CN104332614A - Core-shelled structured lithium ion battery positive composite material and its preparation method - Google Patents

Core-shelled structured lithium ion battery positive composite material and its preparation method Download PDF

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CN104332614A
CN104332614A CN201410452200.0A CN201410452200A CN104332614A CN 104332614 A CN104332614 A CN 104332614A CN 201410452200 A CN201410452200 A CN 201410452200A CN 104332614 A CN104332614 A CN 104332614A
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composite material
ion battery
lithium ion
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anode composite
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CN104332614B (en
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梁叔全
潘安强
刘军
陈涛
曹鑫鑫
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a core-shell structured lithium ion battery positive composite material and its preparation method. The composite material includes a LiFePO4 nanometer core and a Li3V2(PO4)3 shell, the Li3V2(PO4)3 shell is uniformly coated on the periphery of the LiFePO4 nanometer core, and the periphery of the Li3V2(PO4)3 shell is coated with amorphous carbon. The positive composite material has the advantages of high specific capacity, high energy density, good cycle stability, good rate performance and the like. The preparation method comprises the following steps: stirring an iron source compound, a vanadium source compound, a phosphorus source compound, a lithium source compound, a chelating agent and a carbon source in deionized water, and sintering the obtained mixture to obtain the composite material. The preparation method has the advantages of simple process, easy operation, low cost, environmental protection, and suitableness for large-scale and industrialized production.

Description

A kind of nucleocapsid structure lithium ion battery anode composite material and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, be specifically related to a kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO4) 3/ C anode composite material of lithium ion battery and preparation method thereof.
Background technology
Along with the propelled at high velocity of IT application process, the fast development of mobile Internet, the requirement of people to secondary chemical sources of electric energy is more and more higher, and the specific capacity of current battery and fast charging and discharging performance become the bottleneck that mobile internet device grows continuously and fast.Along with ecological deterioration is more and more serious, the extreme weather such as haze, arid, sandstorm persistently overheating, electric automobile and hybrid electric vehicle industry extensively concerned, the clean lithium ion power secondary cell of development high power characteristic has strategic importance.
Positive electrode, as one of the core component of lithium ion battery, has become the study hotspot of the world today.Positive electrode is that in lithium ion battery, most critical is also the part that cost is the highest, and anode material for lithium-ion batteries commercial at present mainly contains stratiform LiCoO 2positive electrode, stratiform LiNiO 2positive electrode, spinel-type LiMn2O 4positive electrode and olivine-type LiFePO 4positive electrode.But, LiCoO 2actual specific capacity be only about 50% of theoretical specific capacity, and world's cobalt resource is limited, and the cobalt resource of China is very rare, causes the expensive of cobalt.Layer structure LiNiO 2synthesis condition very harsh, reappearance is poor, is difficult to the product synthesizing certain stoichiometric proportion.LiMn2O 4environmental pollution is less, and synthesis cost is lower, but its energy density comparatively low and high temperature less stable.
Olivine structural LiFePO 4with its environmentally safe, abundant raw material, the advantages such as cheap, discharge platform is stablized, good cycle, have broad application prospects as electrokinetic cell and energy-storage battery, have attracted the concern of lot of domestic and foreign researcher.LiFePO 4be a kind of the closeest pile structure of six sides of micro-distortion, crystal structure is by MO 6octahedron and PO 4tetrahedron is alternately arranged into spatial skeleton, does not have continuous print MO 6the octahedra network in limit, can not form effective duplet, cause its conductivity poor altogether.In addition, Li in olivine-type structure +one dimension diffusion admittance significantly limit its application in high power electrokinetic cell.In order to overcome its shortcoming, the aspects such as domestic and international researchers are coated by carbon, ion doping, control particle size and optimum synthesis technique are studied.Li 3v 2(PO4) 3there is the features such as stable structure, excellent security performance, good cryogenic property and abundant raw material sources, at the Li of monocline 3v 2(PO4) 3, PO 4tetrahedron and VO 6octahedron constitutes three dimensional skeletal structure by sharing oxygen atom at summit place, each VO 6octahedra by 6 PO 4tetrahedron is around, and each PO 44 VO are had around tetrahedron 6octahedra.So just with (VO 6) 2(PO 4) 3for elementary cell composition Li 3v 2(PO 4) 3three dimensional skeletal structure.Between 3.0 ~ 4.8V, discharge and recharge can show the theoretical capacity of 197mAh/g, and with V3 +/ V4 +at 3.0 ~ 4.3V (vs.Li/Li based on redox reaction +) between can be reversible deviate from/embed two Li +.But at Li 3v 2(PO 4) 3in, due to crystal structure reason metal ion relatively far apart, reduce the mobility of electronics in material to a certain extent, cause the electronic conductivity of material lower, be not suitable for carrying out discharge and recharge under big current.
