CN102437311B - Lithium iron phosphate composite material, its preparation method and application - Google Patents
Lithium iron phosphate composite material, its preparation method and application Download PDFInfo
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- CN102437311B CN102437311B CN201010296661.5A CN201010296661A CN102437311B CN 102437311 B CN102437311 B CN 102437311B CN 201010296661 A CN201010296661 A CN 201010296661A CN 102437311 B CN102437311 B CN 102437311B
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Abstract
The invention is suitable for the technical field of batteries, and provides a lithium iron phosphate composite material, its preparation method and an application. The lithium iron phosphate composite material has a nanoparticle structure with lithium iron phosphate nanocrystals as the core. The external surface of the nanoparticle structure is covered with a nano-carbon particle coating, the external surface of which is covered with grapheme. The chemical composition of the lithium iron phosphate nanocrystals is LiFe1-xMxPO4, wherein M is metal ions and x is being less than 1 and greater than or equal to 0.001. By cladding the nano-carbon particles with the lithium iron phosphate crystals, adding grapheme and adding metal ions in the lithium iron phosphate crystals, conductivity of the lithium iron phosphate composite material in the embodiment of the invention is greatly improved. Simultaneously, the nano particle size of the lithium iron phosphate crystals guarantees rapid charge and discharge of the lithium iron phosphate crystals in the embodiment of the invention.
Description
Technical field
The invention belongs to battery technology field, relate in particular to a kind of composite ferric lithium phosphate material, its preparation method and application.
Background technology
In prior art, anode material for lithium-ion batteries concentrates on the transition metal oxide of lithium as the LiMO of layer structure
2the LiMn of (M=Co, Ni, Mn) and spinel structure
2o
4.As positive electrode, they differ from one another, LiCoO
2cost is high, natural resources shortage, and toxicity is large; LiNiO
2preparation difficulty, poor heat stability; LiMn
2o
4capacity is lower, and cyclical stability is poor.LiFePO
4raw material sources are extensive, cheap, the Heat stability is good of non-environmental-pollution, material, and the security performance of prepared battery is outstanding, become the anode material for lithium-ion batteries of new generation of tool development and application potentiality.But the conductance of prior art composite ferric lithium phosphate material is low, and charge-discharge magnification is low, can not fast charging and discharging.
Summary of the invention
In view of this, the embodiment of the present invention provides a kind of composite ferric lithium phosphate material, solves the technical problem that the battery prepare with composite ferric lithium phosphate material in prior art can not fast charging and discharging.
The present invention realizes like this, a kind of composite ferric lithium phosphate material, described composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain, described nano_scale particle structural outer surface has nanometer carbon particles coating layer, described nanometer carbon particles coating layer outer surface is coated with Graphene, and the chemical composition of described lithium iron phosphate nano crystal grain is: LiFe
1-xm
xpO
4, wherein M is metal ion, 0.001≤x < 1.
The embodiment of the present invention further provides a kind of preparation method of composite ferric lithium phosphate material, comprises the steps:
According to metal M, ferro element and P elements mol ratio, be x: 1-x: 1, preparation molysite mixed solution;
Above-mentioned mixed solution is added in the organic carbon source aqueous solution, and under 20-80 ℃ of bath temperature, hybrid reaction is 0.5～5 hour, and the pH value of hybrid reaction system is controlled at 1～7, and making the coated chemical composition of organic carbon source is Fe
1-xm
xpO
4nano particle, wherein M is metal ion, 0.001≤x < 1;
Nano particle and Li source compound that the above-mentioned organic carbon source making is coated add graphite oxide aqueous solution, stir, mix, and subsequent drying desolventizes, grind and obtain precursor;
Precursor is calcined to 1-24 hour under reducing atmosphere, 400-1000 ℃ temperature conditions, obtain described composite ferric lithium phosphate material.
The embodiment of the present invention also provides the application of above-mentioned composite ferric lithium phosphate material in lithium ion battery or positive electrode.
The composite ferric lithium phosphate material of the embodiment of the present invention, by nanometer carbon particles coated LiFePO 4 for lithium ion batteries crystal grain, Graphene doping and doped metal ion in LiFePO4 crystal grain, the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention is greatly improved, because LiFePO4 crystal grain is nanometer particle size, guaranteed that the composite ferric lithium phosphate material of the embodiment of the present invention can fast charging and discharging simultaneously.
