CN102447096B - 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 PDFInfo
- Publication number
- CN102447096B CN102447096B CN201010299519.6A CN201010299519A CN102447096B CN 102447096 B CN102447096 B CN 102447096B CN 201010299519 A CN201010299519 A CN 201010299519A CN 102447096 B CN102447096 B CN 102447096B
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- source
- solid solution
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
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
Technical field
The present invention relates to battery material technical field, particularly relate to anode material for lithium ion battery and its preparation method and application.
Background technology
Lithium ion battery is secondary cell of new generation after cadmium nickel, Ni-MH battery.Wherein, positive electrode is most important for the important performance such as operating voltage, specific energy, cycle life that improves lithium ion battery.That conventional is LiCoO at present
2, LiMn
2o
4and LiNiO
2.But cobalt resource lacks, and has limited LiCoO
2application, LiNiO
2difficult synthetic, in charge and discharge process, there is obvious exothermic reaction, may cause safety problem, LiMn
2o
4while working near 50 ℃, capacity attenuation is very fast, and this is the factor of its development of restriction.Therefore finding the better new material of cost performance becomes the emphasis of research.
1997, the John B.Goodenough of texas,U.S university etc. were in U.S. Pat 5,910, report take olivine structural as main one dimension tunnel structure positive electrode LiFePO in 382 (being WO1997040541)
4there is good charge and discharge platform, security performance and cycle performance.But, due to PO
4tetrahedron is positioned at FeO
6between layer, adjacent FeO
6octahedra by summit link altogether, with layer structure (LiMO
2, M=Co, Ni) and spinel structure (LiM
2o
4, M=Mn) and the middle MO of rib altogether that exists
6octahedra continuous structure difference, the octahedron on summit has relatively low ionic conductance altogether, and this has hindered Li to a certain extent
+diffusion motion.Therefore, there is the positive electrode LiFePO of one dimension tunnel structure
4can only allow Li
+move in one direction, its one dimension ion channel is easy to be subject to the impact of impurity or dislocation etc. in lattice and is blocked, makes LiFePO
4electric conductivity and current ratio characteristic poor.
For olivine structural LiFePO
4electric conductivity and the poor feature of current ratio characteristic, researcher adopts the mode of preparing solid solution compound or preparing doped compound to improve LiFePO
4chemical property.Wherein, solid solution compound is mainly with olivine structural LiFePO
4for 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), M element is divalent state Co, Ni or Mn (in Table 1).In addition, M2 position (being Fe position) doping is also a kind of positive electrode LiFePO that improves
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 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 is generally not less than 0.8, and its structure is still olivine structural LiFePO
4(in Table 1).
There is the three-dimensional frame structure positive electrode Li of NASCION structure
3v
2(PO
4)
3also can be used as anode material for lithium-ion batteries.Due to the Li in NASICON structure
3v
2(PO
4)
3in all cations all pass through very strong covalent bond and P
5+form stable (PO
4)
3-polyanion group, therefore the oxygen in lattice is difficult for losing, and has stable macroscopic property, even the Li deviating from
+when being greater than 1 with transition metal atoms mol ratio, still there is unusual stability.In addition, due to Li
3v
2(PO
4)
3middle PO
4tetrahedron and VO
6octahedron forms three-dimensional framework structure by sharing nonadjacent oxygen atom, wherein, and each VO
6around octahedra, there are 6 PO
4tetrahedron, and each PO
4tetrahedron has 4 VO around
6octahedron, so just with A
2b
3(wherein A=VO
6, B=PO
4) be unit form three-dimensional frame structure, in each monocrystalline by 4 A
2b
3cell formation, Li
3v
2(PO
4)
3in the lithium ion deintercalation well of each unit, be more conducive to Li
+deintercalation, therefore Li
3v
2(PO
4)
3there is excellent electric conductivity and high rate capability.But, when there being 3mol Li
+while carrying out deintercalation, although its theoretical specific capacity can reach 197.3mAh/g, cycle performance is poor, and decay is serious.
