CN104868120A - Li<2-2x>FexTiO3/Li3PO4 conjugate coated lithium ion phosphate material as well as preparation method and application thereof - Google Patents

Li<2-2x>FexTiO3/Li3PO4 conjugate coated lithium ion phosphate material as well as preparation method and application thereof Download PDF

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CN104868120A
CN104868120A CN201510187965.0A CN201510187965A CN104868120A CN 104868120 A CN104868120 A CN 104868120A CN 201510187965 A CN201510187965 A CN 201510187965A CN 104868120 A CN104868120 A CN 104868120A
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conjugation
lifepo
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CN104868120B (en
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于成龙
惠怀兵
郝欣
高举
曹舒尧
王斐
高丹鹏
王道益
杨龙涛
刘立炳
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Shaanxi University of Science and Technology
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 invention discloses a Li<2-2x>FexTiO3/Li3PO4 conjugate coated lithium ion phosphate material as well as a preparation method and application thereof. The material is obtained by coating LiFePO4 with Li<2-2x>FexTiO3 and Li3PO4 which grow conjugately, wherein x is more than or equal to 0 and less than or equal to 0.7. The conjugate growth coating material of the material is variable in composition and controllable in coating degree. According to the method, the Li<2-2x>FexTiO3 (x being more than or equal to 0 and less than or equal to 0.7) and the Li3PO4 conjugately grow on the surface of a cathode material for a lithium ion battery for modification, the conjugate growth coated cathode material obtained by adopting the method has a uniform surface coating, and the method is mature and reliable.

Description

A kind of Li 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material and its preparation method and application
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, be specifically related to a kind of Li 2- 2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material and its preparation method and application.
Background technology
Lithium ion battery is a kind of novel Green Chemistry power supply, has that voltage is high, the life-span is long, volume is little, self-discharge rate is low, capacity and the advantage such as energy density is large compared with traditional Ni-Cr battery, Ni-MH battery.But because LiFePO 4 does not have continuous print [FeO 6] be total to the octahedra network in limit, therefore can not electron conduction be formed.Simultaneously due to the [PO between octahedron 4] tetrahedron limits the change of cell volume, thus the diffusion of lithium ion deintercalation and electronics is affected, and causes LiFePO 4the electronic conductivity that positive electrode is extremely low and ion diffusivity.Therefore, how LiFePO is improved 4electric conductivity and charge-discharge magnification performance be one of free-revving engine of this material modification.
Relevant research has: the people such as Zhang Dongyun in 2011 are coated to LiFePO in order to study carbon 4the impact of structure take citric acid as carbon source, adopts mechanical activation-high temperature solid-state method, has synthesized the LiFePO of different carbon covering amount 4/ C composite positive pole.The same year, the people such as willow at the different carbon source of the coated middle employing of carbon and different carbon method for coating to LiFePO 4carry out study on the modification.List of references is: Zhang Dongyun, Zhang Peixin, and forest is worshipped, Liu Kun, Yuan Qiuhua, etc. the coated LiFePO of carbon 4structure and Properties research. Journal of Inorganic Materials, 2011 (3): 26; Willow, He Gang, Hong Jianhe, what bright middle .LiFePO 4the progress of carbon source and carbon method for coating in/C composite preparation process. material Leader, 2011 (10): 25.But the preparation method of positive electrode current material, the ionic conductivity of material and electrochemistry can meet the demands, and its Surface coating is uneven, poor controllability.
Summary of the invention
The inventive method object is to provide a kind of Li 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material and its preparation method and application, is intended to the ionic conductivity improving electrode material, thus the chemical property of electrode material under high magnification is significantly improved.The method is the surperficial conjugation growth Li at anode material for lithium-ion batteries 2-2xfe xtiO 3(0≤x≤0.7) and Li 3pO 4carry out modification, coated positive electrode Surface coating is even, method mature and reliable to adopt the method conjugation to grow.
The present invention is achieved through the following technical solutions:
A kind of Li 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material, by Li 2-2xfe xtiO 3and Li 3pO 4conjugation grows coated LiFePO 4, wherein 0≤x≤0.7.
As a further improvement on the present invention, be prepared from by the raw material of following mol ratio:
FeO：LiOH：LiFePO 4：TiO 2＝(0～0.7)：(1.00～2.25)：(0.6～2.6)：1。
As a further improvement on the present invention, material principal phase is olivine-type LiFePO 4.
