CN104752722B - A kind of vanadium phosphate cathode material of doping vario-property, its preparation and application - Google Patents

A kind of vanadium phosphate cathode material of doping vario-property, its preparation and application Download PDF

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CN104752722B
CN104752722B CN201510121618.8A CN201510121618A CN104752722B CN 104752722 B CN104752722 B CN 104752722B CN 201510121618 A CN201510121618 A CN 201510121618A CN 104752722 B CN104752722 B CN 104752722B
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lithium
preparation
vanadium
presoma
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CN104752722A (en
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李月姣
吴锋
周川雄
曹美玲
陈实
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Beijing Institute of Technology BIT
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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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of preparation method of the vanadium phosphate cathode material of doping vario-property, including step:1) after mixing lithium source, vanadium source, phosphorus source, gadolinium source with reducing agent sucrose, plus deionized water grinds the solidliquid mixture obtaining rheology phase；2) rheology phase solidliquid mixture is moved to autoclave, response time 8～15h, obtain presoma；3) presoma is dried；4) dried presoma sinters 3～5h at 300～400 DEG C, obtains material previously treated after natural cooling；5) material previously treated is sintered 6～10h at 700～850 DEG C, after natural cooling, obtain black solid, described black solid is the vanadium phosphate cathode material of Gd2 O3.The present invention also proposes preparation-obtained positive electrode and its application.Method process is simple proposed by the present invention, synthesis temperature is low, suitable large-scale production, and the material granule distribution of the Gd2 O3 synthesizing is more uniform, and chemical property is greatly improved.

Description

A kind of vanadium phosphate cathode material of doping vario-property, its preparation and application
Technical field
The invention belongs to heat exchange material field is and in particular to the answering of a kind of high heat conductance porous material and low-melting-point metal Close phase-change heat-storage material.
Background technology
Lithium ion battery because its energy density height, output power, have extended cycle life, environmental protection the advantages of ground The common concern of the person of studying carefully.In the factors of impact performance of lithium ion battery, shared by positive electrode, battery cost reaches 40%, Become the key of restriction battery development.Positive electrode common at present mainly has layer structure oxide LiMO2(M=Co, Ni, Mn), spinel structure LiMn2O4, olivine structural LiFePO4With monocline Li3V2(PO4)3Deng phosphate material.Wherein, LiFePO4 and phosphoric acid vanadium lithium are because its safety is higher, cheap, have extended cycle life so more there being application prospect.But phosphoric acid Ferrum lithium has that electronic and ionic poorly conductive, heavy-current discharge characteristic be poor and the low defect of lithium ion diffusion coefficient.In contrast, The electronic and ionic electric conductivity of phosphoric acid vanadium lithium is higher, theoretical charge/discharge capacity is bigger, remain to holding under the high charge voltage of 4.8V Stable crystal structure, therefore has more Research Significance.
Currently for the research of positive electrode, it is concentrated mainly on the improvement of synthetic method, and carbon coating is carried out to material With doping vario-property etc..The method of synthesis phosphoric acid vanadium lithium mainly includes high temperature solid-state method, sol-gal process, hydrothermal synthesis method, wet method Solid state reaction of coordination method and Rheological Phase Method etc..High temperature solid-state method is to use pure H2Or with H2With the mixed gas of argon as reducing agent, high temperature Under make substance reaction, process is simple is advantageously implemented industrialization, but its reactant is difficult to mix homogeneously, and particle size is relatively Greatly, granule-morphology is irregular, needs higher temperature and longer response time simultaneously and energy consumption is larger in building-up process.Molten Sol-gel be by stock dispersion in a solvent through hydrolysis generate activated monomer, then by polyreaction formation colloidal sol, gel, Afterwards through being dried and heat treatment obtains material requested, its particle size is little to be evenly distributed but the preparation process of presoma is more multiple Miscellaneous, need to be dried for a long time and be difficult to ensure that in subsequent high temperature sintering and sufficiently uniformly contact, commercial production difficulty is big. Hydrothermal synthesis method is to occur chemical reaction to prepare sample in aqueous by raw material, and uniform particle sizes' specific surface area is greatly but to anti- Answer pressure and temperature requirement higher, during preparation, production cost need to be increased using the high high-temperature high-pressure apparatus of cost.Numerous In technique, Rheological Phase Method, as new effective soft chemical method, has building-up process simplicity, and sintering temperature is low, is more suitable for industry The advantage that metaplasia is produced.Rheological Phase Method is that reactant is passed through suitable mix homogeneously, adds suitable quantity of water or other solvents to be modulated into admittedly Body particle and liquid distribution uniformly thick solid-liquid hybrid system, then reaction obtains required product, work under proper condition Skill is simpler, environmental protection.In the synthesis of anode material for lithium-ion batteries, the application of Rheological Phase Method is more and more extensive.Adopt As anode material for lithium-ion batteries, there is electronic and ionic poorly conductive, lithium ion with the pure phase phosphoric acid vanadium lithium of Rheological Phase Method preparation The low defect of diffusion coefficient, needs to be doped study on the modification to it in the method.
