CN105152155A - Multiple ions co-doped lithium iron phosphate material and preparation method thereof - Google Patents

Multiple ions co-doped lithium iron phosphate material and preparation method thereof Download PDF

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CN105152155A
CN105152155A CN201510546919.5A CN201510546919A CN105152155A CN 105152155 A CN105152155 A CN 105152155A CN 201510546919 A CN201510546919 A CN 201510546919A CN 105152155 A CN105152155 A CN 105152155A
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preparation
lithium
iron phosphate
phosphate
vanadium
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徐德生
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Wuxi Jiabang Electric Power Pipeline Factory
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Wuxi Jiabang Electric Power Pipeline Factory
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention provides a multiple ions co-doped lithium iron phosphate material and a preparation method thereof. This material has a chemical general formula: Li1-zMzFe1-yVy(PO4)1-xFx/C, wherein 0.001</=x</=0.1, 0.001</=y</=0.1, 0.001</=z</=0.1, and M is lithium-doped metal ions. The preparation method includes: preparing vanadium ion doped iron phosphate Fe1-yVyPO4.2H2O containing crystal water, and performing thermal treatment to obtain vanadium doped iron phosphate Fe1-yVyPO4 not containing crystal water; adding a ball-milling medium, allowing ball milling and mixing, performing pre-sintering, performing calcining at high temperature, and performing grinding after cooling to obtain multiple ions co-doped lithium iron phosphate powdered material. The preparation method is simple, energy consumption is low, raw materials are low in price, and industrial production of the material is facilitated.

Description

LiFePO 4 material of a kind of polyion codoped and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery material, particularly relate to LiFePO 4 material of a kind of polyion codoped and preparation method thereof.This material can be used for lithium ion battery, ultracapacitor and capacitor batteries.
Background technology
The olivine-type LiFePO from J.B.Goodnough [J.Electrochem.Soc., 144 (1997) 1188] study group's reported first in 1997 4and used as since anode material for lithium-ion batteries, because of LiFePO 4have nontoxic, Stability Analysis of Structures, specific storage are high, have extended cycle life, cheap for manufacturing cost, safety performance good and the feature such as environmentally friendly and be considered to one of lithium ion power battery cathode material having application prospect most.
But, LiFePO 4congenital lower electronic conductivity and ion conduction rate significantly limit its practical application in lithium-ion-power cell field.In order to overcome the above shortcoming of iron lithium phosphate, investigators both domestic and external have carried out a large amount of research work to it.It mainly contains: 1. conductive doped dose, as conductive carbon [J.Electrochem.Soc., 154 (2007) A389; US7025907B2], conducting metal particles [SolidStateCommun., 129 (2004) 311], conducting metal oxide [CN101222044A] etc., in order to improve the electric conductivity between the surface of lithium iron phosphate particles and particle; 2. particle diameter little [Chem.Mater., 21 (2009) 1557 as far as possible of material are controlled; CN1958440A] shorten iron lithium phosphate body mutually in the evolving path of lithium ion, thus improve its ion conduction rate; 3. foreign cation [CN1785799A; Nat.Mater., 3 (2004) 147; J.AlloysCompd., 503 (2010) 204] its ion conduction rate or electronic conductivity is improved; 4. Doped anions [CN1772604A; CN101293641A; J.PowerSources, 174 (2007) 720; CN101386404A] improve the chemical property especially multiplying power discharging property of iron lithium phosphate.
