CN102447096A - Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof - Google Patents

Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof Download PDF

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CN102447096A
CN102447096A CN2010102995196A CN201010299519A CN102447096A CN 102447096 A CN102447096 A CN 102447096A CN 2010102995196 A CN2010102995196 A CN 2010102995196A CN 201010299519 A CN201010299519 A CN 201010299519A CN 102447096 A CN102447096 A CN 102447096A
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lithium
ion battery
solid solution
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anode material
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CN102447096B (en
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杨岩峰
于锋
张敬杰
宋广智
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates a lithium ferrovanadium phosphate solid solution for a positive material of a lithium ion battery and preparation and application thereof, belonging to the technical field of battery materials. The invention provides a lithium ferrovanadium phosphate solid solution for the positive material of the lithium ion battery; the lithium ferrovanadium phosphate solid solution integrates the advantages of lithium ferric phosphate and lithium vanadium phosphate, overcomes the defects of the prior art caused by using the single lithium ferric phosphate or the single lithium vanadium phosphate as a main body, and has the advantages of good cycle performance, excellent multiplying power performance, high specific capacity, high safety and the like. The invention also provides a preparation method of the lithium ferrovanadium phosphate solid solution for the positive material of the lithium ion battery and the application of the lithium ferrovanadium phosphate solid solution to the positive material of the lithium ion battery with high multiplying power and high power capacity.

Description

A kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution
Technical field
The present invention relates to the battery material technical field, particularly relate to anode material for lithium ion battery.
Background technology
Lithium ion battery is a secondary cell of new generation after cadmium nickel, Ni-MH battery.Wherein, positive electrode is most important for important performances such as the operating voltage that improves lithium ion battery, specific energy, cycle lives.That commonly used is LiCoO at present 2, LiMn 2O 4And LiNiO 2But cobalt resource lacks, and has limited LiCoO 2Application, LiNiO 2Difficult synthetic, tangible exothermic reaction is arranged in charge and discharge process, possibly cause safety problem, LiMn 2O 4When near 50 ℃, working, capacity attenuation is very fast, and this is the factor of its development of restriction.Therefore seek the emphasis that the better new material of cost performance becomes research.
1997, the John B.Goodenough of texas,U.S university etc. were in U.S. Pat 5,910, and that report is main one dimension tunnel structure positive electrode LiFePO with the olivine structural in 382 (being WO1997040541) 4Have favorable charge-discharge platform, security performance and cycle performance.But, because PO 4Tetrahedron is positioned at FeO 6Between the layer, adjacent FeO 6Octahedra through summit link altogether, with layer structure (LiMO 2, M=Co, Ni) and spinel structure (LiM 2O 4, M=Mn) the middle MO of rib altogether that exists 6Octahedra continuous structure is different, and the octahedron on summit has relatively low ionic conductance altogether, and this has hindered Li to a certain extent +Diffusion motion.Therefore, the positive electrode LiFePO that has the one dimension tunnel structure 4Can only allow Li +Move in one direction, its one dimension ion channel is easy to receive the influence of impurity or dislocation etc. in the lattice and blocked, makes LiFePO 4Electric conductivity and current ratio characteristic relatively poor.
To olivine structural LiFePO 4Electric conductivity and the relatively poor characteristics of current ratio characteristic, the researcher adopt more the preparation solid solution compound or the preparation doped compound mode improve LiFePO 4Chemical property.Wherein, solid solution compound is mainly with olivine structural LiFePO 4Be the basis, with other olivine structural compound Ls iCoPO 4, LiNiPO 4, LiMnPO 4Form solid solution, its chemical formula is LiFe xM yPO 4(0＜x＜1,0＜y＜1, x+y=1), the M element is divalent state Co, Ni or Mn (seeing table 1).In addition, M2 position (being the Fe position) doping also is a kind of raising positive electrode LiFePO 4The common technique means of chemical property, the chemical formula of doping afterproduct is LiFe xM yPO 4(0.8≤x＜1,0＜y≤0.2, x+y=1), wherein the M element mainly contains Mg 2+, Ca 2+, Sn 2+, Zn 2+, V 3+, Cr 3+, Mo 3+, Zr 4+, Ti 4+, Nb 5+, W 6+Deng.Compound L iFe after this doping xM yPO 4, the span of x generally is not less than 0.8, and its structure still is olivine structural LiFePO 4(seeing table 1).
