CN102437311A - 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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- CN102437311A CN102437311A CN2010102966615A CN201010296661A CN102437311A CN 102437311 A CN102437311 A CN 102437311A CN 2010102966615 A CN2010102966615 A CN 2010102966615A CN 201010296661 A CN201010296661 A CN 201010296661A CN 102437311 A CN102437311 A CN 102437311A
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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 the battery technology field, relate in particular to a kind of composite ferric lithium phosphate material, its preparation method and application.
Background technology
In the prior art, anode material for lithium-ion batteries concentrates on the transition metal oxide of lithium such as the LiMO of layer structure
2The LiMn of (M=Co, Ni, Mn) and spinel structure
2O
4They differ from one another as positive electrode, LiCoO
2Cost is high, natural resources shortage, and toxicity is big; LiNiO
2The preparation difficulty, poor heat stability; LiMn
2O
4Capacity is lower, and cyclical stability is relatively 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, make it 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 invention provides a kind of composite ferric lithium phosphate material, solves the technical problem that the battery for preparing with composite ferric lithium phosphate material in the prior art can not fast charging and discharging.
The present invention realizes like this; A kind of composite ferric lithium phosphate material; Said composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain; Said nano_scale particle structural outer surface has the nanometer carbon particles coating layer, and said nanometer carbon particles coating layer outer surface is coated with Graphene, and the chemical composition of said lithium iron phosphate nano crystal grain is: LiFe
1-xM
xPO
4, wherein M is a metal ion, 0.001≤x＜1.
The embodiment of the 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 is x: 1-x: 1, and preparation molysite mixed solution;
Above-mentioned mixed solution is added in the organic carbon source aqueous solution, and hybrid reaction is 0.5～5 hour under 20-80 ℃ of bath temperature, and the pH value of hybrid reaction system is controlled at 1～7, and making organic carbon source coating chemical composition is Fe
1-xM
xPO
4Nano particle, wherein M is a metal ion, 0.001≤x＜1;
The nano particle that the above-mentioned organic carbon source that makes is coated adds the graphite oxide aqueous solution with Li source compound, stirs, mixing, and subsequent drying desolventizes, grind and obtain precursor;
Precursor was calcined 1-24 hour under reducing atmosphere, 400-1000 ℃ temperature conditions, obtained said composite ferric lithium phosphate material.
The embodiment of the 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 invention; Mix and doped metal ion in LiFePO4 crystal grain through nanometer carbon particles coated LiFePO 4 for lithium ion batteries crystal grain, Graphene; Make the electric conductivity of composite ferric lithium phosphate material of the embodiment of the invention be greatly improved; Because LiFePO4 crystal grain is nanometer particle size, guaranteed that the composite ferric lithium phosphate material of the embodiment of the invention can fast charging and discharging simultaneously.
Description of drawings
Fig. 1 is the composite ferric lithium phosphate material electron microscope photo scanning (multiplying power * 10000) of the embodiment of the invention;
Fig. 2 is the composite ferric lithium phosphate material X-ray diffractogram of the embodiment of the invention;
Fig. 3 is the composite ferric lithium phosphate material A Bin battery testing figure as a result of the embodiment of the invention.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is done further explain below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of composite ferric lithium phosphate material; Said composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain; Said nano_scale particle structural outer surface has the nanometer carbon particles coating layer; Said nanometer carbon particles coating layer outer surface is coated with Graphene, and the chemical composition of said lithium iron phosphate nano crystal grain is: LiFe
1-xM
xPO
4, wherein M is a metal ion, 0.001≤x＜1.
