phosphate for lithium LiMn
xfe
1-xpO
4(0<x<1) be at LiMnPO
4on the basis of modification, grow up, although Fe
2+introducing can make the conductivity of lithium manganese phosphate increase, but the amplitude improving is limited, is difficult to make the chemical property of material to give full play of.Therefore, emphasis research of the present invention how further to improve the electric conductivity of this iron manganese phosphate for lithium.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, a kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof is provided, not high to solve existing iron manganese phosphate lithium anode material conductivity, prepare discharge capacity of lithium ion battery low, circulation keeps the technical problem of rate variance.
Another object of the embodiment of the present invention is to provide a kind of lithium battery anode that contains this iron manganese phosphate for lithium composite positive pole and lithium battery.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
An iron manganese phosphate for lithium composite positive pole, described iron manganese phosphate for lithium composite positive pole is of a size of nanoscale, and is compounded with graphite alkene in iron manganese phosphate for lithium base material, and the quality of described graphite alkene is the 0.1-10% of described iron manganese phosphate for lithium base material quality.
And a kind of preparation method of iron manganese phosphate for lithium composite positive pole, comprises the steps:
According to the mol ratio of each element of iron manganese phosphate for lithium, nano level lithium source, manganese source, source of iron, phosphorus source are added in solvent and carry out dissolution process, obtain clear solution A;
In described clear solution A, add complexing agent, and carry out mixed processing, obtain mixed liquid B;
In described mixed liquid B, add graphite alkene solution, and carry out mixed processing, obtain mixed liquor C; Wherein, the amount that described graphite alkene solution adds is the theoretical 0.1-10% that generates iron manganese phosphate for lithium quality;
Mixed liquor C is dried, obtains iron manganese phosphate for lithium composite positive pole presoma;
Described iron manganese phosphate for lithium composite positive pole presoma is carried out to milled processed, after 50-300 order sieves in protective atmosphere, heat treatment at 500-900 ℃, then carry out annealing in process.
And, a kind of lithium battery anode, comprise collector and be combined in the positive electrode on described collector, described positive electrode is above-mentioned iron manganese phosphate for lithium composite positive pole or the iron manganese phosphate for lithium composite positive pole prepared by the preparation method of above-mentioned iron manganese phosphate for lithium composite positive pole.
And, a kind of lithium battery, described lithium battery comprises above-mentioned lithium battery anode.
Compared with prior art, above-mentioned iron manganese phosphate for lithium composite positive pole particle is nanoscale, from dwindling primary particle size aspect, shortens Li
+with the migration path of electronics, thereby improve the conductivity of material, improved the chemical property of material.Adopt graphite alkene complex technique, improve the inner conductive of iron manganese phosphate lithium material, effectively reduce the specific insulation of iron manganese phosphate lithium material, improve internal electron conductivity and the lithium ion transmission speed of material, and can not cause the voltage platform of iron manganese phosphate for lithium to reduce.
The preparation method of above-mentioned iron manganese phosphate for lithium composite positive pole adopts complexing agent complexation of metal ions, makes it dispersed at atomic level, and obtains nanometer materials by chemical method.The method make graphite alkene and iron manganese phosphate for lithium reach molecular level other is dispersed, realize graphite alkene compound to iron manganese phosphate for lithium material structure inside, coated than the carbon of particle surface, the electric conductivity of iron manganese phosphate for lithium is had to significant lifting.In addition, by heat treatment and annealing in process at specific temperature, make the formed composite structure of graphite alkene and iron manganese phosphate for lithium stable.