At present, also few to the research report of Fluorin doped, vanadium doping.In LiFePO 4 material, doped with fluorine ion can effectively improve its chemical property, particularly high rate performance.Fluorin doped mainly contains again two kinds of modes: replace oxygen place doped [CN1772604A; J.Inorg.Mater.23 (2008) 587] and replace phosphate radical position doping [J.PowerSources, 174 (2007) 720; CN101386404A].If Ma Zifeng seminar is by ball milling Fe, FePO 4, H 3pO 4, LiF and sucrose reactant, then to calcine 30 minutes at 600 ~ 650 DEG C, synthesized the LiFe (PO that part replaces phosphate radical 4) 1-xf 3x/ C material, makes its high rate performance be significantly improved.Chinese invention patent CN101386404A then adopts lithium salts, ferrous salt, phosphoric acid salt, carbon source to make mixture, by a ball milling and sintering (450-650 DEG C), and then add that fluorochemical carries out ball milling, the method for (650-900 DEG C) that sinters again has prepared a kind of ferrous phosphate doping lithium anode material of efficient fluorine-doped.But although above method improves the high rate performance of iron lithium phosphate all to a great extent, they do not consider the impact of Fluorin doped on LiFePO 4 material discharge potential, and there is LiF and Fe 2(PO 4) impurity such as F or the problem such as doping effect is not remarkable.On the other hand, vanadium doping not only can improve chemical property [J.AlloysCompd., 503 (2010) 204 of iron lithium phosphate to a certain extent; J.Electrochem.Soc., 158 (2011) A26], but also be conducive to the discharge potential improving LiFePO 4 material.The Li that vanadium doping generates 3v 2(PO 4) 3although useful to the specific discharge capacity and discharge potential improving iron lithium phosphate, it also can reduce the lithium ion conduction speed of material.Based on both above shortcomings, the report about fluorine, vanadium codoped aspect may be had not yet to see.
Patent CN102583300A discloses the LiFePO 4 material and preparation method thereof of a kind of fluorine, vanadium ion-doped.The chemical general formula of this LiFePO 4 material 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.Lithium salts, molysite, phosphoric acid salt, carbon source and fluorine, vanadium doping agent are mixed in proportion by it, ball milling, high-temperature calcination, obtain the LiFePO 4 material of fluorine, vanadium ion-doped.Although this patent has carried out mostly being doping vario-property to iron lithium phosphate, but hotchpotch and principal element material are combined by simple raw material mixing, ball milling, roasting by both, the distributing homogeneity of doped element in LiFePO 4 material and the occupy-place in iron lithium phosphate lattice thereof can not be ensured, easily cause the olivine-type crystal structure mutation of iron lithium phosphate, produce dephasign, reduce material electrical property, do not have the effect improving and improve on the contrary.
Summary of the invention
The present invention is directed to problem existing in above-mentioned prior art, there is provided a kind of and can improve carbon-coated LiFePO 4 for lithium ion batteries material of the high rate performance of iron lithium phosphate and the polyion codoped of discharge potential platform and preparation method thereof simultaneously, to meet the performance requriements of lithium-ion-power cell to LiFePO 4 material.
Object of the present invention can be achieved through the following technical solutions:
A LiFePO 4 material for polyion codoped, the LiFePO 4 material chemical general formula of this polyion codoped is Li 1-zm zfe 1-yv y(PO 4) 1-xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, M is the metal ion in the doping of lithium position.
Preferably, described M and F is from fluorochemical MFn, and wherein n is 1,2,3 or 4.
The preparation method of described polyion codoped LiFePO 4 material comprises the following steps:
(1) preparation is containing the tertiary iron phosphate Fe of the doping vanadium ion of crystal water 1-yv ypO 42H 2o;
(2) heat-treated by the tertiary iron phosphate of the doping vanadium ion containing crystal water prepared in step (1), then naturally cooling obtains not containing the tertiary iron phosphate Fe of the doping vanadium of crystal water 1-yv ypO 4;
(3) by lithium source, tertiary iron phosphate Fe 1-yv ypO 4structural formula Li is pressed with fluorochemical MFn 1-zm zfe 1-yv y(PO 4) 1 -xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1 weighs, and adds carbon source and ball-milling medium, liquid phase ball milling is adopted to mix, be placed in nitrogen or argon gas atmosphere, be warming up to 250 ~ 450 DEG C and carry out presintering, be incubated 2 ~ 14 hours, be warming up to 450 ~ 800 DEG C to calcine, be incubated 12 ~ 30 hours; Be cooled to room temperature, grinding, obtains the LiFePO 4 material of fluorine, vanadium ion-doped.
