CN101357756B - Method for preparing lithium battery positive pole material lithium iron phosphate - Google Patents

Method for preparing lithium battery positive pole material lithium iron phosphate Download PDF

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CN101357756B
CN101357756B CN2007101434084A CN200710143408A CN101357756B CN 101357756 B CN101357756 B CN 101357756B CN 2007101434084 A CN2007101434084 A CN 2007101434084A CN 200710143408 A CN200710143408 A CN 200710143408A CN 101357756 B CN101357756 B CN 101357756B
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lithium
iron
sintering
fec
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CN101357756A (en
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许中柱
荣强
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BYD Co Ltd
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BYD Co Ltd
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Priority to KR1020097024880A priority patent/KR20090131680A/en
Priority to EP08734239.0A priority patent/EP2142473B1/en
Priority to JP2010512495A priority patent/JP5181022B2/en
Priority to PCT/CN2008/070883 priority patent/WO2009015565A1/en
Priority to US12/135,128 priority patent/US20090035204A1/en
Publication of CN101357756A publication Critical patent/CN101357756A/en
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a method for preparing anode material of lithium batteries such as lithium iron (II) phosphate, which comprises mixing and sintering lithium source, iron source, phosphorus source and carbon source; wherein, the iron source is the mixture of FeC2O4 and FeCO3 and the molar ratio of FeC2O4 and FeCO3 is 1: 0.5-4. The lithium ferrous phosphate prepared by the method has relatively high purity and specific capacity; furthermore, the method has high operational safety.

Description

A kind of preparation method of lithium battery positive pole material lithium iron phosphate
Technical field
The present invention more particularly, is the preparation method about a kind of lithium battery positive pole material lithium iron phosphate about a kind of preparation method of anode material of lithium battery.
Background technology
The LiFePO of olivine-type 4Have excellent electrochemical properties, be suitable as the positive electrode of lithium battery.LiFePO 4Advantage such as have that cycle performance is good, the high temperature charge-discharge performance is good, the security performance of raw material wide material sources, non-environmental-pollution, the Heat stability is good of material, prepared battery is outstanding, make it be applied to various removable field of power supplies, particularly great market prospects are arranged in the battery of electric vehicle field.
At present, the most generally the LiFePO 4 preparation method of Shi Yonging is a high-temperature solid phase reaction method, high-temperature solid phase reaction method is with Fe source compound, Li source compound, P source compound and the carbon-source cpd preparation method of roasting direct at high temperature, has the advantage that equipment is simple, be convenient to suitability for industrialized production.
CN1948135A discloses the method that a kind of solid reaction process prepares LiFePO 4, this method comprises mixes lithium hydroxide, ferrous oxalate and ammonium dihydrogen phosphate and polychlorostyrene in organic or aqueous medium at normal temperatures and pressures for alkene with mechanical ball milling or churned mechanically mode, the mixture drying is placed in the temperature control reacting furnace, with mobile non-oxidizing gas displacement reaction container, the reaction of segmented program temperature control is 0.3-20 hour in 100-750 ℃ of scope, behind the reactant natural cooling, after mechanical disruption, sieve, get lithium iron phosphate cathode material black solid powder; Wherein the mixed proportion of lithium hydroxide, ferrous oxalate and ammonium dihydrogen phosphate is a benchmark according to lithium, iron, phosphate content, lithium: iron: the mole ratio of phosphate radical is 1: 1: 1, polychlorostyrene is benchmark for the addition of alkene according to the theoretical weight for preparing lithium iron phosphate cathode material, per 100 of preparation is restrained in the lithium iron phosphate cathode materials contain the 2-5% carbon content.
Adopt the above-mentioned solid phase reaction method to prepare in the process of LiFePO 4 and generate Fe easily 2The P dephasign makes that the LiFePO 4 purity that obtains is not high, specific capacity is lower.And the above-mentioned solid phase reaction method prepares and generates H in the process of LiFePO 4 easily 2, H 2Concentration is exploded after reaching explosion limit easily, so the processing safety of this method is lower.
Summary of the invention
The objective of the invention is not high for the LiFePO 4 purity that overcomes existing method preparation, specific capacity is lower and the lower defective of existing method processing safety, and a kind of LiFePO 4 and high preparation method of processing safety that can obtain having higher degree and specific capacity is provided.