Above-mentioned lithium battery anode and lithium battery are owing to containing above-mentioned iron manganese phosphate for lithium composite positive pole, again because this iron manganese phosphate for lithium composite positive pole has excellent as mentioned above electric conductivity, therefore, lithium battery anode chemical property is good, thereby gives this lithium battery high electric discharge gram volume and excellent multiplying power cycle characteristics and high circulation volume conservation rate.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is embodiment of the present invention iron manganese phosphate for lithium composite positive pole preparation method schematic flow sheet;
Fig. 2 is the SEM figure with the iron manganese phosphate for lithium composite positive pole of the embodiment of the present invention 1 preparation;
Fig. 3 is the TEM figure with the iron manganese phosphate for lithium composite positive pole of the embodiment of the present invention 1 preparation;
Fig. 4 is the charging and discharging curve figure with the lithium ion battery of the iron manganese phosphate for lithium composite positive pole of the embodiment of the present invention 1 preparation;
Fig. 5 is for take circulation volume conservation rate curve chart after lithium ion battery 1C rate charge-discharge that the LiFePO4 composite conductor of the embodiment of the present invention 1 preparation is positive electrode 125 times.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides the iron manganese phosphate for lithium composite positive pole that a kind of conductivity is high.This iron manganese phosphate for lithium composite positive pole is of a size of nanoscale, and is compounded with graphite alkene in iron manganese phosphate for lithium base material.
Particularly, this graphite alkene is monolayer carbon atom, is by 1,3-, bis-acetylene bonds, phenyl ring conjugation to be connected to form to the full carbon molecule of two dimensional surface network configuration, there is abundant carbon chemical bond, large conjugated system, wide interplanar distance, good chemical stability and semiconducting behavior.There is special electronic structure, large specific surface and loose structure, superior electrical performance, research shows that the conductive capability of graphite alkene is stronger than Graphene.In above-mentioned iron manganese phosphate for lithium composite positive pole, this graphite alkene is compound to the inner Uniform Doped of iron manganese phosphate for lithium material structure, form the composite material of rock-steady structure, thereby effectively improve the inner conductive of iron manganese phosphate lithium material, effectively reduce the specific insulation of iron manganese phosphate lithium material.In one embodiment, in iron manganese phosphate for lithium composite positive pole, the quality of this graphite alkene is the 0.1-10% of iron manganese phosphate for lithium base material quality.In a preferred embodiment, the quality of this graphite alkene is the 0.5%-5% of iron manganese phosphate for lithium base material quality.By adjusting the content of graphite alkene, indirect regulation graphite alkene, in the distribution of iron manganese phosphate for lithium base material inside, can further improve its electric conductivity and the stability that improves material.
Above-mentioned iron manganese phosphate for lithium composite positive pole size Control is nanoscale, from dwindling primary particle size aspect, shortens Li
+with the migration path of electronics, thereby improve the conductivity of material, improved the chemical property of material.In order further to improve the conductivity of iron manganese phosphate for lithium composite positive pole, in one embodiment, this iron manganese phosphate for lithium composite positive pole size Control is 10-80nm.
Therefore, above-mentioned iron manganese phosphate for lithium composite positive pole adopts graphite alkene compound to iron manganese phosphate for lithium inside configuration, significantly improved the electric conductivity of iron manganese phosphate for lithium, effectively reduce the specific insulation of iron manganese phosphate lithium material, improve internal electron conductivity and the lithium ion transmission speed of material, and can not cause the voltage platform of iron manganese phosphate for lithium to reduce., compare with existing carbon clad structure meanwhile, the stability of this iron manganese phosphate for lithium composite positive pole excellence, the carbon coating layer that can effectively overcome carbon clad structure peels off.In addition, above-mentioned iron manganese phosphate for lithium composite positive pole particle is controlled as nanoscale, from dwindling primary particle size aspect, shortens Li
+with the migration path of electronics, thereby improve the conductivity of material, improved the chemical property of material.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of above-mentioned iron manganese phosphate for lithium composite positive pole, and the method technological process refers to Fig. 1.This iron manganese phosphate for lithium composite positive pole is preparation method comprise the steps:
Step S01: according to the mol ratio of each element of iron manganese phosphate for lithium, nano level lithium source, manganese source, source of iron, phosphorus source are added in solvent and carry out dissolution process, obtain clear solution A;
Step S02: add complexing agent in the described clear solution A preparing to step S01, and carry out mixed processing, obtain mixed liquid B;
Step S03: add graphite alkene solution in the described mixed liquid B of preparing to step S02, and carry out mixed processing, obtain mixed liquor C;
Step S04: mixed liquor C prepared by step S03 is dried, obtains iron manganese phosphate for lithium composite positive pole presoma;
Step S05: described iron manganese phosphate for lithium composite positive pole presoma prepared by step S04 carries out milled processed, after 50-300 order sieves in protective atmosphere, heat treatment at 500-900 ℃, then carry out annealing in process.
