CN102583300A - Fluorine and vanadium ion-doped lithium iron phosphate material and preparation method thereof - Google Patents
Fluorine and vanadium ion-doped lithium iron phosphate material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine and vanadium ion-doped lithium iron phosphate material and a preparation method thereof. The fluorine and vanadium ion-doped lithium iron phosphate material has a general chemical formula of LiFe1-yVy(PO4)1-xF3x/C, wherein x is equal to or greater than 0.01 and less than or equal to 0.5; y is equal to or greater than 0.01 and less than or equal to 0.5; and the sum of x and y is equal to or greater than 0.02 and less than or equal to 1.0. The preparation method provided by the invention comprises the following steps of mixing one or more lithium salts, one or more ferric salts, one or more phosphates, one or more carbon sources and doping agents of one or more fluorides and one or more vanadium compounds according to a certain ratio, adding a mixing medium into the mixture, carrying out ball milling mixing, carrying out pre-sintering, carrying out calcining at a high temperature, cooling, and grinding to obtain the fluorine and vanadium ion-doped lithium iron phosphate material. The preparation method provided by the invention realizes synthesis of the fluorine and vanadium ion-doped lithium iron phosphate material by a carbothermal reduction method which is obtained by improvement of the traditional solid phase method. The fluorine and vanadium ion-doped lithium iron phosphate material has excellent multiplying power charge-discharge performances and discharge potential platform electrochemical performances. The preparation method has simple processes, low energy consumption and low costs of raw materials, and is convenient for industrial production.
Description
Technical field
The present invention relates to the lithium ion battery material field, particularly relate to LiFePO 4 material of a kind of fluorine, vanadium ion codoped and preparation method thereof.This material can be used for lithium ion battery, ultracapacitor and capacitor batteries.
Background technology
From J.B.Goodnough [J.Electrochem.Soc., 144 (1997) 1188] study group's reported first in 1997 olivine-type LiFePO
4And with it as since the anode material for lithium-ion batteries, because of LiFePO
4Have nontoxic, Stability Analysis of Structures, specific storage high, have extended cycle life, cheap for manufacturing cost, safety performance good and characteristics such as environmentally friendly and be considered to that one of lithium ion power battery cathode material of application prospect is arranged most.
Yet, LiFePO
4Congenital lower electronic conductivity and ionic conduction speed have greatly limited its practical application in the lithium-ion-power cell field.In order to overcome the above shortcoming of iron lithium phosphate, domestic and international research person have carried out number of research projects to it.It mainly contains: 1. conductive doped dose, like conductive carbon [J.Electrochem.Soc., 154 (2007) A389; US7025907B2], conducting metal particles [Solid State Commun., 129 (2004) 311], conducting metal oxide [CN101222044A] etc., in order to improve the electric conductivity between iron lithium phosphate particulate surface and the particle; 2. as far as possible little [Chem.Mater., 21 (2009) 1557 of the particle diameter of control material; CN1958440A] shorten the iron lithium phosphate body the evolving path of middle lithium ion mutually, thus improve its ionic conduction speed; 3. foreign cation [CN1785799A; Nat.Mater., 3 (2004) 147; J.Alloys Compd., 503 (2010) 204] improve its ionic conduction speed or electronic conductivity; 4. negatively charged ion [CN1772604A mixes; CN101293641A; J.Power Sources, 174 (2007) 720; CN101386404A] the chemical property multiplying power discharging property especially that improves iron lithium phosphate.
At present, to fluorine doping, the adulterated research report of vanadium and few.The doped with fluorine ion can effectively improve its chemical property, particularly high rate performance in LiFePO 4 material.Fluorine mixes and mainly contains dual mode again: replace oxygen place doped [CN1772604A; J.Inorg.Mater.23 (2008) 587] and replace phosphate radical position doping [J.Power Sources, 174 (2007) 720; CN101386404A].Pass through ball milling Fe, FePO like Ma Zifeng seminar
4, H
3PO
4, LiF and sucrose reactant, 600～650 ℃ of calcinings 30 minutes down, synthesized the LiFe (PO that partly replaces phosphate radical again
4)
1-xF
3x/ C material is significantly improved its high rate performance.Chinese invention patent CN101386404A then adopts lithium salts, ferrous salt, phosphoric acid salt, carbon source to make mixture; Through ball milling and sintering (450-650 ℃), and then add that fluorochemical carries out ball milling, the method for sintering (650-900 ℃) has prepared a kind of ferrous phosphate doping lithium anode material of efficient fluorine-doped again.Yet though above method has all improved the high rate performance of iron lithium phosphate to a great extent, they do not consider that fluorine mixes to the influence of LiFePO 4 material discharge potential, and have LiF and Fe
2(PO
4) problem such as impurity such as F or doping effect be not remarkable.On the other hand, vanadium chemical property [J.Alloys Compd., 503 (2010) 204 of mixing and not only can improve iron lithium phosphate to a certain extent; J.Electrochem.Soc., 158 (2011) A26], but also help improving the discharge potential of LiFePO 4 material.The Li that vanadium mixes and generates
3V
2(PO
4)
3Though specific discharge capacity and discharge potential to improving iron lithium phosphate are useful, it also can reduce the lithium ion conduction speed of material.Possibly not see the report of relevant fluorine, vanadium codoped aspect at present as yet based on the shortcoming more than both.