The present inventor finds, existing high-temperature solid phase reaction method prepares in the process of LiFePO 4 and generates Fe easily 2P dephasign and H 2Reason be FeC 2O 42H 2O at high temperature (for example, 100-750 ℃) decomposes generation a large amount of CO and H 2O is though CO can prevent Fe 2+Be oxidized to Fe 3+, but because the amount of the CO that generates is very big, a part of CO is with Fe 2+And PO 4 3-Be reduced to simple substance Fe and simple substance P respectively, simple substance Fe and simple substance P react down at 600-720 ℃ and generate Fe 2P; H 2O and simple substance Fe reaction generate H 2, H 2Also can be with Fe 2+, PO 4 3-Be reduced to simple substance Fe and simple substance P, and then generate Fe 2P.
The invention provides a kind of preparation method of lithium battery positive pole material lithium iron phosphate, this method comprises mixes lithium source, source of iron, phosphorus source and carbon source and sintering, and wherein, described source of iron is FeC 2O 4And FeCO 3Mixture, FeC 2O 4And FeCO 3Mol ratio be 1: 0.5-4.
Adopt ferrous oxalate to compare as source of iron separately with existing method, it is 1 that the preparation method of LiFePO 4 provided by the invention adopts mol ratio: the FeC of 0.5-4 2O 4And FeCO 3Mixture as source of iron, with lithium source, source of iron, phosphorus source and carbon source sintering the time, the growing amount of CO is less, the CO of generation just plays and prevents Fe 2+Be oxidized to Fe 3+Effect, can be with Fe 2+Be reduced into simple substance Fe or with PO 4 3-Be reduced to simple substance P, thereby avoided Fe 2The generation of P obtains the higher LiFePO 4 of purity, and and then improve the specific capacity of the LiFePO 4 obtain; Simultaneously, owing to there is not H 2O or simple substance Fe generate, and can not generate H 2Thereby, improve processing safety.
Description of drawings
Fig. 1 is the XRD diffraction pattern of the LiFePO 4 that adopts method of the present invention and make;
The XRD diffraction pattern of the LiFePO 4 that Fig. 2 makes for the method that adopts prior art.
Embodiment
Method provided by the invention comprises mixes lithium source, source of iron, phosphorus source and carbon source and sintering, and wherein, described source of iron is FeC 2O 4And FeCO 3Mixture, FeC 2O 4And FeCO 3Mol ratio be 1: 0.5-4.
Described FeC 2O 4And FeCO 3Mol ratio be preferably 1: 1.5-4.FeC 2O 4And FeCO 3Mixture can be by anhydrous oxalic acid is ferrous ferrous according to 1 with Carbon Dioxide: the mol ratio of 0.5-4 is mixed and is obtained, also can be for heating the product that ferrous oxalate obtains, heating condition comprises that heating-up temperature can be 100-350 ℃, is preferably 120-300 ℃; Can be 0.2-6 hour heating time, is preferably 0.5-5 hour.
Can adopt following method to calculate FeC in the product that the heating ferrous oxalate obtains 2O 4And FeCO 3Mol ratio, to weigh the extent of reaction of ferrous oxalate decomposition reaction.
Suppose the FeC of adding 2O 42H 2The O quality is Xg, FeC 2O 42H 2Product FeC after the O heating 2O 4And FeCO 3The quality of mixture be Yg, FeC so 2O 4And FeCO 3Mol ratio be: (179.902Y-115.86X): (143.87X-179.902Y).Wherein, 179.902 is FeC 2O 42H 2The molecular weight of O, 115.86 is FeCO 3Molecular weight, 143.87 is FeC 2O 4Molecular weight.
The heating of described ferrous oxalate is preferably carried out under vacuum condition, decomposes the CO that generates thereby can remove in time, avoids CO with Fe 2+Be reduced into Fe.Pressure under the vacuum condition can be the 100-1000 handkerchief, is preferably the 200-700 handkerchief.At this, pressure is absolute pressure.Can adopt conventional vacuum plant such as vacuum pump or vacuum drying oven to realize above-mentioned vacuum condition.
After ferrous oxalate heats under these conditions, the product that obtains directly can be mixed with lithium source, phosphorus source and carbon source, mix with lithium source, phosphorus source and carbon source again after also the product that obtains can being cooled to room temperature.The speed of cooling can be 1-10 ℃/minute.
Can adopt conventional method that lithium source, source of iron, phosphorus source and carbon source are mixed, under the preferable case, in order to mix more evenly, can be with lithium source, source of iron, phosphorus source and carbon source and dispersant ball milling.The method of described ball milling comprises lithium source, source of iron, phosphorus source and carbon source and dispersant is joined ball milling in the ball mill, oven dry then.Described dispersant can be the organic solvent of routine, and as in methyl alcohol, ethanol and the acetone one or more, the consumption of dispersant is the 70-120 weight % of source of iron, lithium source, phosphorus source and carbon source total amount.As long as the condition of ball milling mixes above-mentioned various material, for example, the ball milling time can be 3-12 hour.As long as the condition of oven dry vapors away described dispersant, for example, the temperature of oven dry can be 30-80 ℃, and the time of oven dry can be 2-10 hour.
The mixed proportion in described lithium source, source of iron and phosphorus source can be its conventional mixed proportion, and for example the mol ratio in source of iron, lithium source, phosphorus source is Fe: Li: P=1: 0.95-1.1: 0.95-1.1.The consumption of carbon source is the 0.5-10 weight % of source of iron, lithium source and phosphorus source total amount.
Described lithium source can be the various lithium compounds that are used to prepare LiFePO 4 of routine, as in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium hydrogen phosphate and the lithium dihydrogen phosphate one or more.
Described phosphorus source can be the various phosphorus compounds that are used to prepare LiFePO 4 of routine, as in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate and the lithium dihydrogen phosphate one or more.
Described carbon source can be the various carbon compounds that are used to prepare LiFePO 4 of routine, as in glucose, sucrose, starch and the carbon black one or more.
The method of described sintering can be the sintering method of the preparation LiFePO 4 of routine; for example; sintering method is included in the inert protective gas, and lithium source, source of iron, phosphorus source and carbon source are carried out first sintering under first sintering temperature, carries out second sintering then under second sintering temperature.
Described first sintering temperature can be 300-450 ℃, and the time of first sintering can be 4-15 hour.Before first sintering, lithium source, source of iron, phosphorus source and carbon source can be warming up to first sintering temperature from normal temperature with 2-20 ℃/minute speed; Behind first sintering, reduce to normal temperature from first sintering temperature with 5-15 ℃/minute speed.
Described second sintering temperature can be 600-800 ℃, and second sintering time can be 10-25 hour.Before second sintering, can be warming up to second sintering temperature from normal temperature with 10-30 ℃/minute speed.Behind second sintering, can reduce to normal temperature with 2-12 ℃/minute speed.
Described inert protective gas can be N 2And/or Ar.
To do further specific descriptions to the present invention by specific embodiment below.
Embodiment 1
With 3047 gram FeC 2O 42H 2O places 280 ℃ vacuum drying oven (vacuum degree 500 handkerchiefs) heating to obtain FeC in 3 hours 2O 4And FeCO 3Mixture, be cooled to normal temperature with 5 ℃/minute speed then.By calculating as can be known FeC in this mixture 2O 4With FeCO 3Mol ratio 1: 3.With above-mentioned mixture that obtains and 626 gram LiCO 3, 1948 the gram NH 4PO 4, 337.6 gram glucose, 4500 gram industrial alcohol mix, and this mixed slurry is placed ball grinder, ball material mass ratio is 2: 1, sealing ball grinder, ball milling 6 hours.The mixed slurry that ball milling is good places 50 ℃ of baking oven oven dry oven dry in 8 hours alcohol.Then, this oven dry material speed with 3 ℃/minute under nitrogen protection is warmed up to 380 ℃,, reduces to normal temperature with 10 ℃/minute speed again 380 ℃ of following sintering 10 hours; Be warmed up to 750 ℃ with 10 ℃/minute speed then,, reduce to normal temperature with 10 ℃/minute speed again, can obtain LiFePO 750 ℃ of following sintering 18 hours 4/ C positive electrode.
The XRD diffraction pattern that adopts this LiFePO 4 that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 1.
Comparative Examples 1
Obtain LiFePO according to the method identical with embodiment 1 4/ C positive electrode, different is, not with FeC 2O 42H 2O is 280 ℃ of heating down, directly with FeC 2O 42H 2O and other material mix.
The XRD diffraction pattern that adopts this LiFePO 4 that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 2.
Embodiment 2
Obtain LiFePO according to the method identical with embodiment 1 4/ C positive electrode, different is, with FeC 2O 42H 2O places 120 ℃ vacuum drying oven (vacuum degree 300 handkerchiefs) heating to obtain FeC in 0.5 hour 2O 4And FeCO 3Mixture, FeC 2O 4With FeCO 3Mol ratio be 1: 1.5.
Embodiment 3
Obtain LiFePO according to the method identical with embodiment 1 4/ C positive electrode, different is, with FeC 2O 42H 2O places 300 ℃ vacuum drying oven (vacuum degree 700 handkerchiefs) heating to obtain FeC in 5 hours 2O 4And FeCO 3Mixture, FeC 2O 4With FeCO 3Mol ratio be 1: 4.
Embodiment 4
Obtain LiFePO according to the method identical with embodiment 1 4/ C positive electrode, different is, with FeC 2O 42H 2O places 200 ℃ vacuum drying oven (vacuum degree 200 handkerchiefs) heating to obtain FeC in 2 hours 2O 4And FeCO 3Mixture, FeC 2O 4With FeCO 3Mol ratio be 1: 2.
Embodiment 5
Obtain LiFePO according to the method identical with embodiment 1 4/ C positive electrode, different is, not with FeC 2O 42H 2The heating product of O directly is 1: 3 FeC with mol ratio as source of iron 2O 4And FeCO 3Mixture and other material mix.
Embodiment 6-10
Embodiment 6-10 is used to measure the performance of the positive electrode that embodiment 1-5 obtains.
Measure the specific capacity of LiFePO 4 according to following steps.
Restrain the positive active material LiFePO that makes by embodiment 1-5 with 100 respectively 4/ C, 3 gram binding agent Kynoar (PVDF) and 2 gram conductive agent acetylene blacks join in the 50 gram N-methyl pyrrolidones, stir, and obtain anode sizing agent.This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, oven dry, roll-in under the 150C then, cuts to make and be of a size of 540 * 43.5 millimeters positive pole, wherein contain the 2.8 gram active component LiFePO that have an appointment 4/ C.
100 gram negative electrode active composition native graphites, 3 gram bonding agent Kynoar, 3 gram conductive agent carbon blacks are joined in the 100 gram N-methyl pyrrolidones, stir, obtain cathode size.This cathode size is coated on the both sides that thickness is 12 microns Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain the 2.6 gram active component native graphites of having an appointment.
Respectively above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF 6Concentration by 1 mol is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in 1: 1 the mixed solvent, this electrolyte is injected the battery aluminum hull with the amount of 3.8g/Ah, lithium rechargeable battery A1-A5 is made in sealing respectively.
The above-mentioned lithium ion A1-A5 battery that makes is placed on test respectively cashier's office in a shop, carries out constant current charge with the 0.2C electric current earlier, the charging upper voltage limit is 3.8 volts, and constant voltage charge is 2.5 hours then; After shelving 20 minutes, be discharged to 3.0 volts with the electric current of 0.2C from 3.8 volts again, the discharge capacity first of record battery, and calculate the specific capacity that positive active material is a LiFePO 4 according to the following equation;
Specific capacity=battery is discharge capacity (MAH)/positive active material weight (gram) first
Measurement result is as shown in table 1.
Comparative Examples 2
This Comparative Examples is used to measure the performance of the positive electrode that Comparative Examples 1 obtains.
Measure the performance of the positive electrode that Comparative Examples 1 obtains according to the method identical with embodiment 6-10, the result is as shown in table 1.
Table 1
The embodiment numbering Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Comparative Examples 2
Specific capacity (MAH/gram) 125 117 115 118 123 106
Fig. 1 is the XRD diffraction pattern of the LiFePO 4 that adopts method of the present invention and prepare, and wherein, the collection of illustrative plates of LiFePO 4 is represented on top, and the collection of illustrative plates of standard LiFePO 4 is represented in the bottom; The XRD diffraction pattern of the LiFePO 4 that Fig. 2 prepares for the method that adopts prior art, wherein, the collection of illustrative plates of LiFePO 4 is represented on top, and the collection of illustrative plates of standard LiFePO 4 is represented at the middle part, and standard Fe is represented in the bottom 2The collection of illustrative plates of P.
As can be seen from Figure 1, adopt the XRD figure spectrum of LiFePO 4 of method of the present invention preparation consistent with standard LiFePO 4 JADE collection of illustrative plates, the thing that material that Fig. 1 surveys has been described is the ferrous lithium thing of pure phosphoric acid phase mutually; As can be seen from Figure 2, adopt the XRD figure spectrum of the LiFePO 4 of control methods (Comparative Examples 1) preparation to have more some assorted peaks, and these assorted peaks are lucky and standard Fe than standard LiFePO 4 JADE collection of illustrative plates 2The collection of illustrative plates unanimity of P, thus there is Fe in the thing of judging material that Fig. 2 surveys in mutually 2The P dephasign.Therefore positive electrode material LiFePO 4 of lithium purity height of the present invention is described.
Data from table 1 as can be seen, the specific capacity of the positive active material LiFePO 4 that the specific capacity of the positive active material LiFePO 4 that embodiment 6-10 records records apparently higher than Comparative Examples 2 illustrates and adopts method of the present invention can significantly improve the specific capacity of the positive active material LiFePO 4 that makes.

Claims (9)

1. the preparation method of a lithium battery positive pole material lithium iron phosphate, this method comprise lithium source, source of iron, phosphorus source and carbon source are mixed and sintering, it is characterized in that described source of iron is FeC 2O 4And FeCO 3Mixture, FeC 2O 4And FeCO 3Mol ratio be 1: 0.5-4.
2. method according to claim 1, wherein, FeC 2O 4And FeCO 3Mol ratio be 1: 1.5-4.
3. method according to claim 1 and 2, wherein, FeC 2O 4And FeCO 3Mixture adopt one of following method preparation:
Method 1: with FeC 2O 4And FeCO 3Mix;
Method 2: heat ferrous oxalate under vacuum condition, heating-up temperature is 100-350 ℃, and be 0.2-6 hour heating time.
4. method according to claim 3, wherein, heating-up temperature is 120-300 ℃, and be 0.5-5 hour heating time, and the pressure under the vacuum condition is the 100-1000 handkerchief.
5. method according to claim 1, wherein, the mol ratio in described source of iron, lithium source and phosphorus source is Fe: Li: P=1: 0.95-1.1: 0.95-1.1, the consumption of carbon source is the 0.5-10 weight % of source of iron, lithium source and phosphorus source total amount.
6. method according to claim 1 or 5, wherein, described lithium source is selected from one or more in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium hydrogen phosphate and the lithium dihydrogen phosphate; Described phosphorus source is selected from one or more in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate and the lithium dihydrogen phosphate; Described carbon source is selected from one or more in glucose, sucrose, starch and the carbon black.
7. method according to claim 1, wherein, the mixed method of described lithium source, source of iron, phosphorus source and carbon source comprises lithium source, source of iron, phosphorus source and carbon source and dispersant ball milling 3-12 hour, dried 2-10 hour down at 30-80 ℃ then, the consumption of dispersant is the 70-120 weight % of source of iron, lithium source, phosphorus source and carbon source total amount.
8. method according to claim 7, wherein, described dispersant is one or more in methyl alcohol, ethanol and the acetone.
9. method according to claim 1, wherein, the method for described sintering is included in the inert protective gas, and lithium source, source of iron, phosphorus source and carbon source are carried out first sintering under first sintering temperature, carries out second sintering then under second sintering temperature; The temperature of described first sintering is 300-450 ℃, and the time of first sintering is 4-15 hour; The temperature of described second sintering is 600-800 ℃, and the time of second sintering is 10-25 hour.
CN2007101434084A 2007-07-31 2007-07-31 Method for preparing lithium battery positive pole material lithium iron phosphate Expired - Fee Related CN101357756B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN2007101434084A CN101357756B (en) 2007-07-31 2007-07-31 Method for preparing lithium battery positive pole material lithium iron phosphate
KR1020097024880A KR20090131680A (en) 2007-07-31 2008-05-05 Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery
EP08734239.0A EP2142473B1 (en) 2007-07-31 2008-05-05 Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery
JP2010512495A JP5181022B2 (en) 2007-07-31 2008-05-05 Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery
PCT/CN2008/070883 WO2009015565A1 (en) 2007-07-31 2008-05-05 Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery
US12/135,128 US20090035204A1 (en) 2007-07-31 2008-06-06 Methods for Synthesizing Lithium Iron Phosphate as a Material for the Cathode of Lithium Batteries

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CN114203989A (en) * 2021-11-30 2022-03-18 五邑大学 FeP/Fe2P/NC composite material and preparation method thereof

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