For the modification of positive electrode, doping method can improve the chemical property of material in itself.Doped chemical Select also to be transitioned in rare earth element by common active metal.Gadolinium element because have good superconduct performance, can be certain The shortcoming overcoming material electronicses ionic conductivity difference in degree, thus improve the chemical property of material.
Content of the invention
In place of the deficiencies in the prior art, the purpose of the present invention is to adopt Rheological Phase Method, is provided by Gd2 O3 preparation There is the lithium ion battery vanadium phosphate cathode material of good chemical property.
Another object of the present invention is to propose obtained Gd2 O3 vanadium phosphate cathode material.
Third object of the present invention is to propose the application of described positive electrode.
Realizing above-mentioned purpose technical scheme of the present invention is：
A kind of preparation method of the vanadium phosphate cathode material of doping vario-property, including step:
1) after mixing lithium source, vanadium source, phosphorus source, gadolinium source with reducing agent sucrose, plus deionized water grinds and obtains rheology phase Solidliquid mixture；Wherein lithium source, vanadium source, phosphorus source, the ratio in gadolinium source, sucrose and water are Li：(V+Gd)：P：Sucrose：Water=(3.0 ～3.3) mol：2mol：3mol：0.2mol：(400～600) ml,
2) rheology phase solidliquid mixture is moved to closed reactor, 70～90 DEG C of reaction temperature, response time 8～15h, obtain To presoma；
3) presoma is dried 3～5 hours at 50～70 DEG C；
4) dried presoma sinters 3～5h at 300～400 DEG C, obtains material previously treated after natural cooling；
5) material previously treated is sintered 6～10h at 700～850 DEG C, obtain black solid after natural cooling, described black Solid is the vanadium phosphate cathode material of the Gd2 O3 adopting Rheological Phase Method preparation.
Reactant different from sol-gal process is in the solution state being completely dissolved, and the reactant of Rheological Phase Method is in non- The solid-liquid two-phase coexistent state being completely dissolved.
Wherein, step 1) in, described lithium source is one of Lithium hydrate, lithium carbonate, lithium acetate, lithium fluoride or lithium oxalate Or multiple, described vanadium source be vanadic anhydride or ammonium metavanadate, described gadolinium source be Gadolinia., phosphorus source be ammonium dihydrogen phosphate, One or more of diammonium phosphate or ammonium phosphate.
Wherein, step 1) in, Gd：(V+Gd)=(0.01～0.1) mol：2mol.
Preferably, Gd：(V+Gd)=(0.01～0.02) mol：2mol.
Wherein, step 4) and step 5) in, it is sintered in carrying out under non-oxidizing gas protection, described non-oxidizing gas are One or more of argon, helium or nitrogen.
Preferably, step 5) in, after material previously treated is ground, it is compacted 5～10min under 5～10MPa pressure, obtains Thickness is the solid sheet of 0.5～1cm, is then sintered.
The positive electrode that preparation method of the present invention prepares.
Lithium ion battery containing positive electrode of the present invention.
The beneficial effects of the present invention is：
Method process is simple proposed by the present invention, synthesis temperature is low, suitable large-scale production, and the material of the Gd2 O3 synthesizing Material distribution of particles is more uniform, and chemical property is greatly improved.Rheological Phase Method is as a kind of new side preparing positive electrode Method, combines conventional solid-state method and hydrothermal synthesis method, the respective advantage of sol-gal process, and technological process is simple, temperature required low, Granule mix homogeneously, suitable large-scale industrial production.The phosphoric acid vanadium lithium of the Gd2 O3 of Rheological Phase Method preparation proposed by the present invention Anode material for lithium-ion batteries has more excellent chemical property.In phase character, Gd3+Ion enters intracell, draws Played the change of cell configuration, but lattice changed less, consistent with the crystalline structure of raw material, and do not have impurities phase or Side reaction product produces.SEM shows, the granule of dopant material has the feature of stratiform accumulation, and the radius of independent granule is about 0.5 ～1 μm, the granule entirety of accumulation horizon is at 10 μm about.On chemical property, this material 0.2C in 3.0-4.3V voltage range Under multiplying power, initial charge capacity is 125.2mAh/g, and discharge capacity is 117.4mAh/g, and efficiency is up to 93.7%, circulates 80 weeks Capability retention is higher than 80% afterwards.