Though above method has all improved the chemical property of iron lithium phosphate aspect to a great extent, following existing problems are arranged still:
1. though fluorine mixes and can effectively improve the high rate performance of iron lithium phosphate, the increase meeting guiding discharge current potential of fluorion obviously reduces, and then influences the specific energy and the specific power of battery, still can not satisfy the requirement of lithium-ion-power cell.
2. though vanadium mixes and can effectively improve the discharge potential of iron lithium phosphate, not obvious to the effect of the high rate performance of raising iron lithium phosphate and ionic conductance, can not satisfy the requirement of lithium-ion-power cell well.
3. single fluorine mixes or single vanadium mixes all is difficult to reach high rate performance and the discharge potential purpose that improves iron lithium phosphate simultaneously, thus limited it in, application in the high-power type consumer.
Summary of the invention
The present invention is directed to existing problem in the above-mentioned prior art; Provide a kind of and can improve the high rate performance of iron lithium phosphate and the fluorine of discharge potential platform, LiFePO 4 material of vanadium ion codoped and preparation method thereof simultaneously, to satisfy the performance requriements of lithium-ion-power cell LiFePO 4 material.
The object of the invention can be realized through following technical scheme:
The LiFePO 4 material of a kind of fluorine, vanadium ion codoped, the LiFePO 4 material chemical general formula of this fluorine, vanadium ion codoped is LiFe
1-yV
y(PO
4)
1-xF
3x/ C, wherein 0.01≤x≤0.5,0.01≤y≤0.5,0.02≤x+y≤1.0.
The preparation method of said fluorine, vanadium ion codoped LiFePO 4 material: lithium source, source of iron, phosphorus source and doping agent are pressed ionic mol ratio Li
+: (Fe
3+Or Fe
2+): V
5+: PO
4 3-: F
-=0.97～1.05: 1-y: y: 1-x: 3x weighing, wherein 0.01≤x≤0.5,0.01≤y≤0.5; 0.02≤x+y≤1.0 add carbon source and blending agent, adopt the liquid phase ball mill mixing even; Place nitrogen or argon gas atmosphere, be warming up to 250～450 ℃ and carry out presintering, be incubated 2～14 hours; Be warming up to 450～800 ℃ and calcine, be incubated 12～30 hours; Be cooled to room temperature, grind, promptly get the LiFePO 4 material of fluorine, vanadium ion codoped;
Described lithium source is one or more in Quilonum Retard, lithium oxalate, Lithium Hydroxide MonoHydrate, Lithium Acetate, lithium nitrate and the lithium fluoride;
Described source of iron is one or more in Ferrox, Iron diacetate, red oxide of iron, tertiary iron phosphate, iron nitrate and the ironic citrate;
Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate;
Described doping agent is fluorochemical and vanadium compounds; Described fluorochemical is lithium fluoride and/or Neutral ammonium fluoride; Described vanadium compounds is Vanadium Pentoxide in FLAKES and/or ammonium vanadate;
Described carbon source is one or more in Zulkovsky starch, glucose, sucrose, Hydrocerol A, Vestolen PP 7052, SEPIGEL 305, Z 150PH, acetylene black and the carbon black;
Described blending agent is deionized water, absolute ethyl alcohol, acetone or industrial spirit;
The add-on of described blending agent is 100～300% of lithium source, source of iron, phosphorus source, fluorochemical and a carbon source total mass;
The add-on of described carbon source is 2～50% of a source of iron quality.
For further realizing the object of the invention, 0.1≤x≤0.5,0.1≤y≤0.5,0.2≤x+y≤1.0.