Hotchpotch substep and LiFePO 4 material being carried out adulterating is to enable doped element distribute also occupy-place uniformly in the lattice of iron lithium phosphate, thus promotes the over-all properties of material.
Preferably, described step (1) preparation is containing the tertiary iron phosphate Fe of the doping vanadium ion of crystal water 1-yv ypO 42H 2the step of O is:
(1-y): y in molar ratio, wherein 0.001≤y≤0.1 takes soluble ferric iron salt and vanadium compounds, add deionized water, be configured to the mixed solution A that concentration is 0.05 ~ 0.1mol/L, wherein concentration can be 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L or 0.1mol/L etc.;
The phosphate solution B of configuration concentration 0.05 ~ 5mol/L, wherein concentration can be 0.05mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L etc.;
Configuration concentration is the ammonia soln of 0.5 ~ 10mol/L, and wherein concentration can be 0.5mol/L, 1mol/L, 2mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L or 10mol/L etc.;
Mixed solution A and phosphate solution B are pumped in reactor and reacts, and regulate pH to be 2 ~ 3 with ammoniacal liquor, such as 2,2.2,2.4,2.6,2.8 or 3 etc.; The tertiary iron phosphate Fe filtered, drying obtains the doping vanadium containing crystal water is carried out after having reacted 1-yv ypO 42H 2o.
Preferably, described soluble ferric iron salt is one or more in Ferrox, Iron diacetate, ferric oxide, tertiary iron phosphate, iron nitrate and ironic citrate, described combination typical case but limiting examples have: the combination of Ferrox, Iron diacetate and ferric oxide, the combination of ferric oxide, tertiary iron phosphate and iron nitrate, the combination etc. of ferric oxide, tertiary iron phosphate, iron nitrate and ironic citrate.
Preferably, described vanadium compounds is the combination etc. of Vanadium Pentoxide in FLAKES and/or ammonium vanadate, such as Vanadium Pentoxide in FLAKES and ammonium vanadate.
Preferably, it is 40 ~ 95 DEG C that mixed solution A and phosphate solution B are pumped in reactor the temperature of reaction of carrying out reacting, and the reaction times is 0.5 ~ 3h, and the stirring velocity of reaction is 800 ~ 2500rpm; Wherein temperature of reaction can be 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 95 DEG C etc.; Reaction times can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h etc.; The stirring velocity of reaction can be 800rpm, 1000rpm, 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, 2200rpm or 2500rpm etc.
Preferably, in described step (2), heat treated temperature is 300 ~ 500 DEG C, and soaking time is 5 ~ 10h, and wherein heat treated temperature can be 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C or 500 DEG C etc.; Soaking time can be 5h, 6h, 7h, 8h, 9h or 10h etc.
Preferably, lithium source in described step (3) is one or more in Quilonum Retard, lithium oxalate, lithium hydroxide, Lithium Acetate, lithium nitrate and lithium fluoride, described combination typical case but limiting examples have:: the combination of Quilonum Retard, lithium oxalate and lithium hydroxide, the combination etc. of lithium hydroxide, Lithium Acetate and lithium nitrate, the combination etc. of lithium hydroxide, Lithium Acetate, lithium nitrate and lithium fluoride.
Preferably, described carbon source is one or more in Zulkovsky starch, glucose, sucrose, citric acid, polypropylene, polyacrylamide, polyvinyl alcohol, acetylene black and carbon black, described combination typical case but limiting examples have: the combination of Zulkovsky starch, dextrose plus saccharose, the combination of sucrose, citric acid, polypropylene and polyacrylamide, the combination etc. of acrylamide, polyvinyl alcohol, acetylene black and carbon black.
Preferably, the add-on of described carbon source is 15 ~ 20% of raw material total mass, such as 15%, 17%, 18%, 19% or 20% etc.
