CN104332614B - A kind of nucleocapsid structure lithium ion battery anode composite material and preparation method thereof - Google Patents
A kind of nucleocapsid structure lithium ion battery anode composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nucleocapsid structure lithium ion battery anode composite material and preparation method thereof, the composite includes LiFePO4Nanometer nucleome and Li3V2(PO4)3Housing, Li3V2(PO4)3Housing is evenly coated at LiFePO4The periphery of nanometer nucleome, Li3V2(PO4)3The periphery of housing is also wrapped on amorphous carbon, the premium properties such as the anode composite material has specific capacity and energy density height, good cycling stability, high rate performance be good；The preparation method is that Fe source compound, vanadium source compound, P source compound, Li source compound, chelating agent and carbon source are stirred into mixing in deionized water; after two-step sintering above-mentioned composite, the preparation method has the advantages that technique is simple, easily operated, cost is low, it is environmentally friendly, be adapted to scale and industrialized production.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, and in particular to a kind of core shell structure
xLiFePO4·Li3V2(PO4)3/ C anode composite material of lithium ion battery and preparation method thereof.
Background technology
With the propelled at high velocity of IT application process, the fast development of mobile Internet, people want to secondary chemical sources of electric energy
More and more higher is sought, specific capacity and the fast charging and discharging performance of current battery turn into the bottle that mobile internet device grows continuously and fast
Neck.As environmental degradation is increasingly severe, persistently overheating, electric automobile and the mixing of the extreme weather such as haze, arid, sandstorm
Power vehicle industry is extensively concerned, and the cleaning lithium ion power secondary cell of development high power characteristic has strategic importance.
Positive electrode is used as one of core component of lithium ion battery, it has also become the study hotspot of the world today.Positive pole
Material is that most critical is also cost highest part in lithium ion battery, at present commercial anode material for lithium-ion batteries master
There is stratiform LiCoO2Positive electrode, stratiform LiNiO2Positive electrode, spinel-type LiMn2O4Positive electrode and olivine-type
LiFePO4Positive electrode.However, LiCoO2Actual specific capacity be only 50% of theoretical specific capacity or so, and world's cobalt resource has
Limit, the cobalt resource of China is very rare, causes the expensive of cobalt.Layer structure LiNiO2Synthesis condition it is very harsh, weight
Existing property is poor, it is difficult to synthesize the product of certain stoichiometric proportion.LiMn2O4Environmental pollution is smaller, and synthesis cost is relatively low, but
It is that its energy density is relatively low, high-temperature stability is poor.
Olivine structural LiFePO4It is environmentally safe with its, abundant raw material, cheap, discharge platform is stable, circulation
The advantages of performance is good, has broad application prospects as electrokinetic cell and energy-storage battery, has attracted lot of domestic and foreign researcher
Concern.LiFePO4It is a kind of most close pile structure of six sides of micro- distortion, crystal structure is by MO6Octahedra and PO4Tetrahedron replaces
Spatial skeleton is arranged in, without continuous MO6Common side octahedral volume grid, it is impossible to form effective electronics pair, cause its electric conductivity
It is poor.In addition, Li in olivine-type structure+One-dimensional diffusion admittance significantly limit it in terms of high power electrokinetic cell
Using.In order to overcome its shortcoming, domestic and international researchers pass through carbon coating, ion doping, control particle size and optimum synthesis
Studied in terms of technique.Li3V2(PO4)3With stable structure, excellent security performance, good cryogenic property with
And the features such as abundant raw material sources, in the Li of monocline3V2(PO4)3, PO4Tetrahedron and VO6Octahedron in apex by sharing
Oxygen atom and constitute three dimensional skeletal structure, each VO6Octahedron is by 6 PO4Tetrahedron is surrounded, and each PO4Around tetrahedron
There are 4 VO6It is octahedra.Thus with (VO6)2(PO4)3Li is constituted for elementary cell3V2(PO4)3Three dimensional skeletal structure.3.0~
Discharge and recharge can show 197mAh/g theoretical capacity between 4.8V, and with V3+/V4+3.0 based on redox reaction
~4.3V (vs.Li/Li+) between can be with reversible two Li of abjection/insertion+.But in Li3V2(PO4)3In, due to crystal structure
The reason for metal ion reduce the mobility of electronics in material relatively far apart, to a certain extent, cause the electronic conduction of material
Rate is relatively low, is not suitable for carrying out discharge and recharge under high current.