By the xLiFePO that physical mixed method or chemically composited method obtain 4li 3v 2(PO 4) 3/ C composite not only can by utilizing Li 3v 2(PO 4) 3high theoretical specific capacity, fast ion conduction and high voltage platform carry out modification LiFePO 4material, can also make the metal ion of bi-material adulterate mutually to improve the chemical property of composite material.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming prior art existence; the nucleocapsid structure lithium ion battery anode composite material that a kind of specific capacity is high, cycle performance is good, high rate performance is good is provided, also provides corresponding and provide that a kind of technique is simple, easy to operate, cost is low, be applicable to the preparation method of the nucleocapsid structure lithium ion battery anode composite material of scale and suitability for industrialized production.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of nucleocapsid structure lithium ion battery anode composite material, comprises LiFePO 4nanometer nucleome and Li 3v 2(PO4) 3housing, described Li 3v 2(PO4) 3housing is evenly coated on LiFePO 4the periphery of nanometer nucleome, described Li 3v 2(PO4) 3the periphery of housing is also coated with amorphous carbon; The chemical formula of described nucleocapsid structure lithium ion battery anode composite material is xLiFePO 4li 3v 2(PO4) 3/ C, wherein the span of x is 3 ~ 9.
In technique scheme, the value of described x is 8, and the mass percent of described amorphous carbon shared by anode composite material of lithium ion battery is 3 ~ 15%.
As a total technical conceive, the present invention also provides a kind of preparation method of nucleocapsid structure lithium ion battery anode composite material, comprises the following steps:
(1) load as the Fe source compound of raw material, vanadium source compound, P source compound, Li source compound, chelating agent and carbon source in closed container according to stoichiometric proportion mixing, in closed container, add deionized water and stir 1 ~ 3h at the temperature lower magnetic force of 60 ~ 80 DEG C and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 10 ~ 20h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, in inert gas shielding atmosphere, rise to 300 ~ 400 DEG C with the heating rate of 2 ~ 8 DEG C/min sinter, insulation 3 ~ 5h, the precursor powder naturally obtained after cooling; In this step, 30 ~ 60min is preferably to the milling time of xerogel precursor mixture; Inert gas preferably passes into heating furnace with the speed of 100 ~ 1000mL/min;
(4) will proceed in heating furnace after the precursor powder obtained grinding evenly; 650 ~ 850 DEG C are risen to 2 ~ 8 DEG C/min heating rate in inert gas or reducibility gas protective atmosphere; calcining at constant temperature 6 ~ 12h, obtains nucleocapsid structure lithium ion battery anode composite material after cooling naturally.In this step, 20 ~ 40min is preferably to the milling time of xerogel precursor mixture;
In above-mentioned preparation method, preferably, described Fe source compound is at least one in ferrous sulfate, ferrous oxalate, iron oxide, ironic citrate, ferric phosphate and ferric nitrate; Described vanadium source compound is at least one in the oxide of vanadium, ammonium metavanadate and lithium vanadate; Described P source compound is at least one in ammonium di-hydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate and ferric phosphate; Described Li source compound is at least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium dihydrogen phosphate; The described chelating agent at least one that to be oxalic acid, citric acid, tartaric acid, polyacrylic acid and mass ratio be in the hydrogen peroxide of 30%; Described carbon source is at least one in acetylene black, graphite powder, superconduction carbon black, citric acid and solvable carbohydrate; The oxide of above-mentioned vanadium is preferably vanadic oxide.
In above-mentioned preparation method, preferably, in described raw material, the mol ratio of ferro element, v element, P elements, 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).
In above-mentioned preparation method, preferably, in described raw material, the content of carbon is 10% of the quality of the anode composite material of lithium ion battery generated.
In above-mentioned preparation method, preferably, the described closed container closed glass jar that is the blue bottle of silk, ground flask or adds a cover; Described heating furnace is tube furnace.
In above-mentioned preparation method, preferably, described inert gas is that argon gas, nitrogen or nitrogen are argon-mixed; Described reducibility gas is the mist of the argon-mixed and hydrogen of argon gas, nitrogen, CO (carbon monoxide converter) gas, nitrogen, and hydrogen or CO (carbon monoxide converter) gas account for 3 ~ 15% of mist volume.
In above-mentioned preparation method, preferably, also have the step that the solidliquid mixture that obtains after to step (1) processes further before the step (2), process refers to and adopts at least one processing method in ultrasonic disperse, hydro-thermal and interpolation dispersant to process solidliquid mixture further.