Accompanying drawing explanation
Fig. 1 is the composite ferric lithium phosphate material electron microscope photo scanning (multiplying power * 10000) of the embodiment of the present invention;
Fig. 2 is the composite ferric lithium phosphate material X-ray diffractogram of the embodiment of the present invention;
Fig. 3 is the composite ferric lithium phosphate material A Bin battery testing result figure of the embodiment of the present invention.
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 described in further detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of composite ferric lithium phosphate material, described composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain, described nano_scale particle structural outer surface has nanometer carbon particles coating layer, described nanometer carbon particles coating layer outer surface is coated with Graphene, and the chemical composition of described lithium iron phosphate nano crystal grain is: LiFe
1-xm
xpO
4, wherein M is metal ion, 0.001≤x < 1.
The composite ferric lithium phosphate material of the embodiment of the present invention is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain.It is basic composition unit that embodiment of the present invention composite material be take nano-scale lithium iron phosphate crystal grain (being lithium iron phosphate nano crystal grain), this nano-scale lithium iron phosphate grain surface has nanometer carbon particles coating layer, form nanometer carbon particles coated LiFePO 4 for lithium ion batteries crystal grain, at this nanometer carbon particles coating layer outer surface, be coated with Graphene simultaneously, specifically, graphene coated is at nanometer carbon particles coated LiFePO 4 for lithium ion batteries nanocrystal outer surface, and preferably this Graphene surface attachment has nanometer carbon particles coated LiFePO 4 for lithium ion batteries crystal grain.By doping metals M ion in LiFePO4 crystal grain, nanometer carbon particles is coated and Graphene adulterates, the electric conductivity of composite ferric lithium phosphate material is greatly enhanced, greatly improved its charge-discharge performance, the polarization phenomena of composite ferric lithium phosphate material in discharging and recharging have been reduced, simultaneously, this composite ferric lithium phosphate material consists of nano ferric phosphate lithium grain, and the particle diameter of LiFePO4 crystal grain is less than 100nm.The combination of high conduction performance and two features of nanometer particle size, makes the composite ferric lithium phosphate material of the embodiment of the present invention have fast charging and discharging performance.Refer to Fig. 1, Fig. 1 shows that embodiment of the present invention composite ferric lithium phosphate material comprises lithium iron phosphate nano crystal grain, and the particle diameter of this lithium iron phosphate nano crystal grain is below 100nm, and it is spherical that this lithium iron phosphate nano crystal grain is class.
Lithium iron phosphate nano crystal grain in the embodiment of the present invention, surface is coated by nanometer carbon particles, and preferably nanometer carbon particles is completely coated, and this nanometer carbon particles is in preparation process, and organic carbon source obtains through calcining, carbonization.Carbon is good electric conducting material, and the LiFePO4 crystal grain in the embodiment of the present invention is coated by nanometer carbon particles, this has increased the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention greatly, improve the charge-discharge magnification of the composite ferric lithium phosphate material of the embodiment of the present invention, greatly alleviated the polarization phenomena in charge and discharge process.
Because Graphene is also very excellent electric conducting material, further greatly improved the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention, the Graphene of the composite ferric lithium phosphate material of the embodiment of the present invention is the aggregation of molecular level Graphene monolithic or this molecular level Graphene monolithic of 2-100.
The chemical composition of this LiFePO4 crystal grain is LiFe
1-xm
xpO
4, wherein, M is metal ion, is preferably the metal ion that chemical price is high, comprises one or more in the metal ions such as magnesium, chromium, copper, zinc, manganese.The value of X is, 0.001≤x < 1, preferred 0.003≤x≤0.3.The M metal ion that adulterates in LiFePO4 lattice, further improves the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention.Metal M ion, in preparation process, is doped in iron phosphate nano particle by coprecipitation method, has guaranteed that metal M uniform ion is doped in iron phosphate nano particle, and the composite ferric lithium phosphate material electric conductivity of the embodiment of the present invention is improved.