Three-dimensional frame structure positive electrode Li with NASCION structure 3V 2(PO 4) 3Also can be used as anode material for lithium-ion batteries.Because Li in the NASICON structure 3V 2(PO 4) 3In all cations all pass through very strong covalent bond and P 5+Constitute stable (PO 4) 3-The polyanion group, so the oxygen in the lattice is difficult for losing, and has stable macroscopic property, even the Li that is deviating from +Still has unusual stability greater than 1 the time with the transition metal atoms mol ratio.In addition, because Li 3V 2(PO 4) 3Middle PO 4Tetrahedron and VO 6Octahedron forms the three-dimensional framework structure through shared nonadjacent oxygen atom, wherein, and each VO 66 PO are arranged around octahedra 4Tetrahedron, and each PO 44 VO are arranged around the tetrahedron 6Octahedron is so just with A 2B 3(A=VO wherein 6, B=PO 4) be that the unit forms three-dimensional frame structure, in each monocrystalline by 4 A 2B 3The unit constitutes, Li 3V 2(PO 4) 3In the lithium ion of each unit can both take off embedding well, help Li more +Take off embedding so Li 3V 2(PO 4) 3Have excellent electric conductivity and high rate capability.Yet, as 3mol Li +When taking off embedding, though its theoretical specific capacity can reach 197.3mAh/g, cycle performance is relatively poor, and decay is serious.
Because NASCION structure Li 3V 2(PO 4) 3Shortcoming, the researcher adopt more the preparation solid solution compound or the preparation doped compound mode improve Li 3V 2(PO 4) 3Chemical property.Wherein, solid solution compound is mainly with NASCION structure Li 3V 2(PO 4) 3Being the basis, with other NASCION structural compounds, mainly is Li 3Fe 2(PO 4) 3Form solid solution, its chemical formula is Li 3Fe xV y(PO 4) 3(0＜x＜2,0＜y＜2, x+y=2), Fe is+3 valence states, V is+3 valence states (seeing table 1).In addition, M2 position (being the V position) Li doped 3V 2(PO 4) 3Positive electrode, i.e. Li 3M xV y(PO 4) 3(0＜x≤0.2,1.8≤y＜2 x+y=2) also are a kind of raising positive electrode Li 3V 2(PO 4) 3The common technique means of chemical property, wherein the M element mainly contains Mg 2+, Fe 2+, Ti 4+, Zr 4+Deng (seeing table 1).Compound L i after this doping 3M xV y(PO 4) 3, being mainly the NASCION structure, the span of x is not more than 0.2, and its matrix still is NASCION structure Li 3V 2(PO 4) 3But also do not collect LiFePO at present 4And Li 3V 2(PO 4) 3Advantage is avoided the material of both shortcomings.
Table 1 olivine structural positive electrode LiFePO 4With NASCION structure Li 3V 2(PO 4) 3Related patent U.S. Patent No. and document
Figure BSA00000292695200031
Summary of the invention
The objective of the invention is to overcome single in the past LiFePO 4Be main body electric conductivity and the relatively poor and single Li of current ratio characteristic 3V 2(PO 4) 3, decay serious defective relatively poor for the main body cycle performance provide a kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution, advantages such as this material has that cyclicity is good, the superior specific capacity height of high rate performance and fail safe height.
The present invention provides a kind of preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution.
The present invention provides the application of ion battery anode material vanadium lithium phosphate iron lithium solid solution on the anode material for lithium-ion batteries of high magnification, high power capacity.