Pass through xLiFePO made from physical mixed method or chemically composited method4·Li3V2(PO4)3/ C composite not only may be used
With by using Li3V2(PO4)3High theoretical specific capacity, fast ion conduction and high voltage platform be modified LiFePO4Material,
The metal ion of two kinds of materials can also be made to adulterate to improve the chemical property of composite mutually.
The content of the invention
The technical problem to be solved in the present invention is to overcome the shortcomings of that prior art exists there is provided a kind of specific capacity height, circulated
The good nucleocapsid structure lithium ion battery anode composite material of functional, high rate performance, also provides and accordingly provides a kind of technique letter
Single, easy to operate, cost is low, be adapted to the system of the nucleocapsid structure lithium ion battery anode composite material of scale and industrialized production
Preparation Method.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of nucleocapsid structure lithium ion battery anode composite material, including LiFePO4Nanometer nucleome and Li3V2(PO4)3Shell
Body, the Li3V2(PO4)3Housing is evenly coated at LiFePO4The periphery of nanometer nucleome, the Li3V2(PO4)3The periphery of housing
It is also wrapped on amorphous carbon；The chemical formula of the nucleocapsid structure lithium ion battery anode composite material is xLiFePO4·Li3V2
(PO4)3/ C, wherein x span are 3~9.
In above-mentioned technical proposal, the value of the x is 8, and the amorphous carbon is in anode composite material of lithium ion battery
Shared mass percent is 3~15%.
As a total technical concept, the present invention also provides a kind of nucleocapsid structure lithium ion battery anode composite material
Preparation method, comprises the following steps：
(1) Fe source compound of raw material, vanadium source compound, P source compound, Li source compound, chelating agent and carbon will be used as
Source is fitted into closed container according to stoichiometric proportion mixing, and deionized water and the temperature at 60~80 DEG C are added into closed container
1~3h of lower magnetic agitation obtains solidliquid mixture；
(2) by closed container open or by obtained solidliquid mixture be transferred to open container continue heating stirring 10~
20h, obtains xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, in inert gas shielding gas
300~400 DEG C are risen to 2~8 DEG C/min heating rate to be sintered, be incubated before being obtained after 3~5h, natural cooling in atmosphere
Drive body powder；It is preferably 30~60min to the milling time of xerogel precursor mixture in this step；Inert gas is preferably
Heating furnace is passed through with 100~1000mL/min speed；
(4) it is transferred in heating furnace, is protected in inert gas or reducibility gas after obtained precursor powder is ground uniformly
650~850 DEG C are risen to 2~8 DEG C/min heating rates, 6~12h of calcining at constant temperature obtains nucleocapsid after natural cooling in shield atmosphere
Structure lithium ion battery anode composite material.Be preferably 20 to the milling time of xerogel precursor mixture in this step~
40min；
In above-mentioned preparation method, it is preferred that the Fe source compound is ferrous sulfate, ferrous oxalate, iron oxide, citric acid
At least one of iron, ferric phosphate and ferric nitrate；The vanadium source compound is in oxide, ammonium metavanadate and the lithium vanadate of vanadium
It is at least one；Phosphorus source compound is in ammonium di-hydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate and ferric phosphate
It is at least one；The Li source compound is at least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium dihydrogen phosphate
Kind；The chelating agent is that oxalic acid, citric acid, tartaric acid, polyacrylic acid and mass ratio are at least one of 30% hydrogen peroxide；
The carbon source is at least one of acetylene black, graphite powder, superconduction carbon black, citric acid and solvable carbohydrate；The oxide of above-mentioned vanadium
Preferably vanadic anhydride.