The preparation method of the LiFePO4 of the embodiment of the present invention, concrete steps are as follows:
A) according to metal M, ferro element and P elements mol ratio, be x: 1-x: 1, preparation molysite mixed solution;
Step a) in, preparation containing chemical composition be Fe
1-xm
xpO
4the solution of nano particle, by containing Fe
3+compound or compound or its solution of its solution, metal M ion, contain PO
4 3-compound or its solution in solvent, react and make.
The above-mentioned Fe that contains
3+compound include but not limited to iron oxide, ferric sulfate, ironic citrate, also can be by containing Fe
2+compound by being oxidized, obtain containing Fe as tri-iron tetroxide, ferrous sulfate, iron ammonium sulfate, ferrous phosphate ammonia, ferrous phosphate, ferrous citrate, ferrous oxide etc.
3+compound, the oxidant using does not have the restriction of kind, the hydrogen peroxide that preferably ammonium persulfate, clorox, quality percentage composition are 30%, one or more in solid hydrogen peroxide, oxidant concentration is 0.2-6mol/L, use excessive oxidant, guarantee that all ferrous ions can both be oxidized to ferric ion.
The compound that contains metal M ion, such as one or more of magnesium chloride, chromium oxide, zinc chloride, copper sulphate etc.
Contain PO
4 3-compound include but not limited to phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, ferrous phosphate ammonia or ammonium phosphate etc., also can use phosphorus pentoxide, phosphorus pentoxide in the aqueous solution and water reaction, generates phosphoric acid.
The source of iron of using in this step (contains Fe
3+or the compound of ferrous ion), can ionize out iron ion or ferrous ion in solvent, the compound of metal M can ionize out M metal ion, and PO (is contained in phosphorus source
4 3-compound) can ionize out phosphate anion, or can not ionize out ion, but three compounds can react in solvent, generate the ferric phosphate precipitation of metal M doping, for example combination of iron oxide, magnesium oxide and phosphoric acid.
In this step, the mol ratio of M metal ion, iron ion and the phosphorus of use is x: (1-x): 1, and the reaction equation of this step is expressed as:
XM+ (1-x) Fe
3++ PO
4 3-→ LiFe
1-xm
xpO
4, wherein, 0.001≤x < 1, M is metal M ion, comprises one or more in the metal ions such as magnesium ion, chromium ion, zinc ion, copper ion, manganese ion.Metal M and iron ion, phosphate anion, by the method for co-precipitation, form the ferric phosphate precipitation of metal M ion doping, obtain the ferric phosphate lattice of metal M doping, when generating precipitation, precipitation surface is with ferric ion, thereby initiation organic carbon source is at its surface aggregate.By this reaction, obtaining containing chemical composition is Fe
1-xm
xpO
4the solution of nano particle.
B) above-mentioned mixed solution is added in the organic carbon source aqueous solution, under 20-60 ℃ of bath temperature, hybrid reaction is 0.5～5 hour, and the pH value of hybrid reaction system is controlled at 1～7, and making the coated chemical composition of organic carbon source is Fe
1-xm
xpO
4nano particle, wherein M is metal ion, 0.001≤x < 1;
This organic carbon source refers to be Fe in chemical composition
1-xm
xpO
4nanoparticle surface polymerization and the organic carbon source that can decompose at 400-1000 ℃ of temperature, preferably aniline monomer or derivatives thereof, pyrrole monomer or derivatives thereof and thiophene monomer or derivatives thereof etc.Add organic carbon source, pass through Fe
1-xm
xpO
4the oxidation of nanoparticle surface ferric ion, making organic carbon source is Fe in chemical composition
1-xm
xpO
4the polymerization of nano particle outer surface, meanwhile, organic carbon source self also can produce polymerization, thus coated chemical composition is Fe
1-xm
xpO
4nano particle.The consumption of organic carbon source is that chemical composition is Fe
1-xm
xpO
4the 8-100% of nano particle quality.Above-mentioned is Fe containing chemical composition
1-xm
xpO
4the solution of nano particle pumps in the organic carbon source aqueous solution by peristaltic pump, by the pH value of alkaline agent or acidizer maintenance system at 1-7, this alkaline agent can be various alkaline agents, preferably ammoniacal liquor, NaOH, potassium hydroxide, potash, saleratus etc., acidizer is acetic acid or hydrochloric acid etc.The temperature of system is controlled to 20-60 ℃ simultaneously, can uses the mode of heating water bath, control the temperature of reaction.Stirring reaction 0.5-5 hour, reactant continues to stir 0.5-5 hour after stopping adding.In this step, the pH value of reaction system is 1-7, belongs to stronger sour environment, and under this environment, making organic carbon source can better be gathered in above-mentioned chemical composition is Fe
1-xm
xpO
4nanoparticle surface.