The object of the invention is realized in the following manner:
A kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution, it consists of: LiFe xV yPO 4, it is characterized in that: x, y represent molar percentage, and span is 0＜x＜1,0＜y＜2/3, and 2x+3y=2, and the chemical valence of Fe is+the divalent attitude that the chemical valence of V is+3 valence states.
Its crystal structure is between olivine structural and NASCION structure.
It can carry out the C element doping; The content of carbon accounts for the 1-30wt% of matrix total amount; Preferred carbon content accounts for the 1-5wt% of matrix total amount; Its carbon source material is carbonaceous organic material or water-insoluble carbon source, like sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, CNT or carbon fiber.
The present invention provides phosphoric acid vanadium iron lithium solid solution to prepare through following method; Its main preparation methods has solid phase method, microwave method, sol-gal process, hydro thermal method, the precipitation method, solvent-thermal method, fuse salt growth method, spray pyrolysis, atomization drying carbothermic method etc., preferred atomization drying carbothermic method of the present invention and solid phase method.
The present invention is the preparation method that example specifies phosphoric acid vanadium iron lithium solid solution with atomization drying carbothermic method and solid phase method, but is not limited to this.
The atomization drying carbothermic method specifically comprises the steps:
The processing that homogenizes of step 1, raw material: according to stoichiometric proportion with lithium source, source of iron, phosphorus source, vanadium source and/or carbon source and/or dispersant is water-soluble or ethanol in be mixed with slurries or solution, and homogenize and handle as precursor liquid A; When the material of water insoluble or ethanol, need add dispersant;
Step 2, presoma preparation: the precursor liquid A that will homogenize after handling carries out drying, sloughs moisture, obtains precursor B;
Step 3, heat treatment: precursor B is placed sintering furnace,, make anode material for lithium ion battery in nonoxidizing atmosphere, 600～800 ℃ of heating down.Preferred 700 ℃ and 750 ℃ of heating-up temperature, be 4～36 hours heating time, is preferably 12 hours.
Wherein, said lithium source is LiOH, LiCO 3, LiAc2H 2O or LiNO 3Said source of iron is Fe, Fe 2O 3, Fe (NO 3) 39H 2O or Fe 2(C 2O 4) 3Said phosphorus source is H 3PO 4, NH 4H 2PO 4Or (NH 4) 2HPO 4Used vanadium source compound is V 2O 5Or NH 4VO 3Said carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, acetylene black, CNT or carbon fiber; Said dispersant is nonionic surface active agent such as hexadecyltrimethylammonium chloride, tween series, NPE etc., or cationic surface active agent such as cetyl trimethyl quaternary ammonium bromides, octadecyl dimethyl benzyl aliquat, cetyl methyl amine etc.
The said processing means that homogenize are high-speed stirred, sand milling, ball milling or mediate and mix.
Drying means is the atomization drying method in the said presoma preparation process.
Sintering furnace in the said heat treatment step is common outer heating high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in the said heat treatment step is the mist of argon gas, nitrogen, CO gas or hydrogen and argon gas or nitrogen.
The consumption of said carbon source is the 1-30wt% that the content of carbon accounts for the matrix total amount.
The consumption of said dispersant is 5.0～10.0g/1000ml solution.
Solid phase method is with conventional solid phase synthesis process, with reference to Chinese patent CN1581537, CN1762798, CN1767238, specifically comprises the steps:
Step 1, the raw material processing that homogenizes: with lithium source, source of iron, phosphorus source, vanadium source and/or carbon source, add entry or ethanol according to stoichiometric proportion, place grinding in ball grinder to obtain precursor A.
Step 2, heat treatment: this precursor A is placed sintering furnace,, make anode material for lithium ion battery in nonoxidizing atmosphere, 600～800 ℃ of heating down.
Wherein, said lithium source is LiCO 3, LiAc2H 2O or LiNO 3Said source of iron is Fe, Fe 2O 3, Fe (NO 3) 39H 2O, FePO 4, FeC 2O 4Or Fe 2(C 2O 4) 3Said phosphorus source is H 3PO 4, NH 4H 2PO 4Or (NH 4) 2HPO 4Used vanadium source compound is V 2O 5Or NH 4VO 3Said carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, CNT or carbon fiber etc.