A kind of Li 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, comprises the following steps:
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=(0 ~ 0.7): (1.00 ~ 2.25): (0.6 ~ 2.6): 1, takes raw material FeO, TiO 2, LiOH is placed in high-pressure bottle, add distilled water wherein and raw material fully dissolved, preparation Li +concentration is the mixed slurry of 0.50 ~ 3.0mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=(0.5 ~ 5): 1, take hydrazine hydrate and add in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 100 ~ 200W, ultrasonicly mixes in mass colour to slurry;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 15 ~ 30h at 200 ~ 240 DEG C of temperature, takes out to obtain hydrothermal product after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 is put into crucible and be placed in open tube furnace, nitrogen flow rate be 30 ~ 110mL/min, pipe pressure 0.01 ~ 0.1MPa, calcining heat 550 ~ 750 DEG C (exceed maximum temperature and phase transition can occur, then Fe can occur lower than minimum temperature 2+oxidation) condition under, calcining 1 ~ 20h; Take out after cooling, namely obtain Li 2-2xfe xtiO 3/ Li 3pO 4conjugation grows coated ferrousphosphate lithium material.
As a further improvement on the present invention, the material in the high-pressure bottle in step 1 is polytetrafluoroethylene, Hastelloy or stainless steel, and pressure is 2 ~ 100MPa.
As a further improvement on the present invention, the mixed slurry in step 1 accounts for 20% ~ 80% of high-pressure bottle volume volume.
As a further improvement on the present invention, the ultrasonic time in step 3 is 1 ~ 10min.
A kind of Li 2-2xfe xtiO 3/ Li 3pO 4the application of conjugation cladded ferrous lithium phosphate material in anode material for lithium-ion batteries.
Compared with prior art, the present invention has the following advantages:
A kind of Li of the present invention 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material, conjugation growth clad material composition is variable, and coated degree is controlled.Li 1.62fe 0.19tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 3 ~ 11nm, and principal phase is still olivine-type LiFePO 4.
The present invention one is kind of a Li 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, utilizes hydrothermal synthesis method to prepare clad material, can make the further refinement of composite material granular, even grain size, pollution-free, energy consumption is low.There is part generation displacement reaction in clad material, make surperficial conjugation grow Li 2-2xfe xtiO 3the positive electrode performance of (0≤x≤0.7) and Li3PO4 is more reliable.The present invention is simple to operate, and technique is easy to control, and manufacturing cycle is short, and cost is low, is easy to large-scale industrial production.Reaction mechanism is: the FeO:LiOH:LiFePO of required proportion 4: TiO 2after mixing, be uniformly dispersed through ultrasonic process, after entering closed high-pressure reaction vessel, first TiO occur 2dissolving-the precipitation process of crystal grain, then, the Li+ in LiOH solution invades TiO 2lattice, forms Li-Ti-O novel substance.In water-heat process, the Fe in a part of FeO 2+ion enters the Li-Ti-O material of formation simultaneously.In later stage nitrogen atmosphere calcination process, LiFePO 4in part Fe 2+also enter Li-Ti-O lattice, namely displacement reaction generates Li while occurring 3pO 4.Final formation Li 2-2xfe xtiO 3and Li 3pO 4conjugation grows coated LiFePO 4, wherein 0≤x≤0.7.What formed after hydro-thermal is coated presoma.Hydrazine hydrate can generate nitrogen and prevent Fe in airtight water heating kettle 2+oxidation.Nitrogen flow rate is under the condition of 30 ~ 110mL/min, pipe pressure 0.01 ~ 0.1MPa, calcining heat 550 ~ 750 DEG C, calcining 1 ~ 20h; Depart from this condition, clearly, battery performance worsens, and what have at all can not discharge and recharge in oxidation.
The Charger transfer internal resistance of application testing result display half-cell of the present invention reduces, Li +ion diffusion coefficient in active material increases, and illustrate that its inside battery charge transfer effciency, ion diffuse efficiency increase, chemical property significantly improves, and Suitable commercial is produced.
Accompanying drawing explanation
Fig. 1 is the Li of embodiment 3 0.62fe 0.69tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the XRD figure of positive electrode.
Fig. 2 is the Li of embodiment 1 1.62fe 0.19tiO 3and Li 3pO 4the coated LiFePO of conjugation growth 4the circulating battery curve of positive electrode.
Fig. 3 is the Li of embodiment 4 1.46fe 0.27tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the FE-SEM figure of positive electrode.
Fig. 4 is the Li of embodiment 5 2tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the FE-SEM figure of positive electrode.
Fig. 5 is the Li of embodiment 3 0.62fe 0.69tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the energy spectrogram of positive electrode.
Fig. 6 is the Li of embodiment 6 1.00fe 0.50tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the FE-SEM figure of positive electrode.