Preferably, described ball-milling medium is deionized water, dehydrated alcohol, acetone or industrial spirit.
Preferably, the add-on lithium source of described ball-milling medium, tertiary iron phosphate Fe 1-yv ypO 4, fluorochemical MFn and carbon source total mass 100 ~ 300%, such as 100%, 150%, 200%, 250% or 300% etc.
Preferably, described in step (3), the mixing time of liquid phase ball milling is preferably 4 ~ 10 hours, such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or 10 hours etc.
Preferably, be warming up to 250 ~ 450 DEG C of temperature rise rates carrying out presintering described in step (3) and be preferably 1 ~ 5 DEG C/min, such as 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min or 5 DEG C/min etc.
Preferably, be warming up to 450 ~ 800 DEG C of temperature rise rates carrying out calcining and be preferably 5 ~ 15 DEG C/min, such as 5 DEG C/min, 7 DEG C/min, 10 DEG C/min, 13 DEG C/min or 15 DEG C/min etc. described in.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
(1) doped metal ion is introduced in body tertiary iron phosphate process before the synthesis, dopant ion is made more easily to enter iron position, ensure that the distributing homogeneity of doped metal ion iron position in iron lithium phosphate lattice, crystal water is removed again by thermal treatment, control temperature rise rate and soaking time, improve the homogeneity of doped metal ion in tertiary iron phosphate and the degree of crystallinity of tertiary iron phosphate;
(2) by the difference doping of substep, ensure that dopant ion is in the material bodies middle homogeneity distributed mutually, improves multiplying power discharging property and the discharge potential platform of iron lithium phosphate simultaneously, thus improves specific power and the specific energy of ferric phosphate lithium cell.
(3) preparation method's technique of the present invention is simple, processing ease, energy consumption are lower, starting material are cheaply easy to get, and the chemical property of resulting materials is superior, Modulatory character strong, and is convenient to carry out industrialized production.
Embodiment
For better understanding the present invention, below by embodiment, the invention will be further described, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) (1-y): y in molar ratio, wherein 0.001≤y≤0.1 takes and Ferrox and ammonium vanadate is joined in 20L deionized water, is configured to the mixed solution A that total concentration of metal ions is 0.07mol/L; Take primary ammonium phosphate to join in 0.2L deionized water and be made into the solution B that concentration is 3mol/L; Compound concentration is the ammonia soln of 8mol/L; Pump in reactor by mixed solution A and solution B, controlling temperature of reaction is 60 DEG C, and stirring velocity is 1200rpm, regulates pH to be 2.5 with ammoniacal liquor, reaction 1.5h, is then filtered by reaction liquid, washing, drying obtain the tertiary iron phosphate Fe of the doping V containing crystal water 0.96v 0.04pO 42H 2o.
(2) Fe will obtained in step (1) 0.96v 0.04pO 42H 2o rises to 400 DEG C of process 8h by room temperature under the temperature rise rate of 5 DEG C/min, and Temperature fall obtains not containing the tertiary iron phosphate Fe of the doping V of crystal water 0.96v 0.04pO 4.
(3) by Li 1-zm zfe 1-yv y(PO 4) 1-xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, takes lithium oxalate, Neutral ammonium fluoride and glucose (it accounts for 17% of raw material total mass), the tertiary iron phosphate Fe obtained with step (2) 0.96v 0.04pO 4ball milling mixes 8 hours, obtains the slurry mixed, and is then placed in the pit furnace of nitrogen atmosphere protection, is warming up to 400 DEG C and carries out presintering, be incubated 8 hours with the heat-up rate of 4 DEG C/min; Then be warming up to 750 DEG C with 10 DEG C/min again to calcine, be incubated 20 hours.Naturally cool to room temperature with stove, take out grinding and sieve (400 order), obtain the LiFePO 4 material of polyion codoped.