Brief description
Fig. 1 is X-ray diffraction (XRD) figure of the Gd2 O3 lithium vanadium phosphate cathode material of embodiment 1 preparation.
Fig. 2 is scanning electron microscope (SEM) figure of the Gd2 O3 lithium vanadium phosphate cathode material of embodiment 1 preparation.
Fig. 3 is Li3V2-xGdx(PO4)3The 0.2C rate charge-discharge curve of (x=0,0.02,0.05,0.08,0.1), Fig. 3 a For 3.0-4.3V, Fig. 3 b is 3.0-4.8V.
Fig. 4 is high rate performance comparison diagram.
When Fig. 5 is that in the range of 3.0-4.3V, charge-discharge magnification is 0.2C, the cycle performance curve of material.
When Fig. 6 is that in the range of 3.0-4.8V, charge-discharge magnification is 0.2C, the cycle performance curve of material.
When Fig. 7 is that in the range of 3.0-4.3V, charge-discharge magnification is respectively 0.2C, 0.5C, 1C and 2C, the high rate performance of material Curve.
When Fig. 8 is that in the range of 3.0-4.8V, charge-discharge magnification is respectively 0.2C, 0.5C, 1C and 2C, the high rate performance of material Curve.
When Fig. 9 is that in the range of 3.0-4.3V, charge-discharge magnification is respectively 0.2C, 0.5C, 1C and 2C, the gadolinium of embodiment 2 preparation The high rate performance curve of doping vario-property vanadium phosphate cathode material.
When Figure 10 is that in the range of 3.0-4.8V, charge-discharge magnification is respectively 0.2C, 0.5C, 1C and 2C, embodiment 2 preparation The high rate performance curve of Gd2 O3 lithium vanadium phosphate cathode material.
Specific embodiment
Below by most preferred embodiment, the present invention to be described.Those skilled in the art institute it should be understood that, embodiment is only used for Illustrate rather than for limiting the scope of the present invention.
In embodiment, if no special instructions, means used are the conventional means in this area.
Embodiment 1：
Take a series of parallel test to determine optimal Gd doping.Using Rheological Phase Method technological process, synthesize Doping is respectively the Li of x=0,0.02,0.05,0.08,0.13V2-xGdx(PO4)3Material.
The step of materials synthesis and test process are as follows：
1) by lithium source Li2CO3, vanadium source V2O5, gadolinium source Gd2O3, phosphorus source NH4H2PO4It is ground in mortar with sucrose, After 30min mix homogeneously, it is added dropwise over 20ml deionized water, grind and obtain uniform rheology phase solidliquid mixture；
2) moving to solidliquid mixture in the hydrothermal reaction kettle being lined with politef set (does not need to stir), at 80 DEG C Pretreatment 12h in baking oven, obtains presoma；
3) presoma is dried 4h in 60 DEG C of baking ovens；
4) presoma is moved in argon tube furnace, sinter 3h under the conditions of 350 DEG C, obtain dark brown after natural cooling pre- Process material；
5) material previously treated is ground, after compacting 10min under 8MPa pressure, obtaining thickness is the solid of 0.5～1cm Piece, sinters 6h at 750 DEG C in moving to argon tube furnace, obtains black solid, described black solid is as adopted after natural cooling Vanadium phosphate cathode material with the Gd2 O3 of Rheological Phase Method synthesis.Material is done with XRD test, the results are shown in Table 1.Material is done SEM, SEM photograph is shown in Fig. 2.In Fig. 2, the lower right corner represents the corresponding material of each Zhang little Tu, and below each Zhang little Tu, scale is 5 microns. As shown in Figure 2, the grain diameter of blank LVP sample is about 2 μm, and granule disperses, and corner angle are obvious.When doping is for x=0.02, It can be seen that the granule in SEM image have stratiform pile up feature, the radius of independent granule about at 0.5～1 μm, accumulation horizon Granule entirety is at 10 μm about.Other doped samples are basically identical with the particle characteristic of blank sample, the granule circle as x=0.05 It is sliding that uniformly, when x increases to 0.08 and 0.1, granule mean radiuss are compared low-doped amount and are increased, and granule disperses, start corner angle occur be in Irregular form, has certain impact to the chemical property of material.