Particularly, in above-mentioned steps S01, the molecular formula of iron manganese phosphate for lithium can be expressed as LiMn
xfe
1-xpO
4, wherein, 0<x<1.Due to Fe
2+replace part Mn
2+ratio, although Fe
2+intervention, can increase cell parameter, improve the conductivity of material, but add Fe
2+ratio excessive, can cause voltage platform to reduce, and the advantage of lithium manganese phosphate maximum is to have high voltage platform (4.1V).Accordingly, in a preferred embodiment, this x is 0.8.
The acquisition side in the nanometer lithium source in this step S01, manganese source, source of iron, phosphorus source adopts milled processed by lithium source, manganese source, source of iron, phosphorus source, makes each raw material particle size reach nanoscale.Wherein, milled processed can adopt ball milling or sand milling PROCESS FOR TREATMENT.In specific embodiment, nanoscale is carried out in lithium source, manganese source, source of iron, phosphorus source and process and can process with reference to the step S11 in embodiment 1.
Wherein, lithium source, manganese source, source of iron, phosphorus source are the respective compound of preparing iron manganese phosphate for lithium routine, for obtain transparent solution A, should select and can be dissolved in lithium source in solvent, manganese source, source of iron, phosphorus source.Therefore, in one embodiment, the solvent of preparing this clear solution A is one or more the admixture solvent being preferably in deionized water, distilled water, ethanol, oxalic acid, methyl alcohol, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO), ethylene glycol.In another embodiment, lithium source can but not only select lithium carbonate, manganese source can but not only select manganese nitrate, source of iron can but not only select ferric nitrate, phosphorus source can but not only select ammonium dihydrogen phosphate.
Above-mentioned nanoscale lithium source, manganese source, source of iron, phosphorus source are dissolved completely, obtain clear solution.
Metal ion in the above-mentioned clear solution A of complexing agent energy complexing adding in above-mentioned steps S02, makes it dispersed at atomic level.In order to improve the complexing power of complexing agent to the metal ion in above-mentioned clear solution A, in one embodiment, this complexing agent is selected at least one in ethylenediamine tetra-acetic acid, organic carbonate, ethyl acetate, Ethyl formate, oxalic acid, alkene, alkynes, aromatic hydrocarbon, ethene.
In another embodiment, the amount that this complexing agent adds is the theoretical 10-50% that generates iron manganese phosphate for lithium quality.
For complexing agent is given full play to, work, in this complexing agent is joined to above-mentioned clear solution A or afterwards, clear solution A is carried out to stir process, the time of stirring should be abundant, as after treating that complexing agent adds, continue stir process 0.5-2 hour.
In above-mentioned steps S03, in order to make graphite alkene fully mix dispersion with above-mentioned mixed liquid B, in one embodiment, adopt the mode dropwise dripping to add in described mixed liquid B this graphite alkene solution.In further preferred embodiment, the mass concentration of this graphite alkene solution is 20%-80%, and the drop rate dropping in described mixed liquid B is 1d/min-10d/min.
Wherein, graphite alkene solution in this step S03 can be prepared as follows: adopt ultrasonic graphite alkene to be dispersed in solvent, this solvent can but not only select ethanol, other can dispersed graphite alkynes and not affect other solvents of mixed liquid B system all passable, concrete as polyethylene glycol, acetone, isopropyl alcohol etc.