The fluorine adopting aforesaid method to prepare, the LiFePO 4 material of vanadium ion-doped make cathode film as positive active material, cathode film to be made up of in mass ratio active substance, acetylene black and tetrafluoroethylene (solid content) at 75: 20: 5, thickness is about 0.1mm, makes positive plate by cathode film roll-in to stainless (steel) wire; Using metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2400); Electrolytic solution is 1mol/LLiPF 6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1: 1), experimental cell is assembled in the glove box of applying argon gas, at room temperature carry out constant current charge-discharge test, 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 156.3mAh/g, 154.0mAh/g, 151.3mAh/g, 144.4mAh/g and 139.9mAh/g; It still maintains more than 99% of initial specific capacities with the specific storage after 0.1C circulation discharge and recharge 30 times.
Embodiment 2
(1) (1-y): y in molar ratio, wherein 0.001≤y≤0.1 takes and Ferrox and ammonium vanadate is joined in 20L deionized water, is configured to the mixed solution A that total concentration of metal ions is 0.1mol/L; Take primary ammonium phosphate to join in 0.2L deionized water and be made into the solution B that concentration is 5mol/L; Compound concentration is the ammonia soln of 10mol/L; Pump in reactor by mixed solution A and solution B, controlling temperature of reaction is 95 DEG C, and stirring velocity is 800rpm, regulates pH to be 3 with ammoniacal liquor, reaction 0.5h, is then filtered by reaction liquid, washing, drying obtain the tertiary iron phosphate Fe of the doping V containing crystal water 0.999v 0.001pO 42H 2o.
(2) Fe will obtained in step (1) 0.999v 0.001pO 42H 2o rises to 500 DEG C of process 5h by room temperature under the temperature rise rate of 1 DEG C/min, and Temperature fall obtains not containing the tertiary iron phosphate Fe of the doping V of crystal water 0.999v 0.001pO 4.
(3) by Li 1-zm zfe 1-yv y(PO 4) 1-xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, takes lithium oxalate, Neutral ammonium fluoride and glucose (it accounts for 20% of raw material total mass), the tertiary iron phosphate Fe obtained with step (2) 0.999v 0.001pO 4ball milling mixes 10 hours, obtains the slurry mixed, and is then placed in the pit furnace of nitrogen atmosphere protection, is warming up to 450 DEG C and carries out presintering, be incubated 2 hours with the heat-up rate of 5 DEG C/min; Then be warming up to 800 DEG C with 15 DEG C/min again to calcine, be incubated 12 hours.Naturally cool to room temperature with stove, take out grinding and sieve (400 order), obtain the LiFePO 4 material of fluorine, vanadium polyion codoped.
Method in employing embodiment 1 is to obtained material, and at room temperature carry out constant current charge-discharge test, 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 156.9mAh/g, 154.7mAh/g, 151.5mAh/g, 144.9mAh/g and 140.3mAh/g; And it still maintains more than 99% of initial specific capacities with the specific storage after 0.1C circulation discharge and recharge 30 times.
Embodiment 3:
(1) (1-y): y in molar ratio, wherein 0.001≤y≤0.1 takes and Ferrox and ammonium vanadate is joined in 20L deionized water, is configured to the mixed solution A that total concentration of metal ions is 0.05mol/L; Take primary ammonium phosphate to join in 0.2L deionized water and be made into the solution B that concentration is 0.05mol/L; Compound concentration is the ammonia soln of 0.5mol/L; Pump in reactor by mixed solution A and solution B, controlling temperature of reaction is 40 DEG C, and stirring velocity is 2500rpm, regulates pH to be 2 with ammoniacal liquor, reaction 3h, is then filtered by reaction liquid, washing, drying obtain the tertiary iron phosphate Fe of the doping V containing crystal water 0.98v 0.02pO 42H 2o.
(2) Fe will obtained in step (1) 0.98v 0.02pO 42H 2o rises to 300 DEG C of process 10h by room temperature under the temperature rise rate of 2.5 DEG C/min, and Temperature fall obtains not containing the tertiary iron phosphate Fe of the doping V of crystal water 0.98v 0.02pO 4.