Sintering furnace in the said heat treatment step is common outer heating high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in the said heat treatment step is the mist of argon gas, hydrogen, nitrogen, CO gas or hydrogen and argon gas or nitrogen.
The consumption of said carbon source is the 1-30wt% that the content of carbon accounts for the matrix total amount.
Phosphoric acid vanadium iron lithium solid solution provided by the invention can be used as positive electrode active materials and in secondary lithium battery, uses.This type secondary cell is applicable to various mobile electronic devices or mobile driven by energy equipment such as electric automobile, PHEV, and accumulation power supplies such as aerospace field, artificial satellite and regional electronics synthesis information system etc., and be not limited to this.
The advantage of phosphoric acid vanadium iron lithium solid solution of the present invention is:
Phosphoric acid vanadium iron lithium solid solution of the present invention, but positive electrode used as charging-discharging lithium ion battery, have that cyclicity is good, safe, high rate performance is superior and the specific capacity advantages of higher, can be mainly used in the lithium ion battery of high magnification, high power capacity.The present invention integrates LiFePO4 and phosphoric acid vanadium lithium advantage, and to have overcome single in the past LiFePO4 be that main body and phosphoric acid vanadium lithium are the defective of main body, is the main body with the solid solution phosphoric acid vanadium iron lithium of novelty, is the choosing of the ideal of preparation high power capacity, high power battery.
The preferred spray drying carbothermic method of the present invention prepares precursor liquid through soft chemical method; Can make the mixing that reaches atomic level between the raw material; Overcome the defective that raw material can not fully contact in the methods such as solid phase method, and the acquisition size is controlled, the material of even particle size distribution.The method technology is simple, but the continuity operation is easy to suitability for industrialized production.
Description of drawings
Fig. 1 LiFe xV yPO 4(0＜x＜1,0＜y＜2/3, X-ray diffractogram 2x+3y=2)
Fig. 2 LiFe xV yPO 4(0＜x＜1,0＜y＜2/3,2x+3y=2) x-ray photoelectron can spectrograms, demonstrate the electron binding energy of Fe, V element
Fig. 3 embodiment 1 particle size distribution figure
Fig. 4 embodiment 1 first charge-discharge figure
Fig. 5 embodiment 4 first charge-discharge figure
Fig. 6 embodiment 6 particulate scan Electronic Speculum figure
Cycle performance figure under Fig. 7 embodiment 6 different multiplying
Fig. 8 embodiment 9 first charge-discharge figure
Embodiment
Further specify the present invention through specific embodiment with atomization drying carbothermic method and solid phase method below, but these embodiment are used for limiting protection scope of the present invention.
Embodiment 1
X gets 0.1, preparation LiFe 0.1V 0.6PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.1: 0.6: 1 takes by weighing lithium nitrate, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate; Soluble in water; Account for the 20wt% adding carbon black of matrix total amount by the content of carbon; Add 5g surfactant Tween 80 then, be made into the suspension slurry of 1000mL with deionized water.Mixture fully stirs 2 hours in high speed dispersor after, obtain finely disseminated suspension slurry as preceding body liquid A.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 200 ℃ and about 100 ℃; Dry powder is collected in cyclone separator, obtains precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the nitrogen atmosphere,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.1V 0.6PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.Laser particle analyzer is measured and is shown that average grain diameter is in 20 μ m left and right sides (see figure 3)s.
Simulated battery is made: with the LiFe that obtains 0.1V 0.6PO 4The n-formyl sarcolysine base pyrrolidone solution of/C and acetylene black and 10% Kynoar (PVDF) is mixed into slurry at normal temperatures and pressures; Evenly be coated on the aluminum substrates; Then 80 ℃ of vacuumizes 12 hours; Be cut into the positive pole of the electrode slice of 1X1cm as simulated battery, the negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF 6/ EC+DMC+DEC.Positive pole, negative pole, electrolyte, barrier film are assembled into simulated battery in the glove box of argon shield.