In above-mentioned preparation method, it is preferred that ferro element in the raw material, v element, P elements, elemental lithium and chelating agent
Mol ratio is (0.7~0.9): (0.1~0.3): (1~1.2): (1.1~1.3): (2.5~3.5).
In above-mentioned preparation method, it is preferred that the content of carbon is the lithium ion cell positive composite wood of generation in the raw material
The 10% of the quality of material.
In above-mentioned preparation method, it is preferred that the closed container is the blue bottle of silk, ground flask or the closed glass of capping
Bottle；The heating furnace is tube furnace.
In above-mentioned preparation method, it is preferred that the inert gas is that argon gas, nitrogen or nitrogen are argon-mixed；The reproducibility
Gas is argon gas, nitrogen, CO gas, argon-mixed and hydrogen the mixed gas of nitrogen, and hydrogen or carbon monoxide
Gas accounts for the 3~15% of mixed gas volume.
In above-mentioned preparation method, it is preferred that the solidliquid mixture obtained after also having before step (2) to step (1)
The step of further handling, further processing refers to using the processing of at least one of ultrasonic disperse, hydro-thermal and addition dispersant
Method is handled solidliquid mixture.
In above-mentioned preparation method, it is preferred that the processing time of the ultrasonic disperse processing is 0.5~4h；At the hydro-thermal
The reaction temperature of reason is 180~220 DEG C, and soaking time is 2~40h；Dispersant employed in the addition dispersant processing
For in paraffin, PVP, polyethylene glycol, hydrazine hydrate, methyl anyl alcohol, polyacrylamide and fatty acid at least
It is a kind of.
Compared with prior art, the advantage of the invention is that：
1st, Li in nucleocapsid structure lithium ion battery anode composite material of the present invention3V2(PO4)3Housing is uniformly coated on
LiFePO4Nanometer nucleome periphery, amorphous carbon is coated on active material periphery, due to the Li of cladding3V2(PO4)3With special
Three dimensional skeletal structure, enables lithium ion quickly deintercalation, and the amorphous carbon coated can effectively suppress particle growth, raising
The electric conductivity of material；The nucleocapsid structure lithium ion battery anode composite material of the present invention utilizes Li3V2(PO4)3The theoretical specific volume of height
Amount, fast ion conduction and high voltage platform can be modified LiFePO4Material, and the metal ion of two kinds of materials mixes mutually
It is miscellaneous, the chemical property of composite can be effectively improved；The nucleocapsid structure lithium ion battery anode composite material tool of the present invention
Higher specific capacity and energy density, good cyclical stability and preferably high rate performance.
2nd, the preparation method of nucleocapsid structure lithium ion battery anode composite material of the present invention is to use a step sol-gel process
Nucleocapsid structure lithium ion battery anode composite material is made, all raw materials are once added, its building-up process can be greatly simplified, its
Technique is simple, easily operated, cost is low, be adapted to scale and industrialized production；Water solvent is used in preparation process and close
The technique of closure system, is on the one hand conducive to quick, the easy reactant presoma uniformly dried, and on the other hand, its is right
It is environment-friendly, environment will not be polluted.Also, the uniformity of solwution method can further increase the dispersed of each component
Property, the chemical property for the nucleocapsid structure lithium ion battery anode composite material that can be effectively improved after synthesis.
3rd, preparation method of the invention can be entered advance using a variety of processing methods to the solidliquid mixture obtained after step (1)
The processing of one step, so can not only obtain uniform, cladding, the nanoscale reactant presoma of narrow size distribution, and a variety of places
Reason method can also appropriate cooperation simultaneously use, production efficiency can be greatly improved, make technique simpler, operability is more preferable.
4th, in preparation method of the invention, high temperature sintering, as protective gas, can effectively be kept away using reducibility gas
The oxidation side reaction for exempting to be brought due to the presence of a small amount of oxygen is occurred, so as to obtain the nucleocapsid structure lithium ion battery of high-purity just
Pole composite.