(3) by Li 1-zm zfe 1-yv y(PO 4) 1-xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, takes lithium oxalate, Neutral ammonium fluoride and glucose (it accounts for 15% of raw material total mass), the tertiary iron phosphate Fe obtained with step (2) 0.98v 0.02pO 4ball milling mixes 4 hours, obtains the slurry mixed, and is then placed in the pit furnace of nitrogen atmosphere protection, is warming up to 250 DEG C and carries out presintering, be incubated 14 hours with the heat-up rate of 1 DEG C/min; Then be warming up to 450 DEG C with 5 DEG C/min again to calcine, be incubated 30 hours.Naturally cool to room temperature with stove, take out grinding and sieve (400 order), obtain the LiFePO 4 material of fluorine, vanadium polyion codoped.
Method in employing embodiment 1 is to obtained material, and at room temperature carry out constant current charge-discharge test, 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 155.3mAh/g, 153.2mAh/g, 150.0mAh/g, 142.9mAh/g and 138.7mAh/g; And it still maintains more than 99% of initial specific capacities with the specific storage after 0.1C circulation discharge and recharge 30 times.
Comparative example 1: the embodiment 1 in patent CN102583300A, adopt the testing method in the embodiment of the present application 1 to carry out performance test to it, obtain the first discharge specific capacity of this material under 0.1C, 0.5C, 1.0C, 2.0C, 5.0C multiplying power and be respectively 147.9mAh/g, 135.5mAh/g, 121.3mAh/g, 100.3mAh/g and 93.2mAh/g; It still maintains more than 98% of initial specific capacities with the specific storage after 0.1C circulation discharge and recharge 30 times.
In sum, can find out that (1) introduces doped metal ion in body tertiary iron phosphate process before the synthesis, dopant ion is made more easily to enter iron position, ensure that the distributing homogeneity of doped metal ion iron position in iron lithium phosphate lattice, crystal water is removed again by thermal treatment, control temperature rise rate and soaking time, improve the homogeneity of doped metal ion in tertiary iron phosphate and the degree of crystallinity of tertiary iron phosphate;
(2) by the difference doping of substep, ensure that dopant ion is in the material bodies middle homogeneity distributed mutually, improves multiplying power discharging property and the discharge potential platform of iron lithium phosphate simultaneously, thus improves specific power and the specific energy of ferric phosphate lithium cell.
(3) preparation method's technique of the present invention is simple, processing ease, energy consumption are lower, starting material are cheaply easy to get, and the chemical property of resulting materials is superior, Modulatory character strong, and is convenient to carry out industrialized production.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from spirit of the present invention and principle change, modification, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (9)

1. a LiFePO 4 material for polyion codoped, is characterized in that, the LiFePO 4 material chemical general formula of this polyion codoped is Li 1-zm zfe 1-yv y(PO 4) 1-xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, M is the metal ion in the doping of lithium position.
2. the LiFePO 4 material of polyion codoped as claimed in claim 1, it is characterized in that, described M and F is from fluorochemical MFn, and wherein n is 1,2,3 or 4.
3. the preparation method of polyion codoped LiFePO 4 material as claimed in claim 1 or 2, it is characterized in that, described preparation method comprises the following steps:
(1) preparation is containing the tertiary iron phosphate Fe of the doping vanadium ion of crystal water 1-yv ypO 42H 2o;
(2) heat-treated by the tertiary iron phosphate of the doping vanadium ion containing crystal water prepared in step (1), then naturally cooling obtains not containing the tertiary iron phosphate Fe of the doping vanadium of crystal water 1-yv ypO 4;
(3) by lithium source, tertiary iron phosphate Fe 1-yv ypO 4structural formula Li is pressed with fluorochemical MFn 1-zm zfe 1-yv y(PO 4) 1 -xf x/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1, weigh, add carbon source and ball-milling medium, adopt liquid phase ball milling to mix, be placed in nitrogen or argon gas atmosphere, be warming up to 250 ~ 450 DEG C and carry out presintering, be incubated 2 ~ 14 hours, be warming up to 450 ~ 800 DEG C and calcine, be incubated 12 ~ 30 hours; Be cooled to room temperature, grinding, obtains the LiFePO 4 material of fluorine, vanadium ion-doped.