Table 1 Li3V2-xGdx(PO4)3Material cell parameter
The main peak type of four kinds of samples is basically identical with blank sample, does not substantially produce impurities phase or side reaction product, table Bright required doping Li can successfully be prepared using Rheological Phase Method3V2-xGdx(PO4)3Material.By the strongest 3 of four kinds of material XRD Characteristic peak collection of illustrative plates and the contrast of corresponding cell parameter find, adulterate Gd3+After ion, the position at peak and peak intensity all have little amplitude variation Change.Wherein, during doping x=0.02, the peak type of material meets best with blank result, and lattice structure calculates gained structure cell Volume is basically unchanged, and has a little lifting.After doping increases to 0.05, the characteristic peak skew of XRD, unit cell volume diminishes, and with The increase unit cell volume doping x is gradually brought to blank sample size, and the skew of characteristic peak is replied.Thus, it can be known that Gd3+From The doping of son causes the change of cell configuration, and dopant ion enters intracell.
6) by prepared positive electrode, acetylene black, Kynoar (PVDF) according to mass ratio be 8：1：1 mixing is all Even, add a certain amount of Solvents N-methyl -2-Pyrrolidone (NMP), put into that agate mortar is mixed to wear into pulpous state, adjust to suitable Viscosity.Slurry is uniformly applied on aluminium foil, 12h is dried at 80 DEG C, be dried and be compacted under the pressure of 8MPa, finally cut Become the electrode slice of a diameter of 10mm.
Table 2 Li3V2-xGdx(PO4)3(x=0,0.02,0.05,0.08,0.1) 0.2C first charge-discharge capacity
7) with above-mentioned electrode slice as positive pole, be to electrode with metal lithium sheet, polypropylene porous film Celgard2400 be every Film, electrolyte adopts 1.0mol/L LiPF6- EC+DMC (volume ratio 1:1), the glove box full of argon is assembled into button 2025 type batteries, then do constant current charge-discharge loop test, charge and discharge in land test system (Wuhan Lan electricity Electronics Co., Ltd.) Electric blanking voltage is 3.0～4.3V and 3.0～4.8V.Result such as table 2 and Fig. 3, Fig. 4.
In Fig. 3, Li3V2-xGdx(PO4)3(x=0,0.02,0.05,0.08,0.1) (0.2C times of charge and discharge cycles curve Rate discharge and recharge, discharge and recharge blanking voltage is 3.0-4.3V (Fig. 3 a), and discharge and recharge blanking voltage is 3.0-4.8V (Fig. 3 b)) by Fig. 3 It can be seen that, doping is 0.02 sample not only first charge-discharge efficiency height, and after 80 circulations, capacity attenuation is more slow, protects Holdup is high, and 0.1 sample is worst, and compared with blank sample, also there is a big difference.
Fig. 4 is Li3V2-xGdx(PO4)3(x=0,0.02,0.05,0.08,0.1) high rate performance comparison diagram (3.0-4.3V (Fig. 4 a), 3.0-4.8V (Fig. 4 b)).In 3.0-4.3V, doping be 0.02 and 0.05 high rate performance equally matched substantially Higher than other dopant materials and blank sample, when voltage brings up to 4.8V, doping is 0.02 properties of sample optimum.Comprehensive The physicochemical characteristic of material and chemical property, doping is 0.02 sample, granule uniformly, efficiency high, cyclical stability first Good, high rate performance is excellent, determines that 0.02 is the material modified doping of phosphoric acid vanadium lithium in subsequent experimental.
Comparative example：
For contrast blank sample be vanadium phosphate cathode material, preparation method with embodiment 1, in step 1) in do not have Add gadolinium source.
Make experimental cell and test chemical property using the method same with embodiment 1.
On chemical property, blank sample discharge capacity first only has 110.7mAh/g (3.0-4.3V), 149.8mAh/ g(3.0-4.8V).On high rate performance, under 3.0-4.3V voltage window, material, after 50 weeks circulate, is transferred in 2C multiplying power Capacitance blank sample compared with first is 41.1%.Gd therefore prepared by the present invention3+Ion doping material can effectively carry The lithium ion diffusion coefficient of high material is thus improve the discharge capacity of LVP material, high rate performance and cycle characteristics.