For by adjusting the content of graphite alkene, realize indirect regulation graphite alkene in the distribution of iron manganese phosphate for lithium base material inside, improve its electric conductivity and the stability that improves material.In one embodiment, the amount that graphite alkene solution adds guarantees that graphite alkene is the theoretical 0.1%-10% that generates iron manganese phosphate for lithium quality, is preferably 0.5-10%.
In above-mentioned steps S04, it is for except desolventizing that mixed liquor C carries out dry object, in one embodiment, this mixed liquor C, at 100～500 ℃, is heated after 2～10 hours, collects solid.Particularly, can in baking oven, carry out.
In above-mentioned steps S05, heat treatment at specific environment and temperature, making iron manganese phosphate for lithium composite positive pole presoma in heat treatment process, change original atom distributes, and in annealing process, realize atom and redistribute, realize graphite alkene compound to iron manganese phosphate for lithium material structure inside, improve the conductivity of iron manganese phosphate for lithium.Inner full and uniform compound to iron manganese phosphate for lithium material structure in order to guarantee graphite alkene, in one embodiment, the heat treated time is 2-24 hour at this 500-900 ℃.In another preferred embodiment, in this heat treated heating process, with the heating rate of 1～15 ℃/min, be warming up to 500-900 ℃.
In addition, annealing conditions also has impact to the chemical property of iron manganese phosphate for lithium composite positive pole and stability.In order to guarantee excellent chemical property and the stability of graphite alkene to iron manganese phosphate lithium material.In one embodiment, this step annealing in process adopts slow annealing to process, as the speed with 1-5 ℃/min in protective atmosphere is cooled to room temperature.
In this heat treatment and annealing in process process, this protective atmosphere refers to inert atmosphere or reducing atmosphere, certainly, if conditions permit can also be vacuum environment.This protective atmosphere is to avoid iron manganese phosphate for lithium composite positive pole presoma oxidized in heat treatment process.
The preparation method of above-mentioned iron manganese phosphate for lithium composite positive pole adopts complexing agent complexation of metal ions, makes it dispersed at atomic level, and obtains nanometer materials by chemical method.The method make graphite alkene and iron manganese phosphate for lithium reach molecular level other is dispersed, realize graphite alkene compound to iron manganese phosphate for lithium material structure inside, coated than the carbon of particle surface, the electric conductivity of iron manganese phosphate for lithium is had to significant lifting.In addition, by heat treatment and annealing in process at specific temperature, make the formed composite structure of graphite alkene and iron manganese phosphate for lithium stable.
On basis based on above-mentioned iron manganese phosphate for lithium composite positive pole embodiment, the embodiment of the present invention also provides a kind of lithium battery anode, and it comprises collector and is combined in the positive electrode on this collector.Wherein, this positive electrode is iron manganese phosphate for lithium composite positive pole mentioned above; Collector can be selected the conventional collector in this area.Like this, this lithium battery anode is owing to containing iron manganese phosphate for lithium composite positive pole mentioned above, and due to this iron manganese phosphate for lithium composite positive pole, to have electric conductivity as above excellent again, stabilized structure, and chemical property is good.Therefore, the stable performance in the course of the work of this lithium battery anode, conductivity is high, stabilized structure.
Correspondingly, on the basis of above-mentioned lithium battery anode embodiment, the embodiment of the present invention also provides a kind of lithium battery, and this lithium battery comprises lithium battery anode mentioned above.Like this, this lithium battery is owing to containing lithium battery anode mentioned above, thereby gives this lithium battery high electric discharge gram volume and excellent multiplying power cycle characteristics and high circulation volume conservation rate characteristic, and this lithium battery stable electrochemical property in charge and discharge cycles process, capacity is high, and the life-span is long.Make it can long-term work under large current condition, therefore, can be for being generalizable on electric automobile.
By a plurality of embodiment, illustrate below the aspects such as above-mentioned lithium battery iron manganese phosphate for lithium composite positive pole and preparation method thereof, lithium battery anode and lithium battery.