At step c) in, nano particle and Li source compound that the above-mentioned organic carbon source making is coated add graphite oxide aqueous solution, stir, mix, and subsequent drying desolventizes, grind and obtain precursor;
The preparation method of graphene oxide is according to improved hummers method (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), adding after graphene oxide, there is organic reaction and organic carbon source and Graphene is connected together in the functional group on the functional group of organic carbon source and graphene oxide surface.The source compound of lithium includes but not limited to one or more in lithia, lithium hydroxide, lithium carbonate, lithium acetate, lithium phosphate, lithium dihydrogen phosphate, lithium fluoride etc.
The quality of graphene oxide is that chemical composition is LiFe
1-xm
xpO
4the 0.1-99% of nano particle quality; The mole of the source compound of lithium and chemical composition are Fe
1-xm
xpO
4the ratio of nano particle mole is 1: 1; Stir process mixes mixed solution.
In this step, dry method is restriction not, and such as heat drying, oven drying etc., after oven dry, grinds product, obtains the precursor of composite ferric lithium phosphate material.
In steps d) in, by precursor, under reducing atmosphere, 400-1000 ℃ temperature conditions, calcining 1-24 hour, obtains composite ferric lithium phosphate material.
The reducing atmosphere of this step comprises various reducing atmospheres, and preferably, such as 10% nitrogen and 90% hydrogen, 20% argon gas and 80% carbon monoxide etc., temperature programming rate is 2-10 ℃/min.After high-temperature calcination, naturally cooling, crystallization obtains the composite ferric lithium phosphate material of the embodiment of the present invention.
Precursor is through calcination processing under reducing atmosphere, and organic carbon source is broken down into carbon simple substance and gas, and LiFePO4 crystal grain is coated by nanometer carbon particles; Graphene oxide is also reduced to Graphene, because being coated with the doping of Graphene of nanometer carbon particles improved the conductivity of composite ferric lithium phosphate material greatly.Meanwhile, through calcination processing, lithium ion diffuses in the ferric phosphate lattice of metal M doping, obtains the lithium iron phosphate nano crystal grain of metal M doping.
The embodiment of the present invention further provides the application of above-mentioned composite ferric lithium phosphate material in lithium ion battery or positive electrode.
The beneficial effect of the composite ferric lithium phosphate material of the embodiment of the present invention:
The composite ferric lithium phosphate material of the embodiment of the present invention is coated by carbon, greatly increased the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention, doped graphene has also improved the electric conductivity of composite material greatly simultaneously, improve the charge-discharge magnification of the composite ferric lithium phosphate material of the embodiment of the present invention, greatly alleviated the polarization phenomena in charge and discharge process.
The M metal ion that adulterates in LiFePO4 lattice, further improves the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention.Metal M ion is in preparation process, and the method by co-precipitation is doped in iron phosphate nano particle, has guaranteed being doped in iron phosphate nano particle of metal M uniform ion, and the composite ferric lithium phosphate material electric conductivity of the embodiment of the present invention is improved.
Therefore the conductivity of the composite ferric lithium phosphate material of the embodiment of the present invention is very high, simultaneously, because the particle diameter of LiFePO4 crystal grain is at nanoscale, these two performances combine, and make the composite ferric lithium phosphate material of the embodiment of the present invention have fast charging and discharging performance.
Below in conjunction with specific embodiment, preparation method of the present invention is described in detail.