Embodiment
Concrete grammar of the present invention is as follows:
1) according to FeO:LiOH:LiFePO 4: TiO 2=(0 ~ 0.7): (1.00 ~ 2.25): (0.6 ~ 2.6): the molar ratio of 1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, and (material can be polytetrafluoroethylene, Hastelloy, stainless steel etc., pressure limit is 2 ~ 100MPa), account for high-pressure bottle volume volume ratio 20% ~ 80% by water and add appropriate distilled water wherein, fully dissolve, make Li +concentration is that (this concentration is Li to 0.50 ~ 3.0mol/L +account for the concentration adding water);
2) LiFePO in molar ratio 4: H 4n 2h 2o=(0.5 ~ 5): 1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 100 ~ 200W, and ultrasonic time is 1 ~ 10min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 15 ~ 30h at 200 ~ 240 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 is put into crucible and be placed in open tube furnace, nitrogen flow rate be 30 ~ 110mL/min, pipe pressure 0.01 ~ 0.1MPa, calcining heat 550 ~ 750 DEG C (exceed maximum temperature and phase transition can occur, then Fe can occur lower than minimum temperature 2+oxidation) condition under, calcining 1 ~ 20h.Take out after cooling, namely obtain Li 2-2xfe xtiO 3(0≤x≤0.7) and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) by electrochemical workstation, electrical performance testing is carried out to the half-cell obtained for positive electrode with this conjugation growth clad material.
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Embodiment 1
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0.2:1.85:2.593:1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 50% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 2.04mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=0.5:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 100W, and ultrasonic time is 5min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 15h at 200 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 80mL/min, pipe pressure 0.01MPa, calcining heat 700 DEG C at nitrogen flow rate, calcining 6h.Take out after cooling, namely obtain Li 0.62fe 0.69tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 1.62fe 0.19tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 10nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.05V, and the polarization on electrode reduces, and the performance of discharge and recharge is improved.
Embodiment 2
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0.4:1.45:2.593:1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 40% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 1.84mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=5:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 200W, and ultrasonic time is 1min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 18h at 200 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 is put into crucible and is placed in open tube furnace, nitrogen flow rate be 90mL/min, under pipe pressure 0.07MPa, calcining heat be the condition of 600 DEG C, calcining 5h.Take out after cooling, namely obtain Li 1.78fe 0.11tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 1.22fe 0.39tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 11nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.08V, and the polarization on electrode obviously reduces, and the performance of discharge and recharge is improved.。
Embodiment 3
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0.7:1.00:0.6:1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 70% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 0.50mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=3:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 200W, and ultrasonic time is 10min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 20h at 240 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 110mL/min, pipe pressure 0.045MPa, calcining heat 550 DEG C at nitrogen flow rate, calcining 20h.Take out after cooling, namely obtain Li 0.44fe 0.78tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 0.62fe 0.69tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 4nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.09V, and the polarization on electrode obviously reduces, and the performance of discharge and recharge is improved.
Embodiment 4
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0.3:1.57:1.713:1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 80% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 0.86mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=4:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 140W, and ultrasonic time is 10min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 24h at 220 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 50mL/min, pipe pressure 0.05MPa, calcining heat 750 DEG C at nitrogen flow rate, calcining 1h.Take out after cooling, namely obtain Li 0.52fe 0.74tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 1.46fe 0.27tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 9nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.02V, and the polarization on electrode reduces, and the performance of discharge and recharge is improved.
Embodiment 5
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0:2.25:1.232:1, takes TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 20% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 3.00mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=1.5:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 160W, and ultrasonic time is 3min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 22h at 230 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 100mL/min, pipe pressure 0.1MPa, calcining heat 650 DEG C at nitrogen flow rate, calcining 12h.Take out after cooling, namely obtain Li 2tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 2tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 6nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.05V, and the polarization on electrode reduces, and the performance of discharge and recharge is improved.
Embodiment 6
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=0.5:1.20:0.648:1, takes FeO, TiO 2powder, LiOH particle are placed in high-pressure bottle, account for high-pressure bottle volume volume ratio 60% and add appropriate distilled water wherein, fully dissolve, make Li by water +concentration is 1.27mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=1:1; Taking hydrazine hydrate adds in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 120W, and ultrasonic time is 7min, until slurry mixes in mass colour;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 30h at 235 DEG C of temperature, takes out after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry under air atmosphere, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 30mL/min, pipe pressure 0.09MPa, calcining heat 750 DEG C at nitrogen flow rate, calcining 15h.Take out after cooling, namely obtain Li 1.00fe 0.50tiO 3and Li 3pO 4conjugation grows coated ferrousphosphate lithium material;
7) obtain clad material surface-feature image by FE-SEM scanning electron microscopy, by X-ray diffractometer, material phase analysis is carried out to clad material, by electrochemical workstation, electric performance test is carried out to the half-cell taking clad material as positive pole.Result shows, Li 1.00fe 0.50tiO 3and Li 3pO 4good in clad material superficial growth trend, coated thickness is approximately 3nm, and principal phase is still olivine-type LiFePO 4.The cyclic voltammetry curve display of half-cell, first time is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.06V, and the polarization on electrode obviously reduces, and the performance of discharge and recharge is improved.