5th, nucleocapsid structure lithium ion battery anode composite material made from preparation method of the invention has specific capacity and energy
The premium properties such as metric density height, good cycling stability, high rate performance be good.
Brief description of the drawings
Fig. 1 is the XRD for the nucleocapsid structure lithium ion battery anode composite material that the embodiment of the present invention 1 is prepared.
Fig. 2 is that the nucleocapsid structure lithium ion battery anode composite material prepared with the embodiment of the present invention 1 is assembled into knob
Detain cycle performance curve map of the battery under 165mA/g, 2.5V-4.5V discharge and recharge systems.
Embodiment
The present invention is described in further detail below in conjunction with Figure of description and specific embodiment.
Embodiment 1
A kind of nucleocapsid structure lithium ion battery anode composite material, including LiFePO4Nanometer nucleome and Li3V2(PO4)3Shell
Body, Li3V2(PO4)3Housing is evenly coated at LiFePO4The periphery of nanometer nucleome, and Li3V2(PO4)3The periphery of housing is also coated
There is amorphous carbon.The chemical formula of the nucleocapsid structure lithium ion battery anode composite material is xLiFePO4·Li3V2(PO4)3/ C, its
In, x span is 3~9, amorphous carbon mass percent shared in anode composite material of lithium ion battery for 3~
15%.
The xLiFePO of above-mentioned core shell structure4·Li3V2(PO4)3/ C anode composite material of lithium ion battery is prepared by following
Method is made：
(1) according to 8:1:11:6:27 stoichiometric proportion weighs the FeSO as raw material4·7H2O、V2O5、NH4H2PO4、
Li2CO3And H2C2O4·2H2O, is 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation
Amount weighs section's qin superconduction carbon black, and the raw material weighed is mixed and loads closed container, then adds 300ml deionizations to closed container
Water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 70 DEG C；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in tube furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
Using the 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion batteries
The XRD results of anode composite material are as shown in figure 1, diffraction maximum position, intensity and width are it can be concluded that sintetics in figure
Crystallinity it is very good, Fig. 2 for synthesis after core shell structure 8LiFePO4·Li3V2(PO4)3/ C lithium ion cell positive composite woods
Expect the cycle performance curve map under 165mA/g, 2.5V-4.5V discharge and recharge systems, it can be seen that it possesses very excellent electricity
Chemical property.
Embodiment 2
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:11:6:27 stoichiometric proportion weighs the FeSO as raw material4·7H2O、V2O5、NH4H2PO4、
Li2CO3And H2C2O4·2H2O, is 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation
Amount weighs section's qin superconduction carbon black, and the raw material weighed is mixed and loads closed container, then adds 300ml deionizations to closed container
Water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 70 DEG C；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 3
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:11:6:27 stoichiometric proportion weighs the FeSO as raw material4·7H2O、V2O5、NH4H2PO4、
Li2CO3And H2C2O4·2H2O, is 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation
Amount weighs section's qin superconduction carbon black, and the raw material weighed is mixed and loads closed container, then adds 300ml deionizations to closed container
Water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 70 DEG C；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h, then is transferred in water heating kettle at 200 DEG C
At a temperature of be incubated 6 hours；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 4
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:11:6:27 stoichiometric proportion weighs the FeSO as raw material4·7H2O、V2O5、NH4H2PO4、
Li2CO3And H2C2O4·2H2O, is 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation
Amount weighs section's qin superconduction carbon black, by FeSO first in closed container4·7H2O and H2C2O4·2H2O is mixed, and is added 300ml and is gone
Ionized water magnetic agitation 2h at a temperature of 70 DEG C obtains thin milky mixt, to remove the SO4 remained in this thin milky mixt2-
Deng foreign ion, cleaned 3 times using centrifugation, and with deionized water, obtain FeC2O4·2H2O yellow paste products.Will