In above-mentioned preparation method, preferably, the processing time of described ultrasonic disperse process is 0.5 ~ 4h; The reaction temperature of described hydrothermal treatment consists is 180 ~ 220 DEG C, and temperature retention time is 2 ~ 40h; The dispersant adopted in the process of described interpolation dispersant is at least one in paraffin, PVP, polyethylene glycol, hydrazine hydrate, methyl anyl alcohol, polyacrylamide and fatty acid.
Compared with prior art, the invention has the advantages that:
1, Li in nucleocapsid structure lithium ion battery anode composite material of the present invention 3v 2(PO4) 3housing is coated on LiFePO equably 4nanometer nucleome is peripheral, and amorphous carbon is coated on active material periphery, due to coated Li 3v 2(PO 4) 3there is special three dimensional skeletal structure, enable lithium ion deintercalation fast, and coated amorphous carbon effectively can suppress particle growth, improve the conductivity of material; Nucleocapsid structure lithium ion battery anode composite material of the present invention utilizes Li 3v 2(PO4) 3high theoretical specific capacity, fast ion conduction and high voltage platform can modification LiFePO 4material, and the metal ion of bi-material adulterates mutually, effectively can improve the chemical property of composite material; The specific capacity that nucleocapsid structure lithium ion battery anode composite material tool of the present invention is higher and energy density, good cyclical stability and preferably high rate performance.
2, the preparation method of nucleocapsid structure lithium ion battery anode composite material of the present invention is that employing one step sol-gel process obtains nucleocapsid structure lithium ion battery anode composite material, all raw materials are once added, can greatly simplify its building-up process, its technique is simple, be easy to operation, cost low, be applicable to scale and suitability for industrialized production; In preparation process, adopt the technique of water solvent and enclosed system, be conducive to quick, the easy reactant presoma obtaining evenly drying on the one hand, on the other hand, it is environmentally friendly, can not to environment.Further, the uniformity of solwution method can increase the uniformly dispersed of each component further, effectively can improve the chemical property of the nucleocapsid structure lithium ion battery anode composite material after synthesis.
3, preparation method of the present invention can adopt multiple processing method to be further processed the solidliquid mixture obtained after step (1), so not only can obtain the nanoscale reactant presoma of even, coated, narrow particle size distribution, and multiple processing method also can adopt in simultaneously appropriate cooperation, can greatly enhance productivity, make technique simpler, operability is better.
4, in preparation method of the present invention, high temperature sintering adopts reducibility gas as protective gas, the oxidation side reaction brought due to the existence of a small amount of oxygen effectively can be avoided to occur, thus obtain highly purified nucleocapsid structure lithium ion battery anode composite material.
5, the nucleocapsid structure lithium ion battery anode composite material that preparation method of the present invention obtains has specific capacity and the premium properties such as energy density is high, good cycling stability, high rate performance are good.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the nucleocapsid structure lithium ion battery anode composite material that the embodiment of the present invention 1 prepares.
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 the cycle performance curve chart of button cell under 165mA/g, 2.5V-4.5V discharge and recharge system.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of nucleocapsid structure lithium ion battery anode composite material, comprises LiFePO 4nanometer nucleome and Li 3v 2(PO4) 3housing, Li 3v 2(PO4) 3housing is evenly coated on LiFePO 4the periphery of nanometer nucleome, and Li 3v 2(PO4) 3the periphery of housing is also coated with amorphous carbon.The chemical formula of this nucleocapsid structure lithium ion battery anode composite material is xLiFePO 4li 3v 2(PO 4) 3/ C, wherein, the span of x is 3 ~ 9, and the mass percent of amorphous carbon shared by anode composite material of lithium ion battery is 3 ~ 15%.
The xLiFePO of above-mentioned nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery is obtained by following preparation method:
(1) FeSO as raw material is taken according to the stoichiometric proportion of 8:1:11:6:27 47H 2o, V 2o 5, NH 4h 2pO 4, Li 2cO 3and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes section's qin superconduction carbon black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in tube furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure adopting the preparation method of the present embodiment to obtain 4li 3v 2(PO 4) 3the XRD result of/C anode composite material of lithium ion battery as shown in Figure 1, by diffraction maximum position in figure, can infer by intensity and width, and the crystallinity of sintetics is very good, and Fig. 2 is the 8LiFePO of nucleocapsid structure after synthesis 4li 3v 2(PO 4) 3the cycle performance curve chart of/C anode composite material of lithium ion battery under 165mA/g, 2.5V-4.5V discharge and recharge system, can find out that it possesses very excellent chemical property.
Embodiment 2
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) FeSO as raw material is taken according to the stoichiometric proportion of 8:1:11:6:27 47H 2o, V 2o 5, NH 4h 2pO 4, Li 2cO 3and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes section's qin superconduction carbon black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 3
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) FeSO as raw material is taken according to the stoichiometric proportion of 8:1:11:6:27 47H 2o, V 2o 5, NH 4h 2pO 4, Li 2cO 3and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes section's qin superconduction carbon black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h, then to proceed in water heating kettle be incubated 6 hours at 200 DEG C of temperature;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 4
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) FeSO as raw material is taken according to the stoichiometric proportion of 8:1:11:6:27 47H 2o, V 2o 5, NH 4h 2pO 4, Li 2cO 3and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes section's qin superconduction carbon black, first in closed container by FeSO 47H 2o and H 2c 2o 42H 2o mixes, and adds 300ml deionized water and obtains thin milky mixt, for removing SO4 residual in this thin milky mixt at 70 DEG C of temperature lower magnetic forces stirring 2h 2-deng foreign ion, adopt centrifugation, and by washed with de-ionized water 3 times, obtain FeC 2o 42H 2o yellow paste product.By V 2o 5, NH 4h 2pO 4, Li 2cO 3add successively in closed container with section qin superconduction carbon black.In closed container, add 300ml deionized water again, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The thin breast of ferrous oxalate and vanadium oxalate solution can be formed, the vanadium oxalate (VOC of solution state when adding thermal agitation in the preparation process of the present embodiment 2o 4) ferrous oxalate (FeC of precipitated form can be wrapped in 2o 4) surface, effective synthetic kernel shell structure; Meanwhile, the vanadium oxalate (VOC of surface parcel 2o 4) can effectively suppress growing up of internal layer LiFePO4 when being converted into phosphoric acid vanadium lithium.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 5
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) FeC as raw material is taken according to the stoichiometric proportion of 8:1:11:12:3 6h 5o 75H 2o, V 2o 5, NH 4h 2pO 4, LiOHH 2o and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes acetylene black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 60 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 6
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) FeC as raw material is taken according to the stoichiometric proportion of 8:1:11:12:2 6h 5o 75H 2o, V 2o 5, NH 4h 2pO 4, LiOHH 2o and C 6h 8o 7the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes acetylene black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 60 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 7
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) according to the stoichiometric proportion of 8:1:3:12:27 by raw material FePO 42H 2o, V 2o 5, NH 4h 2pO 4, LiOHH 2o and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes section's qin superconduction carbon black, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) by proceeding in heating furnace after the precursor powder obtained grinding evenly, in reducibility gas protective atmosphere, rising to 750 DEG C, calcining at constant temperature 8h with 5 DEG C/min heating rate, naturally after cooling, obtaining the 8LiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.
Embodiment 8
A kind of xLiFePO of nucleocapsid structure 4li 3v 2(PO 4) 3the preparation method of/C anode composite material of lithium ion battery, comprises the following steps:
(1) according to the stoichiometric proportion of 8:1:3:12:27 by raw material FePO 42H 2o, V 2o 5, NH 4h 2pO 4, LiOHH 2o and H 2c 2o 42H 2o, the amount being 10% according to the mass ratio of amorphous carbon in the anode composite material of lithium ion battery generated takes sucrose, the raw material mixing taken is loaded closed container, then adds 300ml deionized water to closed container, stir 2h at 70 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 2h;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 12h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, the inert gas formation inert gas shielding atmosphere that flow velocity is 100 ~ 300mL/min is passed in tube furnace, rise to 350 DEG C with the heating rate of 5 DEG C/min to sinter, insulation 4h, the precursor powder naturally obtained after cooling; In this step, milling time is preferably 40min;
(4) will proceed in heating furnace after the precursor powder obtained grinding evenly; 750 DEG C are risen to 5 DEG C/min heating rate in reducibility gas protective atmosphere; calcining at constant temperature 8h, obtains nucleocapsid structure lithium ion battery anode composite material 8LiFePO after cooling naturally 4li 3v 2(PO 4) 3/ C.In this step, milling time is preferably 30min.
The 8LiFePO of the nucleocapsid structure that the preparation method of the present embodiment obtains 4li 3v 2(PO 4) 3/ C anode composite material of lithium ion battery possesses extraordinary crystallinity and very excellent chemical property equally.

Claims (10)

1. a nucleocapsid structure lithium ion battery anode composite material, is characterized in that: comprise LiFePO 4nanometer nucleome and Li 3v 2(PO4) 3housing, described Li 3v 2(PO4) 3housing is evenly coated on LiFePO 4the periphery of nanometer nucleome, described Li 3v 2(PO4) 3the periphery of housing is also coated with amorphous carbon; The chemical formula of described nucleocapsid structure lithium ion battery anode composite material is xLiFePO 4li 3v 2(PO4) 3/ C, wherein the span of x is 3 ~ 9.
2. nucleocapsid structure lithium ion battery anode composite material according to claim 1, is characterized in that: the value of described x is 8, and the mass percent of described amorphous carbon shared by anode composite material of lithium ion battery is 3 ~ 15%.
3. a preparation method for nucleocapsid structure lithium ion battery anode composite material as claimed in claim 1, is characterized in that, comprise the following steps:
(1) load as the Fe source compound of raw material, vanadium source compound, P source compound, Li source compound, chelating agent and carbon source in closed container according to stoichiometric proportion mixing, in closed container, add deionized water and stir 1 ~ 3h at the temperature lower magnetic force of 60 ~ 80 DEG C and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 10 ~ 20h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, in inert gas shielding atmosphere, rise to 300 ~ 400 DEG C with the heating rate of 2 ~ 8 DEG C/min sinter, insulation 3 ~ 5h, the precursor powder naturally obtained after cooling;
(4) will proceed in heating furnace after the precursor powder obtained grinding evenly; 650 ~ 850 DEG C are risen to 2 ~ 8 DEG C/min heating rate in inert gas or reducibility gas protective atmosphere; calcining at constant temperature 6 ~ 12h, obtains nucleocapsid structure lithium ion battery anode composite material after cooling naturally.
4. preparation method according to claim 3, is characterized in that: described Fe source compound is at least one in ferrous sulfate, ferrous oxalate, iron oxide, ironic citrate, ferric phosphate and ferric nitrate; Described vanadium source compound is at least one in the oxide of vanadium, ammonium metavanadate and lithium vanadate; Described P source compound is at least one in ammonium di-hydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate and ferric phosphate; Described Li source compound is at least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium dihydrogen phosphate; The described chelating agent at least one that to be oxalic acid, citric acid, tartaric acid, polyacrylic acid and mass ratio be in the hydrogen peroxide of 30%; Described carbon source is at least one in acetylene black, graphite powder, superconduction carbon black, citric acid and solvable carbohydrate.
5. preparation method according to claim 3, is characterized in that: in described raw material, the mol ratio of ferro element, v element, P elements, 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).
6. preparation method according to claim 3, is characterized in that: in described raw material, the content of carbon is 10% of the quality of the anode composite material of lithium ion battery generated.
7. preparation method according to claim 3, is characterized in that: the closed glass jar that described closed container is the blue bottle of silk, ground flask or adds a cover; Described heating furnace is tube furnace.
8. preparation method according to claim 3, is characterized in that: described inert gas is that argon gas, nitrogen or nitrogen are argon-mixed; Described reducibility gas is the mist of the argon-mixed and hydrogen of argon gas, nitrogen, CO (carbon monoxide converter) gas, nitrogen, and hydrogen or CO (carbon monoxide converter) gas account for 3 ~ 15% of mist volume.
9. preparation method according to claim 3, it is characterized in that: also have the step that the solidliquid mixture that obtains after to step (1) processes further before the step (2), process refers to and adopts at least one processing method in ultrasonic disperse, hydro-thermal and interpolation dispersant to process solidliquid mixture further.
10. preparation method according to claim 9, is characterized in that: the processing time of described ultrasonic disperse process is 0.5 ~ 4h; The reaction temperature of described hydrothermal treatment consists is 180 ~ 220 DEG C, and temperature retention time is 2 ~ 40h; The dispersant adopted in the process of described interpolation dispersant is at least one in paraffin, PVP, polyethylene glycol, hydrazine hydrate, methyl anyl alcohol, polyacrylamide and fatty acid.
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CN106374089A (en) * 2016-10-25 2017-02-01 成都新柯力化工科技有限公司 Lithium iron phosphate-lithium vanadium phosphate nano composite electrode material and preparation method therefor
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
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CN110085810A (en) * 2018-01-25 2019-08-02 天津国安盟固利新材料科技股份有限公司 A kind of preparation method and application of coating modification lithium cobaltate cathode material
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CN110492089A (en) * 2019-09-18 2019-11-22 宁波大学 A kind of carbon coating di-iron trioxide and five potassium vanadate composite material and preparation methods
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
CN111554914A (en) * 2020-05-29 2020-08-18 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
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