From the XRD collection of illustrative plates of Fig. 1, embodiment 3 gained Li 0.62fe 0.69tiO 3and Li 3pO 4conjugation grows coated LiFePO 4positive electrode principal phase is the LiFePO of olivine phase 4.From Fig. 2 circulating battery curve, embodiment 1 gained Li 1.62fe 0.19tiO 3and Li 3pO 4conjugation grows coated LiFePO 4the first time of positive electrode is recycled to cyclic oxidation peak and reduction peak spacing for the third time and reduces 0.05V, and the polarization on electrode obviously reduces, and the performance of discharge and recharge is improved.From the SEM image of Fig. 3, embodiment 4 gained Li 1.46fe 0.27tiO 3and Li 3pO 4conjugation grows coated LiFePO 4positive electrode is evenly distributed.From the SEM image of Fig. 4, embodiment 5 gained Li 2tiO 3and Li 3pO 4conjugation grows coated LiFePO 4positive electrode is evenly distributed, and coating layer homoepitaxial is at LiFePO 4surface.From the power spectrum result of Fig. 5, the Li of embodiment 3 0.62fe 0.69tiO 3and Li 3pO 4conjugation grows coated LiFePO 4positive electrode contains O, P, Ti, Fe tetra-kinds of elements, and Ti constituent content is about 4.35% (mass fraction).From the SEM image of Fig. 6, the Li of embodiment 6 1.00fe 0.50tiO 3and Li 3pO 4conjugation grows coated LiFePO 4positive electrode is evenly distributed, LiFePO 4grown for polyhedron-shaped, corner angle are clearly demarcated.
Embody rule approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.

Claims (8)

1. a Li 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material, is characterized in that, by Li 2-2xfe xtiO 3and Li 3pO 4conjugation grows coated LiFePO 4, wherein 0≤x≤0.7.
2. Li according to claim 1 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material, is characterized in that, is prepared from by the raw material of following mol ratio:
FeO：LiOH：LiFePO 4：TiO 2＝(0～0.7)：(1.00～2.25)：(0.6～2.6)：1。
3. Li according to claim 1 2-2xfe xtiO 3/ Li 3pO 4conjugation cladded ferrous lithium phosphate material, is characterized in that, material principal phase is olivine-type LiFePO 4.
4. Li according to claim 1 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, is characterized in that, comprise the following steps:
1) according to mol ratio FeO:LiOH:LiFePO 4: TiO 2=(0 ~ 0.7): (1.00 ~ 2.25): (0.6 ~ 2.6): 1, takes raw material FeO, TiO 2, LiOH is placed in high-pressure bottle, add distilled water wherein and raw material fully dissolved, preparation Li +concentration is the mixed slurry of 0.50 ~ 3.0mol/L;
2) LiFePO in molar ratio 4: H 4n 2h 2o=(0.5 ~ 5): 1, take hydrazine hydrate and add in the mixed slurry of step 1;
3) gained mixed slurry in step 2 is carried out ultrasonic process, ultrasonic power is 100 ~ 200W, ultrasonicly mixes in mass colour to slurry;
4) be sealed in high-pressure bottle by the slurry mixed in step 3, high-pressure bottle is placed in baking oven and is incubated 15 ~ 30h at 200 ~ 240 DEG C of temperature, takes out to obtain hydrothermal product after cool to room temperature;
5) step 4 gained hydrothermal product is put into baking oven 50 DEG C of oven dry, the sample after oven dry is placed in mortar and grinds even, namely obtain coated presoma;
6) gained presoma powder in step 5 being put into crucible and be placed in open tube furnace, is under the condition of 30 ~ 110mL/min, pipe pressure 0.01 ~ 0.1MPa, calcining heat 550 ~ 750 DEG C at nitrogen flow rate, calcining 1 ~ 20h; Take out after cooling, namely obtain Li 2-2xfe xtiO 3/ Li 3pO 4conjugation grows coated ferrousphosphate lithium material.
5. Li according to claim 4 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, is characterized in that, the material in the high-pressure bottle in step 1 is polytetrafluoroethylene, Hastelloy or stainless steel, and pressure is 2 ~ 100MPa.
6. Li according to claim 4 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, is characterized in that, the mixed slurry in step 1 accounts for 20% ~ 80% of high-pressure bottle volume volume.
7. Li according to claim 4 2-2xfe xtiO 3/ Li 3pO 4the preparation method of conjugation cladded ferrous lithium phosphate material, is characterized in that, the ultrasonic time in step 3 is 1 ~ 10min.
8. the Li described in claims 1 to 3 any one 2-2xfe xtiO 3/ Li 3pO 4the application of conjugation cladded ferrous lithium phosphate material in anode material for lithium-ion batteries.
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