Embodiment 2：
The step of materials synthesis and battery testing process are as follows：
1) by lithium source 0.079mol Li2CO3, vanadium source 0.0495mol V2O5, gadolinium source 0.0005molGd2O3, phosphorus source 0.15mol NH4H2PO4Be ground in mortar with 0.01mol sucrose, after 30min mix homogeneously, be added dropwise over 20ml go from Sub- water, grinds and obtains uniform rheology phase solidliquid mixture；
2) moving to solidliquid mixture in the hydrothermal reaction kettle being lined with politef set (does not need to stir), at 80 DEG C Pretreatment 12h in baking oven, obtains presoma；
3) presoma is dried 4h in 60 DEG C of baking ovens；
4) presoma is moved in argon tube furnace, sinter 3h under the conditions of 350 DEG C, obtain dark brown after natural cooling pre- Process material；
5) material previously treated is ground, after compacting 10min under 8MPa pressure, obtaining thickness is the solid of 0.5～1cm Piece, sinters 6h at 750 DEG C in moving to argon tube furnace, obtains black solid, described black solid is as adopted after natural cooling With the vanadium phosphate cathode material of the Gd2 O3 of Rheological Phase Method synthesis, the molecular formula of this material is Li3V1.98Gd0.02(PO4)3.
6) by prepared positive electrode, acetylene black, Kynoar (PVDF) according to mass ratio be 8：1：1 mixing is all Even, add a certain amount of Solvents N-methyl -2-Pyrrolidone (NMP), put into that agate mortar is mixed to wear into pulpous state, adjust to suitable Viscosity.Slurry is uniformly applied on aluminium foil, 12h is dried at 80 DEG C, be dried and be compacted under the pressure of 8MPa, finally cut Become the electrode slice of a diameter of 10mm.
7) with above-mentioned electrode slice as positive pole, be to electrode with metal lithium sheet, polypropylene porous film Celgard2400 be every Film, electrolyte adopts 1.0mol/L LiPF6- EC+DMC (volume ratio 1:1), the glove box full of argon is assembled into button 2025 type batteries, then do constant current charge-discharge loop test, charge and discharge in land test system (Wuhan Lan electricity Electronics Co., Ltd.) Electric blanking voltage is 3.0～4.3V and 3.0～4.8V.
Fig. 1 is X-ray diffraction (XRD) figure of Gd2 O3 lithium vanadium phosphate cathode material manufactured in the present embodiment, explanation Obtain is the lithium vanadium phosphate material of monocline, and free from admixture phase produces；
First figure of Fig. 2 is the scanning electron microscope (SEM) of Gd2 O3 lithium vanadium phosphate cathode material manufactured in the present embodiment Figure, illustrate the granule of dopant material have stratiform accumulation feature, the radius of independent granule about at 0.5～1 μm, accumulation horizon Grain entirety is at 10 μm about；
When Fig. 5 is that in the range of 3.0-4.3V, charge-discharge magnification is 0.2C, the Gd2 O3 modified phosphate vanadium lithium of embodiment 2 preparation The first charge-discharge curve of positive electrode.Wherein initial charge capacity is 125.2mAh/g, and discharge capacity is 117.4mAh/g, effect Rate is up to 93.7%.
When Fig. 6 is that in the range of 3.0-4.8V, charge-discharge magnification is 0.2C, the Gd2 O3 modified phosphate vanadium lithium of embodiment 2 preparation The first charge-discharge curve of positive electrode.Wherein first charge-discharge capacity is respectively 179.5mAh/g and 161.1mAh/g, efficiency Up to 89.7%.
When Fig. 7 is that in the range of 3.0-4.3V, charge-discharge magnification is 0.2C, the Gd2 O3 modified phosphate vanadium lithium of embodiment 2 preparation The cycle performance curve of positive electrode, after circulating 80 weeks, capability retention is 93.7%.
When Fig. 8 is that in the range of 3.0-4.8V, charge-discharge magnification is 0.2C, the Gd2 O3 modified phosphate vanadium lithium of embodiment 2 preparation The cycle performance curve of positive electrode, after circulating 80 weeks, capability retention is 82%.