Embodiment 1
A kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof, its preparation method comprises the steps:
Step S11: by LITHIUM BATTERY raw material lithium carbonate, manganese nitrate, ferric nitrate, ammonium dihydrogen phosphate, ethylenediamine tetra-acetic acid, ethyl acetate after sand mill is processed 30min, according to mol ratio, be that Li:Mn:Fe:P=1.1:0.8:0.2:1 carries out weighing (theoretical product is 1 mole), and be dissolved in successively in deionized water and oxalic acid, magnetic agitation is to forming clear solution A;
Step S12: take 10g ethylenediamine tetra-acetic acid and add in solution A, magnetic agitation, when solution colour fades to dark brown, adds 4g ethyl acetate, after magnetic agitation 1h, forms mixed solution B;
Step S13: be dispersed in alcohol solvent 0.5g graphite alkene is ultrasonic, ultrasonic time is 1h, forms solution C;
Step S14: solution C is dropwise added drop-wise in the solution B that continues to stir, continues to stir 2h, form mixed solution D;
Step S15: mixed solution D is placed in to baking oven, and 120 ℃ are incubated 4 hours, obtain the pressed powder of iron manganese phosphate for lithium precursor, by this pressed powder, after grinder grinds 2h, 120 ℃ of dry rear 200 eye mesh screens of crossing of vacuum, obtain finely dispersed mixture E;
Step S16: mixture E is put into tube furnace, and under nitrogen protection, heating rate is 2 ℃/min, 680 ℃ are incubated 8 hours, obtain nanometer iron manganese phosphate for lithium composite positive pole.
The iron manganese phosphate for lithium composite positive pole of embodiment 1 preparation is carried out to SEM and tem analysis, and as shown in Figure 2, TEM schemes as shown in Figure 3 its SEM figure.Have Fig. 2, Fig. 3 known, this iron manganese phosphate for lithium composite positive pole is nanoscale, even particle size distribution, and compound with graphite alkene.
Embodiment 2
A kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof, its preparation method comprises the steps:
Step S21: by LITHIUM BATTERY raw material lithium carbonate, manganese nitrate, ferric nitrate, ammonium dihydrogen phosphate, ethylenediamine tetra-acetic acid, ethyl acetate after sand mill is processed 30min, according to mol ratio, be that Li:Mn:Fe:P=1.1:0.8:0.2:1 carries out weighing (theoretical product is 1 mole), and be dissolved in successively in deionized water and oxalic acid, magnetic agitation is to forming clear solution A;
Step S22: take 12g organic carbonate and add in solution A, magnetic agitation, when solution colour fades to dark brown, adds 5g ethyl acetate, after magnetic agitation 1h, forms mixed solution B;
Step S23: be dispersed in alcohol solvent 0.5g graphite alkene is ultrasonic, ultrasonic time is 1h, forms solution C;
Step S24: solution C is dropwise added drop-wise in the solution B that continues to stir, continues to stir 2h, form mixed solution D;
Step S25: mixed solution D is placed in to baking oven, and 100 ℃ are incubated 10 hours, obtain the pressed powder of iron manganese phosphate for lithium precursor, by this pressed powder, after grinder grinds 2h, 120 ℃ of dry rear 300 eye mesh screens of crossing of vacuum, obtain finely dispersed mixture E;
Step S26: mixture E is put into tube furnace, and under nitrogen protection, heating rate is 1/ minute, 900 ℃ are incubated 2.5 hours, obtain nanometer iron manganese phosphate for lithium composite positive pole.