The mixing time of said liquid phase ball milling is preferably 4～10 hours.
Saidly be warming up to 250～450 ℃ of temperature rise rates that carry out presintering and be preferably 1～5 ℃/min.
Saidly be warming up to 450～800 ℃ and carry out the incinerating temperature rise rate and be preferably 5～15 ℃/min.
The present invention compared with prior art has following advantage and beneficial effect:
1. adopt fluorine, vanadium ion codoped method can improve the multiplying power discharging property and the discharge potential platform of iron lithium phosphate simultaneously, thereby improve the specific power and the specific energy of ferric phosphate lithium cell.
2. the present invention can obtain crystallization perfection, the uniform fluorine of particle diameter, vanadium ion codoped LiFePO 4 material through processing parameters such as adjustment calcining temperature, soaking times.Can also reach through the relative doping of regulating and controlling fluorine, vanadium ion lay particular emphasis on improve LiFePO 4 material high rate capability also or improve its discharge potential platform.
3. preparing method's technology of the present invention is simple, processing ease, energy consumption are lower, starting material cheaply are easy to get, and the chemical property of gained material is superior, Modulatory character is strong, and is convenient to carry out industrialized production.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum (XRD) of the LiFePO 4 material (C) of the embodiment of the invention 2 prepared fluorine, vanadium ion codoped LiFePO 4 material (A), fluorine doped iron phosphate lithium material (B) and the fluorine that undopes, v element.
Fig. 2 is the sem photograph (SEM) of prepared fluorine, vanadium ion codoped LiFePO 4 material (A) and fluorine-doped lithium iron phosphate material (B) of the embodiment of the invention 2.
Fig. 3 is the surface-element distribution collection of illustrative plates (EDX) of prepared fluorine, vanadium ion codoped LiFePO 4 material (A) and fluorine-doped lithium iron phosphate material (B) of the embodiment of the invention 2.
Fig. 4 is that the embodiment of the invention 2 prepared fluorine, vanadium ion codoped LiFePO 4 materials are assembled into the first charge-discharge curve behind the test cell, and the charging/discharging voltage scope is 2.5～4.2V, and electrolytic solution is 1mol/L LiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1), charge-discharge magnification is respectively 0.1C, 0.5C, 1.0C, 2.0C, 5.0C.
Fig. 5 is the first charge-discharge curve after the embodiment of the invention 2 prepared non-fluorine-ion-doped LiFePO 4 materials are assembled into test cell, and the charging/discharging voltage scope is 2.5～4.2V, and electrolytic solution is 1mol/L LiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1), charge-discharge magnification is respectively 0.1C, 0.5C, 1.0C, 5.0C.
Embodiment
For better understanding the present invention, below in conjunction with accompanying drawing and embodiment the present invention is described further, but embodiment of the present invention is not limited thereto.
Embodiment 1
Lithium oxalate, tertiary iron phosphate, primary ammonium phosphate, ammonium vanadate and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=0.97: 0.99: 0.01: 0.99: 0.03 weighing; Press 25% of tertiary iron phosphate quality and add glucose, add deionized water, ball mill mixing 10 hours by 300% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 400 ℃ with the heat-up rate of 4 ℃/min and carry out presintering, be incubated 2 hours; Then be warming up to 750 ℃ with 10 ℃/min again and calcine, be incubated 30 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 147.9mAh/g, 135.5mAh/g, 121.3mAh/g, 100.3mAh/g and 93.2mAh/g; Its average discharge potential is respectively 3.370,3.360,3.345,3.305 and 3.240V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 2
Quilonum Retard, red oxide of iron, Secondary ammonium phosphate, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1: 0.9: 0.1: 0.95: 0.15 weighing; Press 5% of red oxide of iron quality and add Zulkovsky starch, add absolute ethyl alcohol, ball mill mixing 6 hours by 150% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 350 ℃ with the heat-up rate of 2 ℃/min and carry out presintering, be incubated 10 hours; Then be warming up to 650 ℃ with 5 ℃/min again and calcine, be incubated 24 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.In order relatively to need, also prepared the LiFePO 4 material of fluorine doped iron phosphate lithium material under the proportioning respectively with forming with undope fluorine, v element at identical preparation condition.