Embodiment mono-
Chemical composition is LiFe
0.8cr
0.2pO
4the preparation method of composite ferric lithium phosphate material, concrete steps are as follows
I) in the aqueous solution, add ferric nitrate, 85% phosphoric acid, chromic nitrate, wherein the total mole number of the molal quantity of P and Fe and Cr ratio be 1: 1, iron nitrate concentration is 2mol/L, the mol ratio of chromic nitrate and ferric nitrate is 1: 4;
II) the ammonia spirit 100ml of preparation 6mol/L;
III) deionized water of 50ml is in beaker and add the aniline monomer of 8g, under the condition stirring (500rpm/min) with peristaltic pump continuously simultaneously by above-mentioned I) obtain solution input and fill in the solution of aniline monomer, the pH value of controlling reaction system with above-mentioned ammonia spirit is 2.0, at 50 ℃, react 2 hours, the flow of controlling peristaltic pump is 0.45ml/min, after stirring reaction 2 hours, continue to stir 2 hours, precipitation centrifuge washing is obtained to the Fe of polyaniline-coated
0.8cr
0.2pO
4nano particle.
IV) preparation graphene oxide solution, the preparation method of graphene oxide is according to improved hummers method, (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), then 10g is dissolved in the water of 10mL, the graphite oxide aqueous solution that to form concentration be 1g/mL, obtains the solution system of brown;
V) get the Fe of above-mentioned polyaniline-coated
0.8cr
0.2pO
4nano particle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and add 10.2gLiAc2H in mixed systems
2o, fully violent is stirred to even mixing, obtains mixed liquor;
VI) dry dewatering: by step V) resulting mixed liquor stirs and is warming up to 70 ℃, until system becomes after muddy, puts into 80 ℃ of air dry ovens and continues dry remaining moisture of removing, and obtains composite ferric lithium phosphate material precursor;
VII) high temperature Ar/H
2reduction: by above-mentioned VI) precursor that obtains is put into tube furnace, rises to 800 ℃ and be incubated 12h, and pass into Ar/H from room temperature
2(volume ratio is 90: 10) gas, programming rate is 5 ℃/min, the naturally cooling composite ferric lithium phosphate material that obtains the embodiment of the present invention.
Battery assembling and performance test
Get respectively composite ferric lithium phosphate material of the present invention, acetylene black, polyvinylidene fluoride (PVDF) in mass ratio the ratio of 84: 8: 8 prepare, after evenly mixing, be coated on and on aluminium foil, make positive plate, next take lithium metal as negative pole, polypropylene film is barrier film, the LiPF of 1mol/L
6ethylene carbonate (EC) and the mixed liquor of dimethyl carbonate (DMC) (volume ratio 1: 1) be electrolyte, in the glove box of argon gas atmosphere, when moisture is less than 1.0ppm, be assembled in order button cell, to be tested after standing 12h.
The system that discharges and recharges of battery is: during charging, presses specific capacity size and the charge-discharge magnification of battery and sets charging and discharging currents, carry out constant current charge-discharge, and after cell voltage reaches 4.2V, system rest 10min.The 0.2C that charges herein, discharging current is 1C, during electric discharge, when cell voltage drops to 2.4V, circuit stops electric discharge (1C=170mA/g) automatically, then enters next circulation.
Refer to Fig. 2 and Fig. 3, Fig. 2 is composite ferric lithium phosphate material X-ray diffraction test structure prepared by the embodiment of the present invention.In Fig. 2, can find out, this composite ferric lithium phosphate material diffraction maximum is sharp-pointed, and contrast JPCPDS (40-1499) standard card is known, and this material has perfect crystalline, single olivine structural.From figure, it can also be seen that, what carbon and graphite were rare adds, and does not affect crystal structure.
Fig. 3 explanation, under 1C condition, the discharge capacity of material is 151mAh/g, approaches theoretical capacity and has good high rate performance.
Embodiment bis-
Chemical composition is LiFe
0.7cr
0.3pO
4the preparation method of composite ferric lithium phosphate material, concrete steps are as follows
I) in the aqueous solution, add ferric nitrate, chromic nitrate, iron nitrate concentration is 2mol/L, and the mol ratio of chromic nitrate and ferric nitrate is 3: 7;
II) the ammonia spirit 100ml of preparation 3mol/L;
III) deionized water of 50ml is in beaker and add aniline monomer and the ammonium di-hydrogen phosphate (P is 1: 1 with the total mole number ratio of iron and chromium) of 8g, under the condition stirring (500rpm/min) with peristaltic pump continuously simultaneously by above-mentioned I) the solution input solution III that obtains) and solution in, the pH value of controlling reaction system with above-mentioned ammonia spirit is 4.0, at 50 ℃, react 2 hours, the flow of controlling peristaltic pump is 0.45ml/min, after solution has been beaten, continue to stir 2 hours, precipitation centrifuge washing is obtained to the Fe of polyaniline-coated
0.7cr
0.3pO
4nano particle.