Embodiment 3
A kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof, its preparation method comprises the steps:
Step S31: by LITHIUM BATTERY raw material lithium carbonate, manganese nitrate, ferric nitrate, ammonium dihydrogen phosphate, ethylenediamine tetra-acetic acid, ethyl acetate after sand mill is processed 30min, according to mol ratio, be that Li:Mn:Fe:P=1.1:0.8:0.2:1 carries out weighing (theoretical product is 1 mole), and be dissolved in successively in deionized water and oxalic acid, magnetic agitation is to forming clear solution A;
Step S32: take 8g oxalic acid and add in solution A, magnetic agitation, when solution colour fades to dark brown, adds 3g aromatic hydrocarbon, after magnetic agitation 1h, forms mixed solution B;
Step S33: be dispersed in alcohol solvent 0.5g graphite alkene is ultrasonic, ultrasonic time is 1h, forms solution C;
Step S34: solution C is dropwise added drop-wise in the solution B that continues to stir, continues to stir 2h, form mixed solution D;
Step S35: mixed solution D is placed in to baking oven, and 450 ℃ are incubated 2 hours, obtain the pressed powder of iron manganese phosphate for lithium precursor, by this pressed powder, after grinder grinds 2h, 120 ℃ of dry rear 50 eye mesh screens of crossing of vacuum, obtain finely dispersed mixture E;
Step S36: mixture E is put into tube furnace, and under nitrogen protection, heating rate is 15/ minute, 900 ℃ are incubated 2.5 hours, obtain nanometer iron manganese phosphate for lithium composite positive pole.
Embodiment 4
A kind of iron manganese phosphate for lithium composite positive pole and preparation method thereof, its preparation method comprises the steps:
Step S41: by LITHIUM BATTERY raw material lithium carbonate, manganese nitrate, ferric nitrate, ammonium dihydrogen phosphate, ethylenediamine tetra-acetic acid, ethyl acetate after sand mill is processed 30min, according to mol ratio, be that Li:Mn:Fe:P=1.1:0.8:0.2:1 carries out weighing (theoretical product is 1 mole), and be dissolved in successively in dimethyl sulfoxide (DMSO), magnetic agitation is to forming clear solution A;
Step S42: take 14g aromatic hydrocarbon and add in solution A, magnetic agitation, treats that solution colour fades to dark brown, forms mixed solution B;
Step S43: be dispersed in alcohol solvent 0.5g graphite alkene is ultrasonic, ultrasonic time is 1h, forms solution C;
Step S44: solution C is dropwise added drop-wise in the solution B that continues to stir, continues to stir 2h, form mixed solution D;
Step S45: mixed solution D is placed in to baking oven, and 300 ℃ are incubated 5 hours, obtain the pressed powder of iron manganese phosphate for lithium precursor, by this pressed powder, after grinder grinds 2h, 120 ℃ of dry rear 50 eye mesh screens of crossing of vacuum, obtain finely dispersed mixture E;
Step S46: mixture E is put into tube furnace, and under nitrogen protection, heating rate is 8/ minute, 700 ℃ are incubated 12 hours, obtain nanometer iron manganese phosphate for lithium composite positive pole.
Comparison example 1
Adopt raw material and preparation process in embodiment 1, only with Graphene, replace graphite alkene and prepare positive electrode.
Comparison example 2
Adopt raw material and preparation process in embodiment 1, only with carbon nano-fiber, replace graphite alkene and prepare positive electrode.
Comparison example 3
Adopt raw material and preparation process in embodiment 1, only with superconduct graphite, replace graphite alkene and prepare positive electrode.
Lithium ion battery embodiment
The iron manganese phosphate for lithium composite positive pole of preparing with embodiment 1-4 respectively and comparative example 1-3 positive electrode are active material, acetylene black is conductive agent, and Kynoar is binding agent, is made into anode pole piece, take metal lithium sheet as negative pole, be assembled in a conventional manner lithium ion battery.
The performance test of lithium ion battery:
The various embodiments described above lithium ion battery is carried out respectively to following performance test, and test result is as shown in table 1 below.Wherein, in each embodiment in table 1, charge-discharge test voltage is 2.0～4.25V, and in embodiment 1, as shown in Figure 4, after 1C rate charge-discharge 125 times, circulation volume conservation rate curve as shown in Figure 5 for the charging and discharging curve of lithium ion battery.