V2O5、NH4H2PO4、Li2CO3Sequentially added with section qin superconduction carbon black in closed container.Again 300ml is added into closed container to go
Ionized water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 70 DEG C；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The thin breast of ferrous oxalate and oxalic acid vanadium solution, the solution shape in heating stirring can be formed in the preparation process of the present embodiment
Vanadium oxalate (the VOC of state2O4) ferrous oxalate (FeC of precipitated form can be wrapped in2O4) surface, it is effectively synthesized core shell structure；Together
When, the vanadium oxalate (VOC of surface parcel2O4) it can effectively suppress growing up for internal layer LiFePO4 when being converted into phosphoric acid vanadium lithium.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 5
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:11:12:3 stoichiometric proportion weighs the FeC as raw material6H5O7·5H2O、V2O5、
NH4H2PO4、LiOH·H2O and H2C2O4·2H2O, according to the matter of amorphous carbon in the anode composite material of lithium ion battery of generation
The raw material weighed is mixed loading closed container, then adds 300ml to closed container and gone by amount than weighing acetylene black for 10% amount
Ionized water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 60 DEG C；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 6
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:11:12:2 stoichiometric proportion weighs the FeC as raw material6H5O7·5H2O、V2O5、
NH4H2PO4、LiOH·H2O and C6H8O7, it is according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation
10% amount weighs acetylene black, and the raw material weighed is mixed and loads closed container, then adds 300ml deionizations to closed container
Water, magnetic agitation 2h obtains solidliquid mixture at a temperature of 60 DEG C；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 7
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:3:12:27 stoichiometric proportion is by raw material FePO4·2H2O、V2O5、NH4H2PO4、LiOH·H2O
And H2C2O4·2H2O, claims according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation for 10% amount
Section's qin superconduction carbon black is taken, the raw material weighed is mixed and loads closed container, then 300ml deionized waters are added to closed container,
Magnetic agitation 2h obtains solidliquid mixture at a temperature of 70 DEG C；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and the 8LiFePO of core shell structure is obtained after natural cooling4·Li3V2
(PO4)3/ C anode composite material of lithium ion battery.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Embodiment 8
A kind of xLiFePO of core shell structure4·Li3V2(PO4)3The preparation method of/C anode composite material of lithium ion battery,
Comprise the following steps：
(1) according to 8:1:3:12:27 stoichiometric proportion is by raw material FePO4·2H2O、V2O5、NH4H2PO4、LiOH·H2O
And H2C2O4·2H2O, claims according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery of generation for 10% amount
Sucrose is taken, the raw material weighed is mixed and loads closed container, then 300ml deionized waters are added to closed container, in 70 DEG C of temperature
Lower magnetic agitation 2h obtains solidliquid mixture；
Ultrasonic disperse processing is carried out to obtained solidliquid mixture, processing time is 2h；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue heating stirring 12h, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, stream is passed through into tube furnace
Speed is 100~300mL/min inert gas formation inert gas shielding atmosphere, and 350 DEG C are risen to 5 DEG C/min heating rate
It is sintered, is incubated the precursor powder obtained after 4h, natural cooling；Milling time is preferably 40min in this step；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, with 5 in reducibility gas protective atmosphere
DEG C/min heating rates rise to 750 DEG C, calcining at constant temperature 8h, and nucleocapsid structure lithium ion battery positive pole composite wood is obtained after natural cooling
Expect 8LiFePO4·Li3V2(PO4)3/C.Milling time is preferably 30min in this step.
The 8LiFePO of core shell structure made from the preparation method of the present embodiment4·Li3V2(PO4)3/ C lithium ion cell positives
Composites possess extraordinary crystallinity and very excellent chemical property.
Claims (6)
1. a kind of nucleocapsid structure lithium ion battery anode composite material, it is characterised in that：Including LiFePO4Nanometer nucleome and Li3V2
(PO4)3Housing, the Li3V2(PO4)3Housing is evenly coated at LiFePO4The periphery of nanometer nucleome, the Li3V2(PO4)3Housing
Periphery be also wrapped on amorphous carbon；The chemical formula of the nucleocapsid structure lithium ion battery anode composite material is xLiFePO4·
Li3V2(PO4)3/ C, wherein x span are 3~9；
The preparation method of described nucleocapsid structure lithium ion battery anode composite material, comprises the following steps：
(1) it will be pressed as the Fe source compound of raw material, vanadium source compound, P source compound, Li source compound, chelating agent and carbon source
It is fitted into according to stoichiometric proportion mixing in closed container, deionized water and the magnetic at a temperature of 60~80 DEG C is added into closed container
Power stirs 1~3h and obtains solidliquid mixture；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue 10~20h of heating stirring, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, in inert gas shielding atmosphere
300~400 DEG C are risen to 2~8 DEG C/min heating rate to be sintered, and are incubated the presoma obtained after 3~5h, natural cooling
Powder；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, in inert gas or reducibility gas protection gas
650~850 DEG C are risen to 2~8 DEG C/min heating rates, 6~12h of calcining at constant temperature obtains core shell structure after natural cooling in atmosphere
Anode composite material of lithium ion battery；
The Fe source compound be ferrous sulfate, ferrous oxalate, iron oxide, ironic citrate, ferric phosphate and ferric nitrate at least
It is a kind of；The vanadium source compound is at least one of oxide, ammonium metavanadate and lithium vanadate of vanadium；Phosphorus source compound is
At least one of ammonium di-hydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate and ferric phosphate；The Li source compound is
At least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium dihydrogen phosphate；The chelating agent is oxalic acid, lemon
Acid, tartaric acid, polyacrylic acid and mass ratio are at least one of 30% hydrogen peroxide；The carbon source is acetylene black, graphite powder
At least one of with superconduction carbon black；
The step of solidliquid mixture obtained after also having before step (2) to step (1) is further handled, further processing
Refer to handle solidliquid mixture using at least one of ultrasonic disperse, hydro-thermal and addition dispersant processing method；
The processing time of the ultrasonic disperse processing is 0.5~4h；The reaction temperature of the hydro-thermal process is 180~220 DEG C, is protected
The warm time is 2~40h；Dispersant employed in the addition dispersant processing is paraffin, PVP, poly- second
At least one of glycol, hydrazine hydrate, methyl anyl alcohol, polyacrylamide and fatty acid.
2. nucleocapsid structure lithium ion battery anode composite material according to claim 1, it is characterised in that：The x's takes
It is worth for 8, amorphous carbon mass percent shared in anode composite material of lithium ion battery is 3~15%.
3. a kind of preparation method of nucleocapsid structure lithium ion battery anode composite material as claimed in claim 1, its feature exists
In comprising the following steps：
(1) it will be pressed as the Fe source compound of raw material, vanadium source compound, P source compound, Li source compound, chelating agent and carbon source
It is fitted into according to stoichiometric proportion mixing in closed container, deionized water and the magnetic at a temperature of 60~80 DEG C is added into closed container
Power stirs 1~3h and obtains solidliquid mixture；
(2) closed container is opened or obtained solidliquid mixture is transferred into open container and continue 10~20h of heating stirring, obtain
Obtain xerogel precursor mixture；
(3) it is transferred to after obtained xerogel precursor mixture is ground uniformly in heating furnace, in inert gas shielding atmosphere
300~400 DEG C are risen to 2~8 DEG C/min heating rate to be sintered, and are incubated the presoma obtained after 3~5h, natural cooling
Powder；
(4) it is transferred to after obtained precursor powder is ground uniformly in heating furnace, in inert gas or reducibility gas protection gas
650~850 DEG C are risen to 2~8 DEG C/min heating rates, 6~12h of calcining at constant temperature obtains core shell structure after natural cooling in atmosphere
Anode composite material of lithium ion battery；
The Fe source compound be ferrous sulfate, ferrous oxalate, iron oxide, ironic citrate, ferric phosphate and ferric nitrate at least
It is a kind of；The vanadium source compound is at least one of oxide, ammonium metavanadate and lithium vanadate of vanadium；Phosphorus source compound is
At least one of ammonium di-hydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate and ferric phosphate；The Li source compound is
At least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium dihydrogen phosphate；The chelating agent is oxalic acid, lemon
Acid, tartaric acid, polyacrylic acid and mass ratio are at least one of 30% hydrogen peroxide；The carbon source is acetylene black, graphite powder
At least one of with superconduction carbon black；
The step of solidliquid mixture obtained after also having before step (2) to step (1) is further handled, further processing
Refer to handle solidliquid mixture using at least one of ultrasonic disperse, hydro-thermal and addition dispersant processing method；
The processing time of the ultrasonic disperse processing is 0.5~4h；The reaction temperature of the hydro-thermal process is 180~220 DEG C, is protected
The warm time is 2~40h；Dispersant employed in the addition dispersant processing is paraffin, PVP, poly- second
At least one of glycol, hydrazine hydrate, methyl anyl alcohol, polyacrylamide and fatty acid.
4. preparation method according to claim 3, it is characterised in that：Ferro element in the raw material, v element, P elements,
The mol ratio of elemental lithium and chelating agent is (0.7~0.9): (0.1~0.3): (1~1.2): (1.1~1.3): (2.5~3.5).
5. preparation method according to claim 3, it is characterised in that：The content of carbon is the lithium ion of generation in the raw material
The 10% of the quality of battery anode composite material.
6. preparation method according to claim 3, it is characterised in that：The closed container be the blue bottle of silk, ground flask or
The closed glass jar of capping；The heating furnace is tube furnace.
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| CN105845974A (en) * | 2016-06-06 | 2016-08-10 | 四川国润新材料有限公司 | Preparation method for positive electrode material NaFePO4/C of sodium ion battery |
| CN106374089B (en) * | 2016-10-25 | 2018-06-12 | 北京中科东青纳米科技有限公司 | A kind of LiFePO4-phosphoric acid vanadium lithium nanometer combined electrode material and preparation method thereof |
| CN108155358A (en) * | 2017-12-11 | 2018-06-12 | 浙江天能能源科技股份有限公司 | A kind of preparation method of lithium ion battery nickle cobalt lithium manganate anode composite material |
| CN108075122A (en) * | 2017-12-14 | 2018-05-25 | 电子科技大学 | A kind of preparation method of lithium ion battery composite cathode material |
| CN110085810B (en) * | 2018-01-25 | 2022-06-10 | 天津国安盟固利新材料科技股份有限公司 | Preparation method and application of coated modified lithium cobaltate positive electrode material |
| CN110061226B (en) * | 2019-05-07 | 2020-04-10 | 湖南金富力新能源股份有限公司 | Titanium suboxide-coated positive electrode material, preparation method of positive electrode material and lithium ion battery |
| CN110492089B (en) * | 2019-09-18 | 2022-03-04 | 宁波大学 | Carbon-coated ferric oxide and potassium pentavanadate composite material and preparation method thereof |
| CN111554914B (en) * | 2020-05-29 | 2021-09-21 | 重庆工商大学 | Lithium iron phosphate-sodium vanadium phosphate-carbon composite material and preparation method and application thereof |
| CN113991070A (en) * | 2021-09-14 | 2022-01-28 | 陕西创普斯新能源科技有限公司 | Lithium iron phosphate composite material and preparation method and application thereof |
| EP4418363A1 (en) * | 2021-10-22 | 2024-08-21 | Contemporary Amperex Technology Co., Limited | Positive electrode active material, positive electrode sheet, secondary battery, battery module, battery pack, and electric device |
| CN114864940A (en) * | 2022-04-08 | 2022-08-05 | 中国科学院青岛生物能源与过程研究所 | High-mechanical-strength coating-layer-containing cathode material, and preparation method and application thereof |
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