The composite ferric lithium phosphate material of the embodiment of the invention is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain.Embodiment of the invention composite material is the basic composition unit with nano-scale lithium iron phosphate crystal grain (being lithium iron phosphate nano crystal grain); This nano-scale lithium iron phosphate grain surface has the nanometer carbon particles coating layer; Form nanometer carbon particles coated LiFePO 4 for lithium ion batteries crystal grain; Simultaneously be coated with Graphene at this nanometer carbon particles coating layer outer surface; Specifically, Graphene is coated on 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.Coat and the Graphene doping through doping metals M ion, nanometer carbon particles in the LiFePO4 crystal grain; Make the electric conductivity of composite ferric lithium phosphate material be greatly enhanced; Improve its charge-discharge performance greatly, reduced the polarization phenomena of composite ferric lithium phosphate material in discharging and recharging, simultaneously; This composite ferric lithium phosphate material is made up of the 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 characteristics of nanometer particle size makes the composite ferric lithium phosphate material of the embodiment of the invention have fast charging and discharging performance.See also Fig. 1, Fig. 1 shows that embodiment of the 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 this lithium iron phosphate nano crystal grain type of being is spherical.
Lithium iron phosphate nano crystal grain in the embodiment of the invention, the surface is coated by nanometer carbon particles, and preferably nanometer carbon particles coats fully, and this nanometer carbon particles is in the 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 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 invention greatly; Improve the charge-discharge magnification property of the composite ferric lithium phosphate material of the embodiment of the invention, greatly alleviated the polarization phenomena in the charge and discharge process.
Because Graphene also is very excellent electric conducting material; Further improved the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the invention greatly, the Graphene of the composite ferric lithium phosphate material of the embodiment of the 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 a metal ion, is preferably the high metal ion of chemical price, comprises in the metal ions such as magnesium, chromium, copper, zinc, manganese one or more.The value of X is 0.001≤x＜1, preferred 0.003≤x≤0.3.Doping M metal ion in the LiFePO4 lattice further improves the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the invention.The metal M ion is doped in the iron phosphate nano particle through coprecipitation method in the preparation process, has guaranteed that the metal M ion evenly is doped in the iron phosphate nano particle, makes the composite ferric lithium phosphate material electric conductivity of the embodiment of the invention be improved.
The method preparing phosphate iron lithium of the embodiment of the invention, concrete steps are following:
A) be x: 1-x according to metal M, ferro element and P elements mol ratio: 1, preparation molysite mixed solution;
In step a), it is Fe that preparation contains chemical composition
1-xM
xPO
4The solution of nano particle is through containing Fe
3+Compound or its solution, metal M ion compound or its solution, 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 such as tri-iron tetroxide, ferrous sulfate, iron ammonium sulfate, ferrous phosphate ammonia, ferrous phosphate, ferrous citrate, ferrous oxide etc. obtain containing Fe through oxidation
3+Compound; Employed oxidant does not have the restriction of kind; Preferably ammonium persulfate, clorox, quality percentage composition be 30% hydrogen peroxide, in the solid hydrogen peroxide solution one or more; Oxidant concentration is 0.2-6mol/L, uses excessive oxidant, guarantees that all ferrous ions can both be oxidized to ferric ion.
The compound that contains the metal M ion, for example 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 with water reaction, generate phosphoric acid.
The source of iron of using in this step (promptly contains Fe
3+Or the compound of ferrous ion), in solvent, can ionization go out iron ion or ferrous ion, compounds of metal M can ionization go out the M metal ion, and PO (is contained in the phosphorus source
4 3-Compound) can ionization go out phosphate anion, perhaps can not ionization go out ion, but three compounds can react in solvent, generate metal M doped iron phosphate deposition, the for example combination of iron oxide, magnesia and phosphoric acid.