The simulated battery electrochemical property test: carry out electrochemical property test on the appearance discharging and recharging, discharge and recharge test with C/10, the first charge-discharge amount reaches the 112mAh/g (see figure 4).
Embodiment 2
X gets 0.2, preparation LiFe 0.2V 0.53PO 4Positive electrode.Solid phase method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.2: 0.53: 1 takes by weighing lithium carbonate, ferric phosphate, vanadic oxide; Account for the 1wt% adding sucrose of matrix total amount by the content of carbon; Add distilled water, placed grinding in ball grinder 12 hours, obtain precursor A.
Step 2, heat treatment: this precursor A is placed sintering furnace,, make anode material for lithium ion battery LiFe nitrogen, 800 ℃ of following heating 12 hours 0.2V 0.53PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Embodiment 3
X gets 0.3, preparation LiFe 0.3V 0.47PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.3: 0.47: 1 takes by weighing lithium carbonate, ferric nitrate, ammonium metavanadate, diammonium hydrogen phosphate; Soluble in water; Account for the 30wt% adding acetylene black of matrix total amount by the content of carbon; Add the 5g hexadecyltrimethylammonium chloride then, be made into the suspension slurry of 1000mL with deionized water.Mixture fully stirs 2 hours in high speed dispersor after, obtain finely disseminated suspension slurry as preceding body liquid A.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃; Dry powder is collected in cyclone separator, obtains precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the argon gas atmosphere,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.3V 0.47PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Embodiment 4
X gets 0.4, preparation LiFe 0.4V 0.4PO 4Positive electrode.Solid phase method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.4: 0.4: 1 takes by weighing lithium carbonate, di-iron trioxide, vanadic oxide, ammonium dihydrogen phosphate; Account for the 25wt% adding CNT of matrix total amount by the content of carbon; Add ethanol; Place ball mill, grind 12h.Obtain precursor A.
Step 2, heat treatment: this precursor A is placed sintering furnace,, make anode material for lithium ion battery LiFe argon gas, 700 ℃ of following heating 12 hours 0.4V 0.4PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.Laser particle analyzer is measured and is shown that average grain diameter is about 20 μ m.
Simulated battery making and electrochemical property test step are of implementing 1.Under the C/10, the first charge-discharge amount reaches the 137mAh/g (see figure 5), has excellent cycle performance.
Embodiment 5
X gets 0.5, preparation LiFe 0.5V 0.34PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.5: 0.34: 1 takes by weighing lithium acetate, Fe 2(C 2O 4) 3, ammonium metavanadate, phosphoric acid, soluble in water, the 25wt% that accounts for the matrix total amount by the content of carbon adds citric acid, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in high speed dispersor after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the argon gas atmosphere,, obtain anode material for lithium ion battery LiFe at 600 ℃ of following heat treatment 36h 0.5V 0.34PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Embodiment 6
X gets 0.6, preparation LiFe 0.6V 0.27PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.6: 0.27: 1 takes by weighing lithium hydroxide, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate; Soluble in water; The 18wt% that accounts for the matrix total amount by the content of carbon adds sucrose, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 220 ℃ and about 100 ℃; Dry powder is collected in cyclone separator, obtains precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the nitrogen atmosphere,, obtain anode material for lithium ion battery LiFe at 800 ℃ of following heat treatment 4h 0.6V 0.27PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.Laser particle analyzer is measured and is shown that average grain diameter is about 20 μ m.The scanning electron microscopy (see figure 6) shows, the LiFe that obtains 0.6V 0.27PO 4/ C powder body material is spherical in shape.
Simulated battery making and electrochemical property test step are of implementing 1.Under the C/10, the first charge-discharge amount reaches 151mAh/g, has the excellent cycle performance (see figure 7).
Embodiment 7
X gets 0.7, preparation LiFe 0.7V 0.2PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.7: 0.2: 1 takes by weighing lithium carbonate, iron oxide, vanadium oxide, ammonium dihydrogen phosphate; Soluble in water; The 10wt% that accounts for the matrix total amount by the content of carbon adds water soluble starch, is made into the emulsion of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃; Dry powder is collected in cyclone separator, obtains precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the nitrogen atmosphere,, obtain anode material for lithium ion battery LiFe at 750 ℃ of following heat treatment 12h 0.7V 0.2PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Embodiment 8
X gets 0.8, preparation LiFe 0.8V 0.14PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.8: 0.14: 1 takes by weighing lithium carbonate, iron oxide, vanadic oxide, ammonium dihydrogen phosphate; Soluble in water; The 20wt% that accounts for the matrix total amount by the content of carbon adds polyethylene glycol, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃; Dry powder is collected in cyclone separator, obtains precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the nitrogen atmosphere,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.8V 0.14PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Embodiment 9
X gets 0.9, preparation LiFe 0.9V 0.07PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.9: 0.07: 1 takes by weighing lithium hydroxide, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate; Soluble in water; The 25wt% that accounts for the matrix total amount by the content of carbon adds sucrose, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the nitrogen atmosphere,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 10h 0.9V 0.07PO 4/ C, this material are the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and showing does not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is seen Fig. 2, shows that the chemical valence of Fe is+the divalent attitude, and the chemical valence of V is+3 valence states.
Simulated battery making and electrochemical property test step are of implementing 1.Under the C/10, the first charge-discharge amount reaches the 124mAh/g (see figure 8).
Embodiment 10
X gets 0.1, preparation LiFe 0.1V 0.6PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.1: 0.6: 1 takes by weighing lithium nitrate, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate, soluble in water, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in high speed dispersor after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under hydrogen and the nitrogen mixture body,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.1V 0.6PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 11
X gets 0.2, preparation LiFe 0.2V 0.53PO 4Positive electrode.Solid phase method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.2: 0.53: 1 takes by weighing lithium nitrate, ferrous oxalate, ammonium metavanadate, diammonium hydrogen phosphate, places grinding in ball grinder 12 hours, obtains precursor A.
Step 2, heat treatment: this precursor A is placed sintering furnace, under the mist of hydrogen and argon gas, 800 ℃ of down heating 12 hours, make anode material for lithium ion battery LiFe 0.2V 0.53PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 12
X gets 0.3, preparation LiFe 0.3V 0.47PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.3: 0.47: 1 takes by weighing lithium carbonate, ferric nitrate, ammonium metavanadate, diammonium hydrogen phosphate; Soluble in water; Mixture fully stirs 2 hours in high speed dispersor after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the mist of hydrogen and argon gas,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.3V 0.47PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 13
X gets 0.4, preparation LiFe 0.4V 0.4PO 4Positive electrode.Solid phase method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.4: 0.4: 1 takes by weighing lithium carbonate, di-iron trioxide, vanadic oxide, ammonium dihydrogen phosphate, places ball mill, grinds 12h.Obtain precursor A.
Step 2, heat treatment: this precursor A is placed sintering furnace,, make anode material for lithium ion battery LiFe the mist of hydrogen and nitrogen, 700 ℃ of following heating 12 hours 0.4V 0.4PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 14
X gets 0.5, preparation LiFe 0.5V 0.34PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.5: 0.34: 1 takes by weighing lithium acetate, Fe2 (C2O4) 3, ammonium metavanadate, phosphoric acid, soluble in water, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in high speed dispersor after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the mist of hydrogen and argon gas,, obtain anode material for lithium ion battery LiFe at 600 ℃ of following heat treatment 36h 0.5V 0.34PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 15
X gets 0.6, preparation LiFe 0.6V 0.27PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.6: 0.27: 1 takes by weighing lithium hydroxide, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate, soluble in water, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the gaseous mixture of hydrogen and argon gas,, obtain anode material for lithium ion battery LiFe at 800 ℃ of following heat treatment 4h 0.6V 0.27PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 16
X gets 0.7, preparation LiFe 0.7V 0.2PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.7: 0.2: 1 takes by weighing lithium carbonate, iron oxide, vanadium oxide, ammonium dihydrogen phosphate, soluble in water, is made into the emulsion of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the mist of hydrogen and nitrogen,, obtain anode material for lithium ion battery LiFe at 800 ℃ of following heat treatment 12h 0.7V 0.2PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 17
X gets 0.8, preparation LiFe 0.8V 0.14PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.8: 0.14: 1 takes by weighing lithium carbonate, iron oxide, vanadium oxide, ammonium dihydrogen phosphate, soluble in water, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the mist of hydrogen and nitrogen,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 12h 0.8V 0.14PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.
Embodiment 18
X gets 0.9, preparation LiFe 0.9V 0.07PO 4Positive electrode.The atomization drying carbothermic method.
Step 1, the raw material processing that homogenizes: according to Li: Fe: V: the P mol ratio is 1: 0.9: 0.07: 1 takes by weighing lithium hydroxide, ferric nitrate, ammonium metavanadate, ammonium dihydrogen phosphate, soluble in water, is made into the solution of 1000mL with deionized water.Mixture fully stirs 2 hours in homogenizer after, body liquid A before obtaining.
Step 2, presoma preparation: preceding body liquid A is carried out drying and dehydrating with the centrifugal spraying drying machine; Under nebulizer gas pressure 0.2MPa; Slurries add in the spray dryer with the speed of 15mL/min; Inlet temperature and outlet temperature remain on respectively about 260 ℃ and about 100 ℃, and dry powder is collected in cyclone separator, obtain precursor B.
Step 3, heat treatment: this precursor B is placed high-temperature atmosphere furnace, under the mist of hydrogen and nitrogen,, obtain anode material for lithium ion battery LiFe at 700 ℃ of following heat treatment 10h 0.9V 0.07PO 4, this material is the black powder.Its X ray diffracting spectrum (XRD) is seen Fig. 1, and its x-ray photoelectron power spectrum (XPS) is seen Fig. 2.

Claims (9)

1. ion battery anode material vanadium lithium phosphate iron lithium solid solution, it consists of: LiFe xV yPO 4, x, y represent molar percentage, 0＜x＜1,0＜y＜2/3, and 2x+3y=2, and the chemical valence of Fe is+the divalent attitude that the chemical valence of V is+3 valence states.
2. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1 is characterized in that crystal structure is between olivine structural and NASCION structure.
3. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1 and 2 is characterized in that used Li source compound is LiOH, LiCO 3, LiAc2H 2O or LiNO 3Used source of iron is Fe, Fe 2O 3, Fe (NO 3) 39H 2O or Fe 2(C 2O 4) 3Used vanadium source compound is V 2O 5Or NH 4VO 3Used P source compound is H 3PO 4, NH 4H 2PO 4Or (NH 4) 2HPO 4
4. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1 and 2 is characterized in that carrying out its C element doping, and the content of carbon accounts for the 1-30wt% of matrix total amount.
5. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1 and 2 is characterized in that the content of carbon accounts for the 1-5wt% of matrix total amount.
6. the preparation method of the described ion battery anode material vanadium lithium phosphate iron of claim 1 a lithium solid solution is characterized in that using solid phase method, microwave method, sol-gal process, hydro thermal method, the precipitation method, solvent-thermal method, spray pyrolysis, the preparation of atomization drying carbothermic method.
7. the preparation method of the described ion battery anode material vanadium lithium phosphate iron of claim 6 a lithium solid solution is characterized in that using the preparation of atomization drying carbothermic method.
8. the preparation method of the described ion battery anode material vanadium lithium phosphate iron of claim 6 a lithium solid solution is characterized in that using solid phase method.
9. the described ion battery anode material vanadium lithium phosphate iron of claim 1 a lithium solid solution is used, and is used for secondary lithium battery.
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