Fluorine, vanadium ion codoped LiFePO 4 material (A), fluorine doped iron phosphate lithium material (B) and the fluorine that undopes of method for preparing, the LiFePO 4 material (C) of v element are carried out the powder X-ray diffraction, and its collection of illustrative plates is as shown in Figure 1.Visible by Fig. 1; The introduction of fluorine, vanadium ion does not change the crystalline structure of iron lithium phosphate; Its main diffraction peak (diffraction peak that mainly refers to 011,111,121 and 311 crystal faces) all belongs to the diffraction peak (seeing the No.40-1499 of JCPDS standard card) of rhombic system olivine-type iron lithium phosphate; But other inferior diffraction peak (other diffraction peaks except that main diffraction peak) weakened even disappearance, and squint to high diffraction angle direction in the peak position of main diffraction peak.This explanation fluorine, vanadium ion have got into LiFePO
4In the lattice.It should be noted that in the vanadium ion codoped LiFePO 4 material (A) and micro-Li also occurred
3V
2(PO
4)
3, it is a kind ofly to have high discharge potential (about 3.6～4.2V) anode material for lithium-ion batteries helps to improve the discharge potential of LiFePO 4 material.For the influence of further research fluorine, vanadium ion codoped to LiFePO 4 material; Fluorine, vanadium ion codoped LiFePO 4 material (A) and fluorine-doped lithium iron phosphate material (B) have been carried out ESEM (SEM) and surface-element distribution (EDX) research, and its result sees Fig. 2 and Fig. 3.Can see from Fig. 2; Fluorine, vanadium ion codoped LiFePO 4 material (A) are made up of class sphere and rod shaped particles not of uniform size; Size is between 100～500nm, and fluorine-doped lithium iron phosphate material (B) is a spherical particle, and size is between 300～500nm.Fluorine, the particle diameter that vanadium ion codoped LiFePO 4 material is littler help to improve the rate of migration of lithium ion in the iron lithium phosphate body, and then improve the ionic conduction speed of material.Can know that from the EDX distribution diagram of element spectrum of Fig. 3 have F, V, O, P, Fe and C element in fluorine, the vanadium ion codoped LiFePO 4 material (A), F, V element content are respectively 0.74wt.%, 2.5wt.% again; And do not have V element, the content of F element in the fluorine-doped lithium iron phosphate material (B) is 0.69wt.%.Synthesizing map 1-3 can explain that fluorine, v element successfully are doped in the LiFePO 4 material, and its crystalline structure and surface topography have been played the great influence effect.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1); In the glove box of applying argon gas, be assembled into Experimental cell; Under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power, carry out the constant current charge-discharge test under the room temperature respectively, the charging/discharging voltage scope is 2.5～4.2V, sees Fig. 4.Visible by Fig. 4; The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 159.9mAh/g, 150.9mAh/g, 141.7mAh/g, 132.3mAh/g and 120.5mAh/g; Its average discharge potential is respectively 3.390,3.392,3.380,3.350 and 3.290V; And in low range (like 0.1C) when discharging and recharging; Second small charge and discharge platform near 3.6～3.8V, occurred, this secondary charge and discharge platform fades away along with the increase of charge-discharge magnification.Material each multiplying power (0.1C-5C) down the specific discharge capacity behind the cycle charge-discharge 30 times kept 98.70%, 99.10%, 98.25%, 97.92% and 98.08% of they initial discharge specific storagies respectively.In order relatively to need, descend the battery of the fluorine-doped lithium iron phosphate material of preparation also to carry out the constant current charge-discharge test to the same terms, the charging/discharging voltage scope is 2.5～4.2V, sees Fig. 5.Visible by Fig. 5; The first discharge specific capacity of fluorine-doped lithium iron phosphate material under 0.1C, 0.5C, 1.0C, 5.0C multiplying power is respectively 155mAh/g, 145mAh/g, 132mAh/g and 117mAh/g; Its average discharge potential then is respectively 3.383,3.350,3.303 and 3.15V; The specific discharge capacity that its cycle charge-discharge is 30 times is respectively 98.42%, 98.35%, 98.20% and 98.0%, all is lower than the capability retention of fluorine, vanadium ion codoped LiFePO 4 material.This explanation fluorine, vanadium ion codoped can improve the lithium ion rate of diffusion and the electronic conductivity of LiFePO 4 material effectively, and have suppressed polarization of electrode, thereby have improved specific discharge capacity, multiplying power specific storage and the discharge potential of material.
Embodiment 3
Lithium Acetate, iron nitrate, ammonium phosphate, ammonium vanadate and lithium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1.02: 0.95: 0.05: 0.9: 0.3 weighing; Press 50% of iron nitrate quality and add sucrose, add acetone, ball mill mixing 8 hours by 100% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 300 ℃ with the heat-up rate of 1 ℃/min and carry out presintering, be incubated 6 hours; Then be warming up to 550 ℃ with 15 ℃/min again and calcine, be incubated 18 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 157.1mAh/g, 142.3mAh/g, 131.5mAh/g, 125.5mAh/g and 119.2mAh/g; Its average discharge potential is respectively 3.389,3.372,3.361,3.345 and 3.275V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 4
Lithium nitrate, Iron diacetate, phosphoric acid, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1.05: 0.7: 0.3: 0.99: 0.03 weighing; Press 2% of Iron diacetate quality and add SEPIGEL 305, add industrial spirit, ball mill mixing 4 hours by 200% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 250 ℃ with the heat-up rate of 5 ℃/min and carry out presintering, be incubated 14 hours; Then be warming up to 450 ℃ with 8 ℃/min again and calcine, be incubated 12 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 145.5mAh/g, 132.7mAh/g, 121.0mAh/g, 109.8mAh/g and 99.6mAh/g; Its average discharge potential is respectively 3.478,3.465,3.39,3.360 and 3.324V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 5
Lithium Hydroxide MonoHydrate, iron nitrate, phosphoric acid, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1.02: 0.9: 0.1: 0.8: 0.6 weighing; Press 15% of iron nitrate quality and add Vestolen PP 7052, add acetone, ball mill mixing 8 hours by 250% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 450 ℃ with the heat-up rate of 5 ℃/min and carry out presintering, be incubated 10 hours; Then be warming up to 650 ℃ with 5 ℃/min again and calcine, be incubated 18 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 156.2mAh/g, 142.9mAh/g, 134.8mAh/g, 129.1mAh/g and 122.5mAh/g; Its average discharge potential is respectively 3.360,3.361,3.348,3.317 and 3.235V, and has still kept more than 97% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 6
Lithium fluoride, ironic citrate and red oxide of iron, Secondary ammonium phosphate, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1: 0.5: 0.5: 0.9: 0.3 weighing; Press 10% of ironic citrate and red oxide of iron quality and add Hydrocerol A, add industrial spirit, ball mill mixing 6 hours by 200% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 400 ℃ with the heat-up rate of 2 ℃/min and carry out presintering, be incubated 6 hours; Then be warming up to 800 ℃ with 5 ℃/min again and calcine, be incubated 12 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 145.3mAh/g, 140.7mAh/g, 134.2mAh/g, 125.5mAh/g and 108.9mAh/g; Its average discharge potential is respectively 3.681,3.570,3.462,3.441 and 3.350V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 7
Quilonum Retard, Ferrox and red oxide of iron, Secondary ammonium phosphate, ammonium vanadate and lithium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=0.97: 0.95: 0.05: 0.5: 1.5 weighings; Press 15% of ironic citrate and red oxide of iron quality and add acetylene black, add absolute ethyl alcohol, ball mill mixing 10 hours by 150% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 300 ℃ with the heat-up rate of 1 ℃/min and carry out presintering, be incubated 8 hours; Then be warming up to 650 ℃ with 5 ℃/min again and calcine, be incubated 30 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 148.3mAh/g, 143.8mAh/g, 131.4mAh/g, 123.5mAh/g and 121.7mAh/g; Its average discharge potential is respectively 3.320,3.311,3.302,3.304 and 3.214V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 8
Quilonum Retard, tertiary iron phosphate and red oxide of iron, Secondary ammonium phosphate, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1: 0.7: 0.3: 0.99: 0.03 weighing; Press 5% of tertiary iron phosphate and red oxide of iron quality and add carbon black, add absolute ethyl alcohol, ball mill mixing 10 hours by 200% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 350 ℃ with the heat-up rate of 2 ℃/min and carry out presintering, be incubated 10 hours; Then be warming up to 650 ℃ with 5 ℃/min again and calcine, be incubated 24 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 149.3mAh/g, 139.1mAh/g, 121.1mAh/g, 115.6mAh/g and 104.4mAh/g; Its average discharge potential is respectively 3.490,3.442,3.382,3.351 and 3.34V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
Embodiment 9
Quilonum Retard, red oxide of iron, Secondary ammonium phosphate, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride are pressed ionic mol ratio Li
+: Fe
3+: V
5+: PO
4 3-: F
-=1.02: 0.5: 0.5: 0.5: 1.5 weighings; Press 15% of tertiary iron phosphate and red oxide of iron quality and add carbon black, add absolute ethyl alcohol, ball mill mixing 10 hours by 200% of reactant materials total mass again; The slurry that obtains mixing; Be placed on then in the pit furnace of nitrogen atmosphere protection, be warming up to 350 ℃ with the heat-up rate of 2 ℃/min and carry out presintering, be incubated 10 hours; Then be warming up to 650 ℃ with 5 ℃/min again and calcine, be incubated 24 hours.Naturally cool to room temperature with stove, take out to grind and sieve in (400 order), promptly get the LiFePO 4 material of fluorine, vanadium ion codoped.
Adopt the fluorine of method for preparing, the LiFePO 4 material of vanadium ion codoped to process cathode film as positive active material; Cathode film is made up of by mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5; The about 0.1mm of thickness processes positive plate with the cathode film roll-in to stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/LLiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out the constant current charge-discharge test, and the charging/discharging voltage scope is 2.5～4.2V.The first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power is respectively 144.1mAh/g, 139.8mAh/g, 126.1mAh/g, 120.6mAh/g and 114.7mAh/g; Its average discharge potential is respectively 3.690,3.642,3.482,3.451 and 3.44V, and has still kept more than 98% of initial specific storage with the specific storage behind the 0.1C multiplying power cycle charge-discharge 30 times.
As stated, can realize the present invention preferably.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from spirit of the present invention and principle change, modification, substitute, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the LiFePO 4 material of a fluorine, vanadium ion codoped is characterized in that the LiFePO 4 material chemical general formula of this fluorine, vanadium ion codoped is LiFe
1-yV
y(PO
4)
1-xF
3x/ C, wherein 0.01≤x≤0.5,0.01≤y≤0.5,0.02≤x+y≤1.0.
2. the preparation method of the said fluorine of claim 1, vanadium ion codoped LiFePO 4 material is characterized in that: lithium source, source of iron, phosphorus source and doping agent are pressed ionic mol ratio Li
+: (Fe
3+Or Fe
2+): V
5+: PO
4 3-: F
-=0.97～1.05: 1-y: y: 1-x: 3x weighing, wherein 0.01≤x≤0.5,0.01≤y≤0.5; 0.02≤x+y≤1.0 add carbon source and blending agent, adopt the liquid phase ball mill mixing even; Place nitrogen or argon gas atmosphere, be warming up to 250～450 ℃ and carry out presintering, be incubated 2～14 hours; Be warming up to 450～800 ℃ and calcine, be incubated 12～30 hours; Be cooled to room temperature, grind, promptly get the LiFePO 4 material of fluorine, vanadium ion codoped;
Described lithium source is one or more in Quilonum Retard, lithium oxalate, Lithium Hydroxide MonoHydrate, Lithium Acetate, lithium nitrate and the lithium fluoride;
Described source of iron is one or more in Ferrox, Iron diacetate, red oxide of iron, tertiary iron phosphate, iron nitrate and the ironic citrate;
Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate;
Described doping agent is fluorochemical and vanadium compounds; Described fluorochemical is lithium fluoride and/or Neutral ammonium fluoride; Described vanadium compounds is Vanadium Pentoxide in FLAKES and/or ammonium vanadate;
Described carbon source is one or more in Zulkovsky starch, glucose, sucrose, Hydrocerol A, Vestolen PP 7052, SEPIGEL 305, Z 150PH, acetylene black and the carbon black;
Described blending agent is deionized water, absolute ethyl alcohol, acetone or industrial spirit;
The add-on of described blending agent is 100～300% of lithium source, source of iron, phosphorus source, fluorochemical and a carbon source total mass;
The add-on of described carbon source is 2～50% of a source of iron quality.
3. the preparation method of fluorine according to claim 2, vanadium ion codoped LiFePO 4 material is characterized in that: 0.1≤x≤0.5,0.1≤y≤0.5,0.2≤x+y≤1.0.
4. the preparation method of fluorine according to claim 2, vanadium ion codoped LiFePO 4 material is characterized in that: the mixing time of said liquid phase ball milling is 4～10 hours.
5. the preparation method of fluorine according to claim 2, vanadium ion codoped LiFePO 4 material is characterized in that: said to be warming up to 250～450 ℃ of temperature rise rates that carry out presintering be 1～5 ℃/min.
6. the preparation method of fluorine according to claim 2, vanadium ion codoped LiFePO 4 material is characterized in that: saidly be warming up to 450～800 ℃ to carry out the incinerating temperature rise rate be 5～15 ℃/min.
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