When Fig. 9 is that in the range of 3.0-4.3V, charge-discharge magnification is respectively 0.2C, 0.5C, 1C and 2C, manufactured in the present embodiment The high rate performance curve of Gd2 O3 lithium vanadium phosphate cathode material.Figure 10 is that in the range of 3.0-4.8V, charge-discharge magnification is respectively When 0.2C, 0.5C, 1C and 2C, the high rate performance curve of Gd2 O3 lithium vanadium phosphate cathode material manufactured in the present embodiment.
Embodiment 3:
The step of materials synthesis and battery testing process are as follows：
1) by lithium source 0.15mol LiOH, vanadium source 0.0495mol V2O5, gadolinium source 0.0005mol Gd2O3, phosphorus source 0.15mol(NH4)2HPO4It is ground in mortar with 0.01mol sucrose, after 30min mix homogeneously, be added dropwise over 20ml and go Ionized water, grinds and obtains uniform rheology phase solidliquid mixture；
2) solidliquid mixture is moved in the hydrothermal reaction kettle being lined with politef set, pretreatment in 80 DEG C of baking ovens 10h, obtains presoma；
3) presoma is dried 4h in 60 DEG C of baking ovens；
4) presoma is moved in argon tube furnace, sinter 3h under the conditions of 380 DEG C, obtain dark brown after natural cooling pre- Process material；
5) material previously treated is ground, after compacting 10min under 8MPa pressure, obtaining thickness is the solid of 0.5～1cm Piece, sinters 7h at 750 DEG C in moving to argon tube furnace, obtains black solid, described black solid is as adopted after natural cooling With the vanadium phosphate cathode material of the Gd2 O3 of Rheological Phase Method synthesis, the molecular formula of this material is Li3V1.98Gd0.02(PO4)3.
Form battery with resulting materials, battery testing process is with embodiment 1.In the range of 3.0-4.3V, charge-discharge magnification is During 0.2C, initial charge capacity is 123.8mAh/g, and discharge capacity is 115.0mAh/g, and efficiency reaches 92.9%, after circulating 80 weeks Capability retention is 93.7%.
In the range of 3.0-4.8V charge-discharge magnification be 0.2C when, first charge-discharge capacity be respectively 178.9mAh/g and 160.7mAh/g, efficiency is up to 89.8%.After circulating 80 weeks, capability retention is 82%.
Above embodiment is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered Row limits, on the premise of without departing from design spirit of the present invention, the technical side to the present invention for this area ordinary skill technical staff Various modifications and improvement that case is made, all should fall in the protection domain of claims of the present invention determination.

Claims (6)

1. a kind of preparation method of the vanadium phosphate cathode material of doping vario-property is it is characterised in that include step:
1) after mixing lithium source, vanadium source, phosphorus source, gadolinium source with reducing agent sucrose, plus deionized water grinds the solid-liquid obtaining rheology phase Mixture；Wherein lithium source, vanadium source, phosphorus source, the ratio in gadolinium source, sucrose and water are Li：(V+Gd)：P：Sucrose：Water=(3.0～ 3.3)mol：2mol：3mol：0.2mol：(400～600) ml, Gd：(V+Gd)=(0.01～0.02) mol：2mol；
2) rheology phase solidliquid mixture is moved to closed reactor, 70～90 DEG C of reaction temperature, response time 8～15h, before obtaining Drive body；
3) presoma is dried 3～5 hours at 50～70 DEG C；
4) dried presoma sinters 3～5h at 300～400 DEG C, obtains material previously treated after natural cooling；
5) material previously treated is sintered 6～10h at 700～850 DEG C, obtain black solid after natural cooling, described black solid It is the vanadium phosphate cathode material of Gd2 O3.
2. preparation method according to claim 1 is it is characterised in that step 1) in, described lithium source is Lithium hydrate, carbonic acid One or more of lithium, lithium acetate, lithium fluoride or lithium oxalate, described vanadium source is vanadic anhydride or ammonium metavanadate, described gadolinium Source is Gadolinia., and phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium phosphate or ammonium phosphate.
3. preparation method according to claim 1 is it is characterised in that step 4) and step 5) in, it is sintered in non-oxidizable Carry out under gas shield, described non-oxidizing gas are one or more of argon, helium or nitrogen.
4. preparation method according to claim 1 is it is characterised in that step 5) in, after material previously treated is ground, 5 It is compacted 5～10min under～10MPa pressure, obtain the solid sheet that thickness is 0.5～1cm, be then sintered.
5. the positive electrode that the arbitrary described preparation method of Claims 1 to 4 prepares.
6. the lithium ion battery containing positive electrode described in claim 5.
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