IV) preparation graphene oxide solution, the preparation method of graphene oxide is according to improved hummers method, (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), then 10g is dissolved in the water of 10mL, the graphene aqueous solution that to form concentration be 1g/mL, obtains the solution system of brown;
V) get the Fe of above-mentioned polyaniline-coated
0.7cr
0.3pO
4nano particle 0.1mol, graphite oxide aqueous solution evenly mix (wherein containing graphene oxide 5g), and add 10.2gLiAc2H in mixed system
2o, fully violent is stirred to even mixing, obtains mixed liquor;
VI) dry dewatering: by step V) resulting mixed liquor stirs and is warming up to 70 ℃, until system becomes after muddy, puts into 80 ℃ of air dry ovens and continues dry remaining moisture of removing, and obtains composite ferric lithium phosphate material precursor;
VII) high temperature Ar/H
2reduction: by above-mentioned VI) precursor that obtains is put into tube furnace, rises to 800 ℃ and be incubated 12h, and pass into Ar/H from room temperature
2(volume ratio is 9: 1) gas, programming rate is 5 ℃/min, the naturally cooling chemical composition that obtains is LiFe
0.7cr
0.3pO
4composite ferric lithium phosphate material.
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 (9)
1. a composite ferric lithium phosphate material, described composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain, described nano_scale particle structural outer surface has the complete coating layer of nanometer carbon particles, described nanometer carbon particles coating layer outer surface is coated with Graphene, and the chemical composition of described lithium iron phosphate nano crystal grain is: LiFe
1-xm
xpO
4, wherein M is metal ion, 0.001≤x < 1, and wherein, described M is selected from least one in magnesium, chromium, copper, zinc.
2. composite ferric lithium phosphate material as claimed in claim 1, is characterized in that, described Graphene is the Graphene aggregation that molecular level Graphene monolithic or 2-100 layer molecular level Graphene monolithic form.
3. composite ferric lithium phosphate material as claimed in claim 1, is characterized in that, described lithium iron phosphate nano size of microcrystal is in 1-100 nanometer.
4. composite ferric lithium phosphate material as claimed in claim 1, is characterized in that, the span of described x is 0.003≤x≤0.3.
5. composite ferric lithium phosphate material as claimed in claim 1, is characterized in that, described Graphene surface attachment has nano-scale lithium iron phosphate crystal grain.
6. a preparation method for composite ferric lithium phosphate material, comprises the steps:
According to metal M, ferro element and P elements mol ratio, be x:1-x:1, preparation molysite mixed solution;
Above-mentioned mixed solution is added in the organic carbon source aqueous solution, and under 20-80 ℃ of bath temperature, hybrid reaction is 0.5～5 hour, and the pH value of hybrid reaction system is controlled at 1～4, and making the coated chemical composition of organic carbon source is Fe
1-xm
xpO
4nano particle, wherein M is metal ion, 0.001≤x < 1;
Nano particle and Li source compound that the above-mentioned organic carbon source making is coated add graphite oxide aqueous solution, stir, mix, and subsequent drying desolventizes, grind and obtain precursor;
Precursor is calcined to 1-24 hour under reducing atmosphere, 400-1000 ℃ temperature conditions, obtain described composite ferric lithium phosphate material.
7. preparation method as claimed in claim 6, is characterized in that, described organic carbon source is selected from aniline monomer or derivatives thereof, pyrrole monomer or derivatives thereof and thiophene monomer or derivatives thereof more than one.
8. preparation method as claimed in claim 6, is characterized in that, described M is selected from more than one in magnesium, chromium, copper, zinc, manganese metal ion.
9. the application of the composite ferric lithium phosphate material as described in claim 1-5 any one in positive electrode or lithium ion battery.
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| WO2023023894A1 (en) * | 2021-08-23 | 2023-03-02 | 宁德时代新能源科技股份有限公司 | Carbon-coated lithium iron phosphate positive electrode active material, method for preparing same, positive electrode pole piece comprising same, and lithium-ion battery |
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