Due to NASCION structure Li
3v
2(PO
4)
3shortcoming, researcher adopts the mode of preparing solid solution compound or preparing doped compound to improve Li
3v
2(PO
4)
3chemical property.Wherein, solid solution compound is mainly with NASCION structure Li
3v
2(PO
4)
3for basis, with other NASCION structural compounds, be mainly 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 (in Table 1).In addition M2 position (being 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) is also a kind of positive electrode Li that improves
3v
2(PO
4)
3the common technique means of chemical property, wherein M element mainly contains Mg
2+, Fe
2+, Ti
4+, Zr
4+deng (in Table 1).Compound L i after this doping
3m
xv
y(PO
4)
3, being mainly NASCION structure, the span of x is not more than 0.2, and its matrix is still NASCION structure Li
3v
2(PO
4)
3.But also do not collect at present LiFePO
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)
3patents and document
Summary of the invention
The object of the invention is to overcome single LiFePO in the past
4for main body electric conductivity with current ratio characteristic is poor and single Li
3v
2(PO
4)
3for main body cycle performance is poor, the serious defect that decays, a kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution is provided, this material has that cyclicity is good, the superior specific capacity of high rate performance is high and the advantage such as fail safe is high.
The invention provides a kind of preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution.
The 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.
Object of the present invention realizes 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, span is 0 < x < 1,0 < y < 2/3, and 2x+3y=2, the chemical valence of Fe is+divalent state that the chemical valence of V is+3 valence states.
Its crystal structure is between olivine structural and NASCION structure.
It can carry out 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, as sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, carbon nano-tube or carbon fiber.
The invention provides phosphoric acid vanadium iron lithium solid solution is prepared by the 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., the preferred atomization drying carbothermic method of the present invention and solid phase method.
The present invention illustrates the preparation method of phosphoric acid vanadium iron lithium solid solution as an example of atomization drying carbothermic method and solid phase method example, but is not limited to this.
Atomization drying carbothermic method specifically comprises the steps:
The processing that homogenizes of step 1, raw material: according to stoichiometric proportion by 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 process as precursor liquid A; When having the material of water insoluble or ethanol, need to add dispersant;
Step 3, heat treatment: precursor B is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, makes anode material for lithium ion battery.Preferably 700 ℃ and 750 ℃ of heating-up temperatures, be 4~36 hours heating time, is preferably 12 hours.
Wherein, described lithium source is
liAc2H
2o or LiNO
3; Described source of iron is Fe, Fe
2o
3, Fe (NO
3)
39H
2o or Fe
2(C
2o
4)
3; Described phosphorus source is H
3pO
4, NH
4h
2pO
4or (NH
4)
2hPO
4; Vanadium source compound used is V
2o
5or NH
4vO
3; Described carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, acetylene black, carbon nano-tube or carbon fiber; Described dispersant be nonionic surface active agent as hexadecyltrimethylammonium chloride, tween series, NPE etc., or cationic surface active agent is as cetyl trimethyl quaternary ammonium bromides, octadecyl dimethyl benzyl aliquat, cetyl methyl amine etc.
The described processing means that homogenize are high-speed stirred, sand milling, ball milling or mediate and mix.
In described presoma preparation process, drying means is atomization drying method.
Sintering furnace in described heat treatment step is common external heat high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in described heat treatment step is the mist of argon gas, nitrogen, CO (carbon monoxide converter) gas or hydrogen and argon gas or nitrogen.
The consumption of described carbon source is the 1-30wt% that the content of carbon accounts for matrix total amount.
The consumption of described 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:
Wherein, described lithium source
liAc2H
2o or LiNO
3; Described source of iron is Fe, Fe
2o
3, Fe (NO
3)
39H
2o, FePO
4, FeC
2o
4or Fe
2(C
2o
4)
3; Described phosphorus source is H
3pO
4, NH
4h
2pO
4or (NH
4)
2hPO
4; Vanadium source compound used is V
2o
5or NH
4vO
3; Described carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, carbon nano-tube or carbon fiber etc.
Sintering furnace in described heat treatment step is common external heat high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in described heat treatment step is the mist of argon gas, hydrogen, nitrogen, CO (carbon monoxide converter) gas or hydrogen and argon gas or nitrogen.
The consumption of described carbon source is the 1-30wt% that the content of carbon accounts for matrix total amount.