In this step, the mol ratio of M metal ion, iron ion and the phosphorus that uses 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 the metal M ion, comprises in the metal ions such as magnesium ion, chromium ion, zinc ion, copper ion, manganese ion one or more.Metal M and iron ion, phosphate anion through the method for co-precipitation, form the ferric phosphate deposition of metal M ion doping; Obtain metal M doped iron phosphate lattice; When generating deposition, precipitation surface has ferric ion, thereby causes organic carbon source at its surface aggregate.Through 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, hybrid reaction is 0.5～5 hour under 20-60 ℃ of bath temperature, and the pH value of hybrid reaction system is controlled at 1～7, and making organic carbon source coating chemical composition is Fe
1-xM
xPO
4Nano particle, wherein M is a metal ion, 0.001≤x＜1;
This organic carbon source is meant to be Fe in chemical composition
1-xM
xPO
4Nanoparticle surface polymerization and the organic carbon source that under 400-1000 ℃ of temperature, can decompose, preferably aniline monomer or derivatives thereof, pyrrole monomer or derivatives thereof and thiophene monomer or derivatives thereof etc.Add organic carbon source, through Fe
1-xM
xPO
4The oxidation of nanoparticle surface ferric ion makes that organic carbon source is Fe in chemical composition
1-xM
xPO
4The polymerization of nano particle outer surface, simultaneously, organic carbon source self also can produce polymerization, thus the coating 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.The above-mentioned chemical composition that contains is Fe
1-xM
xPO
4The solution of nano particle pumps in the organic carbon source aqueous solution through peristaltic pump; With 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.Temperature with system is controlled at 20-60 ℃ simultaneously, can use the mode of water-bath heating, the temperature of control reaction.Stirring reaction 0.5-5 hour, after stopping to add, reactant continues to stir 0.5-5 hour.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 accumulate in above-mentioned chemical composition is Fe
1-xM
xPO
4Nanoparticle surface.
In step c), the nano particle that the above-mentioned organic carbon source that makes is coated adds the graphite oxide aqueous solution with Li source compound, stirs, mixing, 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); After adding graphene oxide, organic reaction takes place and makes organic carbon source and Graphene be 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, the 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 makes mixed solution mix.
In this step, dry method is restriction not, and for example heat drying, oven drying etc. after the oven dry, grind product, obtain the precursor of composite ferric lithium phosphate material.
In step d), precursor under reducing atmosphere, 400-1000 ℃ temperature conditions, was calcined 1-24 hour, obtain composite ferric lithium phosphate material.
The reducing atmosphere of this step comprises various reducing atmospheres, preferably for example 10% nitrogen and 90% hydrogen, 20% argon gas and 80% carbon monoxide etc., and the temperature programming rate is 2-10 ℃/min.After the high-temperature calcination, natural cooling, crystallization obtains the composite ferric lithium phosphate material of the embodiment of the invention.
Precursor is through calcination processing under the reducing atmosphere, and organic carbon source is broken down into carbon simple substance and gas, makes LiFePO4 crystal grain coated by nanometer carbon particles; Graphene oxide also is reduced to Graphene, because the coating of nanometer carbon particles and the doping of Graphene make the conductivity of composite ferric lithium phosphate material improve greatly.Simultaneously, through calcination processing, lithium ion diffuses in the metal M doped iron phosphate lattice, obtains metal M doped iron phosphate lithium nanocrystal.
The embodiment of the 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 invention:
The composite ferric lithium phosphate material of the embodiment of the invention coats through carbon; Increased the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the invention greatly; Doped graphene has also improved the electric conductivity of composite material greatly simultaneously; Improve the charge-discharge magnification property of the composite ferric lithium phosphate material of the embodiment of the invention, greatly alleviated the polarization phenomena in the charge and discharge process.
Doping M metal ion in the LiFePO4 lattice further improves the electric conductivity of the composite ferric lithium phosphate material of the embodiment of the invention.The metal M ion is in the preparation process, and the method through co-precipitation is doped in the iron phosphate nano particle, has guaranteed that the metal M ion is doped in the iron phosphate nano particle uniformly, makes the composite ferric lithium phosphate material electric conductivity of the embodiment of the invention be improved.
Therefore the conductivity of the composite ferric lithium phosphate material of the embodiment of the 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 invention have fast charging and discharging performance.
Below in conjunction with specific embodiment preparation method of the present invention is set forth in detail.
Embodiment one
Chemical composition is LiFe
0.8Cr
0.2PO
4The preparation method of composite ferric lithium phosphate material, concrete steps are following
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 stirring condition (500rpm/min) with peristaltic pump continuously simultaneously with above-mentioned I) obtain the solution input and fill in the solution of aniline monomer, using the pH value of above-mentioned ammonia spirit control reaction system is 2.0, reacts 2 hours down at 50 ℃; The flow of control peristaltic pump is 0.45ml/min; Behind the stirring reaction 2 hours, continue to stir 2 hours, the deposition centrifuge washing is obtained the Fe that polyaniline coats
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, forming concentration is the graphite oxide aqueous solution of 1g/mL, obtains the solution system of brown;
V) get the Fe that above-mentioned polyaniline coats
0.8Cr
0.2PO
4Nano particle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and in mixed system, add 10.2gLiAc2H
2O fully violent is stirred to even mixing, obtains mixed liquor;
VI) drying dewaters: with step V) resulting mixed liquor stirs and is warming up to 70 ℃, after system becomes muddy, puts into 80 ℃ of air dry ovens and continues dry remaining moisture of removing, and obtains the composite ferric lithium phosphate material precursor;
VII) high temperature Ar/H
2Reduction: with above-mentioned VI) precursor that obtains is put into tube furnace, rises to 800 ℃ and be incubated 12h from room temperature, and feeds Ar/H
2(volume ratio is 90: 10) gas, programming rate is 5 ℃/min, natural cooling obtains the composite ferric lithium phosphate material of the embodiment of the invention.
Battery assembling and performance test
Getting composite ferric lithium phosphate material of the present invention, acetylene black, polyvinylidene fluoride (PVDF) respectively prepares in 84: 8: 8 ratio of mass ratio; Be coated on after evenly mixing and process positive plate on the aluminium foil; Next be negative pole with the lithium metal, polypropylene film is a 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, be assembled into button cell in order during less than 1.0ppm in moisture, leave standstill behind the 12h to be tested.
The system of discharging and recharging of battery is: during charging, press specific capacity size and the charge-discharge magnification of battery and set charging and discharging currents, carry out constant current charge-discharge, treat that cell voltage reaches 4.2V after, the rest 10min of system.This paper 0.2C that charges, discharging current is 1C, when treating during discharge that cell voltage drops to 2.4V, circuit stops discharge (1C=170mA/g) automatically, gets into next circulation then.
See also Fig. 2 and Fig. 3, Fig. 2 is the composite ferric lithium phosphate material X-ray diffraction test structure of embodiment of the invention preparation.By finding out among Fig. 2, this composite ferric lithium phosphate material diffraction maximum is sharp-pointed, and contrast JPCPDS (40-1499) standard card can know, this material has perfect crystalline, single olivine structural.From figure, it can also be seen that the adding that carbon and graphite are rare does not influence crystal structure.
Fig. 3 explanation, the discharge capacity of material is 151mAh/g under the 1C condition, has high rate performance preferably near theoretical capacity.
Embodiment two
Chemical composition is LiFe
0.7Cr
0.3PO
4The preparation method of composite ferric lithium phosphate material, concrete steps are following
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 stirring condition (500rpm/min) with peristaltic pump continuously simultaneously with above-mentioned I) solution that obtains input solution III) and solution in; Using the pH value of above-mentioned ammonia spirit control reaction system is 4.0; 50 ℃ of down reactions 2 hours, the flow of control peristaltic pump is 0.45ml/min, treat that solution has been beaten after; Continue to stir 2 hours, the deposition centrifuge washing is obtained the Fe that polyaniline coats
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, forming concentration is the graphene aqueous solution of 1g/mL, obtains the solution system of brown;
V) get the Fe that above-mentioned polyaniline coats
0.7Cr
0.3PO
4Nano particle 0.1mol, graphite oxide aqueous solution evenly mix (wherein containing graphene oxide 5g), and in mixed system, add 10.2gLiAc2H
2O fully violent is stirred to even mixing, obtains mixed liquor;
VI) drying dewaters: with step V) resulting mixed liquor stirs and is warming up to 70 ℃, after system becomes muddy, puts into 80 ℃ of air dry ovens and continues dry remaining moisture of removing, and obtains the composite ferric lithium phosphate material precursor;
VII) high temperature Ar/H
2Reduction: with above-mentioned VI) precursor that obtains is put into tube furnace, rises to 800 ℃ and be incubated 12h from room temperature, and feeds Ar/H
2(volume ratio is 9: 1) gas, programming rate is 5 ℃/min, it is LiFe that natural cooling obtains chemical composition
0.7Cr
0.3PO
4Composite ferric lithium phosphate material.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. composite ferric lithium phosphate material; Said composite ferric lithium phosphate material is that kernel is the nano_scale particle structure of lithium iron phosphate nano crystal grain; Said nano_scale particle structural outer surface has nano carbon particulate coating layer; Said nano carbon particulate coating layer outer surface is coated with Graphene, and the chemical composition of said lithium iron phosphate nano crystal grain is: LiFe
1-xM
xPO
4, wherein M is a metal ion, 0.001≤x＜1.
2. composite ferric lithium phosphate material as claimed in claim 1 is characterized in that, said Graphene is the Graphene aggregation that molecular level Graphene monolithic or said 2-100 layer molecular level Graphene monolithic constitute.
3. composite ferric lithium phosphate material as claimed in claim 1 is characterized in that, said nano-scale lithium iron phosphate size of microcrystal is in the 1-100 nanometer.
4. composite ferric lithium phosphate material as claimed in claim 1 is characterized in that said M is selected from one or more in the metal ions such as magnesium, chromium, copper, zinc, manganese.
5. composite ferric lithium phosphate material as claimed in claim 1 is characterized in that, the span of said x is 0.003≤x≤0.3.
6. composite ferric lithium phosphate material as claimed in claim 1 is characterized in that, said Graphene surface attachment has nano-scale lithium iron phosphate crystal grain.
7. the preparation method of a composite ferric lithium phosphate material comprises the steps:
According to metal M, ferro element and P elements mol ratio is x: 1-x: 1, and preparation molysite mixed solution;
Above-mentioned mixed solution is added in the organic carbon source aqueous solution, and hybrid reaction is 0.5～5 hour under 20-80 ℃ of bath temperature, and the pH value of hybrid reaction system is controlled at 1～7, and making organic carbon source coating chemical composition is Fe
1-xM
xPO
4Nano particle, wherein M is a metal ion, 0.001≤x＜1;
The nano particle that the above-mentioned organic carbon source that makes is coated adds the graphite oxide aqueous solution with Li source compound, stirs, mixing, and subsequent drying desolventizes, grind and obtain precursor;
Precursor was calcined 1-24 hour under reducing atmosphere, 400-1000 ℃ temperature conditions, obtained said composite ferric lithium phosphate material.
8. preparation method as claimed in claim 7 is characterized in that, said organic carbon source be selected from aniline monomer or derivatives thereof, pyrrole monomer or derivatives thereof, and the thiophene monomer or derivatives thereof in one or more.
9. preparation method as claimed in claim 7 is characterized in that said M is selected from one or more in the metal ions such as magnesium, chromium, copper, zinc, manganese.
10. like each described composite ferric lithium phosphate material application in lithium ion battery or positive electrode of claim 1-6.
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| CN107994214A (en) * | 2017-11-14 | 2018-05-04 | 山东丰元化学股份有限公司 | A kind of high-performance iron phosphate lithium composite material and preparation method thereof |
| CN108832122A (en) * | 2015-06-23 | 2018-11-16 | 上海交通大学 | Improve the method for electrochemical performances of lithium iron phosphate using copper/graphene |
| CN109841855A (en) * | 2019-01-30 | 2019-06-04 | 天津大学 | The preparation method of elctro-catalyst based on two cobalt of Copper-cladding Aluminum Bar phosphatization |
| 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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| CN104022283A (en) * | 2014-06-09 | 2014-09-03 | 上海交通大学 | Method for improving electrochemical characteristics of lithium iron phosphate by use of graphene/polyaniline |
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| CN106450214A (en) * | 2016-11-08 | 2017-02-22 | 成都新柯力化工科技有限公司 | Layered lithium iron phosphate composite material and preparation method thereof |
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| CN109841855B (en) * | 2019-01-30 | 2021-08-10 | 天津大学 | Preparation method of electrocatalyst based on copper-doped cobaltous phosphide |
| 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 |
| US11721804B2 (en) | 2021-08-23 | 2023-08-08 | Contemporary Amperex Technology Co., Limited | Carbon-coated lithium iron phosphate positive active material, method for preparing same, positive electrode plate containing same, and lithium-ion battery |
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