Table 1
From above-mentioned table 1 and Fig. 4,5, the iron manganese phosphate for lithium composite positive pole providing with the embodiment of the present invention has high electric discharge gram volume and excellent multiplying power cycle characteristics and high circulation volume conservation rate with the lithium ion battery of positive electrode, apparently higher than the correlated performance of lithium ion battery in comparison example 1-3.Therefore, containing positive electrode that above-described embodiment provides can long-term work under large current condition, can be used on the special installations such as high power energy storage device, also for its popularization and application on electric automobile provides guarantee.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an iron manganese phosphate for lithium composite positive pole, it is characterized in that: described iron manganese phosphate for lithium composite positive pole is of a size of nanoscale, and in iron manganese phosphate for lithium base material, be compounded with graphite alkene, the quality of described graphite alkene is the 0.1%-10% of described iron manganese phosphate for lithium base material quality.
2. iron manganese phosphate for lithium composite positive pole as claimed in claim 1, is characterized in that: the quality of described graphite alkene is the 0.5%-5% of described iron manganese phosphate for lithium base material quality; And/or
Described iron manganese phosphate for lithium composite positive pole is of a size of 10-80nm.
3. a preparation method for iron manganese phosphate for lithium composite positive pole, comprises the steps:
According to the mol ratio of each element of iron manganese phosphate for lithium, nano level lithium source, manganese source, source of iron, phosphorus source are added in solvent and carry out dissolution process, obtain clear solution A;
In described clear solution A, add complexing agent, and carry out mixed processing, obtain mixed liquid B;
In described mixed liquid B, add graphite alkene solution, and carry out mixed processing, obtain mixed liquor C; Wherein, the amount that described graphite alkene solution adds guarantees that graphite alkene is the theoretical 0.1-10% that generates iron manganese phosphate for lithium quality;
Mixed liquor C is dried, obtains iron manganese phosphate for lithium composite positive pole presoma;
Described iron manganese phosphate for lithium composite positive pole presoma is carried out to milled processed, after 50-300 order sieves in protective atmosphere, heat treatment at 500-900 ℃, then carry out annealing in process.
4. the preparation method of iron manganese phosphate for lithium composite positive pole as claimed in claim 3, is characterized in that: at described 500-900 ℃, the heat treated time is 2-24 hour.
5. the preparation method of the iron manganese phosphate for lithium composite positive pole as described in claim 3 or 4, is characterized in that: it is that described graphite alkene solution is dropwise dropped in described mixed liquid B that described graphite alkene solution adds the mode in described mixed liquid B.
6. the preparation method of iron manganese phosphate for lithium composite positive pole as claimed in claim 5, is characterized in that: the mass concentration of described graphite alkene solution is 20%-80%, and the drop rate dropping in described mixed liquid B is 1d/min-10d/min.
7. the preparation method of iron manganese phosphate for lithium composite positive pole as claimed in claim 3, is characterized in that: in described clear solution A, adding in the step of complexing agent, the amount that described complexing agent adds is the theoretical 10-50% that generates iron manganese phosphate for lithium quality.
8. as the preparation method of the iron manganese phosphate for lithium composite positive pole of claim 3,4,6,7 as described in arbitrary, it is characterized in that: described complexing agent is at least one in ethylenediamine tetra-acetic acid, organic carbonate, ethyl acetate, Ethyl formate, oxalic acid, alkene, alkynes, aromatic hydrocarbon, ethene.
9. a lithium battery anode, comprise and it is characterized in that collector and be combined in the positive electrode on described collector: described positive electrode is the arbitrary described iron manganese phosphate for lithium composite positive pole of claim 1-2 or the iron manganese phosphate for lithium composite positive pole prepared by the preparation method of the arbitrary described iron manganese phosphate for lithium composite positive pole of claim 3-8.
10. a lithium battery, is characterized in that, described lithium battery comprises lithium battery anode claimed in claim 9.
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