Phosphoric acid vanadium iron lithium solid solution provided by the invention can be used as positive electrode active materials and uses in secondary lithium battery.This class secondary cell is applicable to various mobile electronic devices or mobile driven by energy equipment as electric automobile, hybrid electric vehicle, and the accumulation power supplies such as aerospace field, artificial satellite and region 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, as can charging-discharging lithium ion battery positive electrode, has that cyclicity is good, safe, high rate performance is superior and 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 LiFePO4 be in the past the defect that main body and phosphoric acid vanadium lithium are main body, take novel solid solution phosphoric acid vanadium iron lithium as main body, is the choosing of preparing the ideal of high power capacity, high power battery.
The present invention's dried carbon thermal reduction of preferably spraying is prepared precursor liquid by soft chemical method, can make to reach between raw material the mixing of atomic level, overcome the defect that the method Raws such as solid phase method can not fully contact, and obtained that particle size is controlled, the material of even particle size distribution.The method technique is simple, can continuity operate, and is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 LiFe
xv
ypO
4the X-ray diffractogram of (0 < x < 1,0 < y < 2/3,2x+3y=2)
Fig. 2 LiFe
xv
ypO
4the x-ray photoelectron energy spectrogram of (0 < x < 1,0 < y < 2/3,2x+3y=2), demonstrates 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
Below by specific embodiment, with atomization drying carbothermic method and solid phase method, further illustrate the present invention, but these embodiment are not used for limiting protection scope of the present invention.
X gets 0.1, preparation LiFe
0.1v
0.6pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.1v
0.6pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, 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 (seeing Fig. 3).
Simulated battery is made: by the LiFe obtaining
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 in aluminum substrates, then 80 ℃ of vacuumizes 12 hours, be cut into the electrode slice of 1X1cm as the positive pole of simulated battery, the negative pole of simulated battery is used 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.
Simulated battery electrochemical property test: carry out electrochemical property test discharging and recharging on instrument, discharge and recharge test with C/10, first charge-discharge amount reaches 112mAh/g (seeing Fig. 4).
X gets 0.2, preparation LiFe
0.2v
0.53pO
4positive electrode.Solid phase method.
Embodiment 3
X gets 0.3, preparation LiFe
0.3v
0.47pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under argon gas atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.3v
0.47pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, 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.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 137mAh/g (seeing Fig. 5), has good cycle performance.
X gets 0.5, preparation LiFe
0.5v
0.34pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under argon gas atmosphere, heat treatment 36h at 600 ℃, obtains anode material for lithium ion battery LiFe
0.5v
0.34pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
Embodiment 6
X gets 0.6, preparation LiFe
0.6v
0.27pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 4h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.6v
0.27pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, 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.Scanning electron microscopy (seeing Fig. 6) shows, the LiFe obtaining
0.6v
0.27pO
4/ C powder body material is spherical in shape.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 151mAh/g, has good cycle performance (seeing Fig. 7).
Embodiment 7
X gets 0.7, preparation LiFe
0.7v
0.2pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 750 ℃, obtains anode material for lithium ion battery LiFe
0.7v
0.2pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
X gets 0.8, preparation LiFe
0.8v
0.14pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.8v
0.14pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
X gets 0.9, preparation LiFe
0.9v
0.07pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 10h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.9v
0.07pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows 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 shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 124mAh/g (seeing Fig. 8).
X gets 0.1, preparation LiFe
0.1v
0.6pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under hydrogen and nitrogen mixture body, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.1v
0.6pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 11
X gets 0.2, preparation LiFe
0.2v
0.53pO
4positive electrode.Solid phase method.
X gets 0.3, preparation LiFe
0.3v
0.47pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and argon gas, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.3v
0.47pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
X gets 0.4, preparation LiFe
0.4v
0.4pO
4positive electrode.Solid phase method.