4. preparation method as claimed in claim 3, is characterized in that, described step (1) preparation is containing the tertiary iron phosphate Fe of the doping vanadium ion of crystal water 1-yv ypO 42H 2the step of O is:
(1-y): y in molar ratio, wherein 0.001≤y≤0.1 takes soluble ferric iron salt and vanadium compounds, adds deionized water, is configured to the mixed solution A that concentration is 0.05 ~ 0.1mol/L;
The phosphate solution B of configuration concentration 0.05 ~ 5mol/L;
Configuration concentration is the ammonia soln of 0.5 ~ 10mol/L;
Mixed solution A and phosphate solution B are pumped in reactor and reacts, and regulate pH to be 2 ~ 3 with ammoniacal liquor; The tertiary iron phosphate Fe filtered, drying obtains the doping vanadium containing crystal water is carried out after having reacted 1-yv ypO 42H 2o;
Preferably, described soluble ferric iron salt is one or more in Ferrox, Iron diacetate, ferric oxide, tertiary iron phosphate, iron nitrate and ironic citrate;
Preferably, described vanadium compounds is Vanadium Pentoxide in FLAKES and/or ammonium vanadate;
Preferably, it is 40 ~ 95 DEG C that mixed solution A and phosphate solution B are pumped in reactor the temperature of reaction of carrying out reacting, and the reaction times is 0.5 ~ 3h, and the stirring velocity of reaction is 800 ~ 2500rpm.
5. the preparation method as described in claim 3 or 4, is characterized in that, in described step (2), heat treated temperature is 300 ~ 500 DEG C, and soaking time is 5 ~ 10h.
6. the preparation method as described in one of claim 3-5, is characterized in that, the lithium source described in step (3) is one or more in Quilonum Retard, lithium oxalate, lithium hydroxide, Lithium Acetate, lithium nitrate and lithium fluoride;
Preferably, described carbon source is one or more in Zulkovsky starch, glucose, sucrose, citric acid, polypropylene, polyacrylamide, polyvinyl alcohol, acetylene black and carbon black;
Preferably, the add-on of described carbon source is 15 ~ 20% of raw material total mass;
Preferably, described ball-milling medium is deionized water, dehydrated alcohol, acetone or industrial spirit;
Preferably, the add-on of described ball-milling medium is lithium source, tertiary iron phosphate Fe 1-yv ypO 4, fluorochemical MFn and carbon source total mass 100 ~ 300%.
7. the preparation method as described in one of claim 3-6, is characterized in that: described in step (3), the mixing time of liquid phase ball milling is 4 ~ 10 hours.
8. the preparation method as described in one of claim 3-7, is characterized in that: being warming up to 250 ~ 450 DEG C of temperature rise rates carrying out presintering described in step (3) is 1 ~ 5 DEG C/min.
9. the preparation method as described in one of claim 3-8, is characterized in that: described in be warming up to 450 ~ 800 DEG C of temperature rise rates carrying out calcining be 5 ~ 15 DEG C/min.
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CN109980186A (en) * 2017-12-27 2019-07-05 中国电子科技集团公司第十八研究所 Modified metal pyrophosphate doped positive electrode material
CN111540901A (en) * 2020-06-29 2020-08-14 株洲冶炼集团科技开发有限责任公司 Method for preparing lithium iron phosphate (LEP) by using lithium iron (III) phosphate

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CN105845913A (en) * 2016-05-23 2016-08-10 无锡市嘉邦电力管道厂 Multi-ion co-doping lithium iron phosphate material and preparation method thereof
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