Embodiment 14
X gets 0.5, preparation LiFe
0.5v
0.34pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and argon gas, heat treatment 36h at 600 ℃, obtains anode material for lithium ion battery LiFe
0.5v
0.34pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
X gets 0.6, preparation LiFe
0.6v
0.27pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the gaseous mixture of hydrogen and argon gas, heat treatment 4h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.6v
0.27pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 16
X gets 0.7, preparation LiFe
0.7v
0.2pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 12h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.7v
0.2pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 17
X gets 0.8, preparation LiFe
0.8v
0.14pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.8v
0.14PO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 18
X gets 0.9, preparation LiFe
0.9v
0.07pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 10h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.9v
0.07pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Claims (7)
1. an ion battery anode material vanadium lithium phosphate iron lithium solid solution, it consists of: LiFe
xv
yp0
4, x, y represent molar percentage, 0<x<1,0<y<2/3, and 2x+3y=2, the chemical valence of Fe is+divalent state, the chemical valence of V is+3 valence states, and its crystal structure is between olivine and NASCION.
2. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1, is characterized in that Li source compound used is lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate; Source of iron used is iron oxide, ferric nitrate or ferrous oxalate; Vanadium source compound used is ammonium metavanadate; P source compound used is phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
3. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1, is characterized in that carrying out carbon doping, and the content of carbon accounts for LiFe
xv
ypO
4the 1-5wt% of/C total amount.
4. a preparation method for ion battery anode material vanadium lithium phosphate iron lithium solid solution claimed in claim 1, is characterized in that using atomization drying carbothermic method or solid phase method.
5. the preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 4, is characterized in that using atomization drying carbothermic method to carry out according to following steps:
The processing that homogenizes of step 1, raw material: according to stoichiometric proportion by lithium source, source of iron, phosphorus source, vanadium source, carbon source and dispersant is water-soluble or ethanol in be mixed with slurries or solution, and homogenize and process as precursor liquid A; When having the material of water insoluble or ethanol, need to add dispersant;
Step 2, precursor preparation: the precursor liquid A after treatment that will homogenize carries out atomization drying, obtains precursor B;
Step 3, heat treatment: precursor B is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, 4~36 hours heating times, makes anode material for lithium ion battery.
6. the preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 4, is characterized in that using solid phase method to carry out according to following steps:
Step 1, the raw material processing that homogenizes: by lithium source, source of iron, phosphorus source, vanadium source and carbon source, add water or ethanol according to stoichiometric proportion, be placed in grinding in ball grinder and obtain precursor A;
Step 2, heat treatment: this precursor A is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, makes anode material for lithium ion battery.
7. an application for ion battery anode material vanadium lithium phosphate iron lithium solid solution claimed in claim 1, for secondary lithium battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010299519.6A CN102447096B (en) | 2010-10-08 | 2010-10-08 | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010299519.6A CN102447096B (en) | 2010-10-08 | 2010-10-08 | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102447096A CN102447096A (en) | 2012-05-09 |
CN102447096B true CN102447096B (en) | 2014-05-07 |
Family
ID=46009372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010299519.6A Active CN102447096B (en) | 2010-10-08 | 2010-10-08 | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102447096B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102709552A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery |
CN103050698A (en) * | 2013-01-15 | 2013-04-17 | 四川大学 | Vanadium lithium iron phosphate anode material and preparation method thereof |
CN103227325B (en) * | 2013-04-09 | 2015-03-11 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery cathode material and preparation method thereof |
CN105226275A (en) * | 2015-07-15 | 2016-01-06 | 徐茂龙 | A kind of modification fluorophosphoric acid vanadium lithium anode material of lithium battery and preparation method thereof |
CN107146877B (en) * | 2017-05-03 | 2021-02-19 | 武汉理工大学 | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery |
CN107579304A (en) * | 2017-09-06 | 2018-01-12 | 湖南省正源储能材料与器件研究所 | A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate |
CN113060717A (en) * | 2021-03-26 | 2021-07-02 | 天津斯科兰德科技有限公司 | Preparation method of lithium iron vanadium phosphate positive electrode material |
CN113264516B (en) * | 2021-07-21 | 2021-09-28 | 温州玖源锂电池科技发展有限公司 | Preparation method of lithium iron vanadium phosphate carbon nanotube modified ternary cathode material |
CN114023956A (en) * | 2021-11-01 | 2022-02-08 | 段镇忠 | Vanadium-containing phosphate alkali metal ion battery positive electrode material and preparation method and application thereof |
CN116281932A (en) * | 2023-04-18 | 2023-06-23 | 上海量孚新能源科技有限公司 | Lithium iron manganese phosphate and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
CN101304083A (en) * | 2006-05-11 | 2008-11-12 | 立凯电能科技股份有限公司 | Composite material being suitable for preparing anode of secondary battery as well as battery made by the same |
JP2008277152A (en) * | 2007-04-27 | 2008-11-13 | Tdk Corp | Active material, electrode, battery, and manufacturing method of active material |
CN101442142A (en) * | 2007-11-23 | 2009-05-27 | 丰田自动车株式会社 | Lithium-ion secondary battery, assembled battery, hybrid automobile, and battery system |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003297537A1 (en) * | 2002-12-23 | 2004-07-22 | A 123 Systems, Inc. | High energy and power density electrochemical cells |
-
2010
- 2010-10-08 CN CN201010299519.6A patent/CN102447096B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101304083A (en) * | 2006-05-11 | 2008-11-12 | 立凯电能科技股份有限公司 | Composite material being suitable for preparing anode of secondary battery as well as battery made by the same |
JP2008277152A (en) * | 2007-04-27 | 2008-11-13 | Tdk Corp | Active material, electrode, battery, and manufacturing method of active material |
CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
CN101442142A (en) * | 2007-11-23 | 2009-05-27 | 丰田自动车株式会社 | Lithium-ion secondary battery, assembled battery, hybrid automobile, and battery system |
Also Published As
Publication number | Publication date |
---|---|
CN102447096A (en) | 2012-05-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102447096B (en) | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof | |
Pan et al. | Hydrothermal synthesis of well-dispersed LiMnPO4 plates for lithium ion batteries cathode | |
JP5509918B2 (en) | Method for producing positive electrode active material for lithium ion battery, positive electrode active material for lithium ion battery, electrode for lithium ion battery, and lithium ion battery | |
CN103109399B (en) | A kind of containing lithium salts-graphene composite material and preparation method thereof | |
CN101675001B (en) | Synthesis of an limpo4 compound and use as an electrode material in a lithium accumulator | |
JP5165515B2 (en) | Lithium ion secondary battery | |
CN101826617B (en) | Preparation method of lithium iron phosphate | |
Borgel et al. | LiMn0. 8Fe0. 2PO4/Li4Ti5O12, a possible Li-ion battery system for load-leveling application | |
Cong et al. | (PO4) 3− polyanions doped LiNi1/3Co1/3Mn1/3O2: an ultrafast-rate, long-life and high-voltage cathode material for Li-ion rechargeable batteries | |
CN101734637A (en) | Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery | |
CN103165896A (en) | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification | |
Zhang et al. | Multicore-shell carbon-coated lithium manganese phosphate and lithium vanadium phosphate composite material with high capacity and cycling performance for lithium-ion battery | |
CN102738463A (en) | Surface coating modification method of lithium vanadium phosphate cathode material by use of EDTA as carbon source | |
Guo et al. | Protective and ion conductive: High-Rate Ni-Rich cathode with enhanced cyclic stability via One-Step bifunctional dual-layer coating | |
US20200251717A1 (en) | Anode layer and all sold state battery | |
Du et al. | A three volt lithium ion battery with LiCoPO4 and zero-strain Li4Ti5O12 as insertion material | |
CN103299458B (en) | Preparation is for the method for high voltage nano-complex negative electrode (4.9V) of Li-ion batteries piles | |
Wang et al. | AlPO4-Li3PO4 dual shell for enhancing interfacial stability of Co-free Li-rich Mn-based cathode | |
CN102267692B (en) | Self-sacrificing template method for preparing nanoscale lithium ferrous phosphate | |
CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application | |
Zhong et al. | Synthesis and characterization of triclinic structural LiVPO 4 F as possible 4.2 V cathode materials for lithium ion batteries | |
JP6394391B2 (en) | Method for producing polyanionic positive electrode active material composite particles | |
Hu et al. | Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor | |
KR102537059B1 (en) | Anode for lithium secondary batteries and manufacturing method thereof | |
Zhang et al. | The Effects of Au Loading on the Electrochemical Properties of Fe 1.5 (PO 4)(OH) Cathode Material for Lithium-Ion Batteries |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |