CN1797823A - Anode material lithium ferric phosphate containing oxygen vacancy in use for secondary battery of lithium ion, and application - Google Patents

Anode material lithium ferric phosphate containing oxygen vacancy in use for secondary battery of lithium ion, and application Download PDF

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CN1797823A
CN1797823A CNA2004101016183A CN200410101618A CN1797823A CN 1797823 A CN1797823 A CN 1797823A CN A2004101016183 A CNA2004101016183 A CN A2004101016183A CN 200410101618 A CN200410101618 A CN 200410101618A CN 1797823 A CN1797823 A CN 1797823A
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oxygen
battery
lithium
iron phosphate
life
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CN100377392C (en
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李泓
黄学杰
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Chemical formula of anode material is LiFe1-xMxPO4-y Nz, where M as Li, Na, K, Ag, Cu; 0<=x<=0.1, 0<y<=1, 0<=z<=0.5, and x, y, z can not be equal to zero at same time; moreover, following conditions are met: (1) when x=0, z=0, then 0<y<=1; (2) when x=0, z is not equal to 0 then y>=3z/2; (3) when z=0, x is not equal to 0, then y>=x/2; (4) when x is not equal to 0, z is not equal to 0, then y>=x/2+3z/2. Furthermore, process for coating carbon on surface of the anode material can be carried out in order to raise electronic and ionic conductivities of anode material. Comparing with current art, the disclosed anode material possesses better performance in high magnification. Combined with regular cathode, electrolyte and diaphragm, the anode material can constitute secondary battery of lithium ion suitable to devices driven by mobile energy sources.

Description

The lithium iron phosphate positive material and uses thereof that is used for the oxygen-containing vacancy of serondary lithium battery
Technical field
The present invention relates to a kind of positive electrode that is used for serondary lithium battery, specifically relate to lithium iron phosphate positive material of a kind of oxygen-containing vacancy that is used for serondary lithium battery and uses thereof.
Background technology
At first in U.S. Pat A 5,910,382, proposed in 1997, with LiFePO by J.B.Goodenough etc. 4Positive electrode as serondary lithium battery.In the same year, M.Armand etc. are at U.S. Pat A6, disclose LiFePO in 514,640 4Carry out the material that mix in the iron position and phosphate potential substitutes.LiFePO 4It is a kind of positive electrode active materials that is mainly used in serondary lithium battery with olivine structural.It is cheap to have the prices of raw and semifnished materials, and storage is abundant, environmentally safe, and when serondary lithium battery was used, security performance was very good, and lithium storage content is higher, and voltage is than advantages such as height.But, LiFePO 4The class material also exists electronic conductivity and the low shortcoming of ionic conductivity.This class material is during as the positive electrode active materials of serondary lithium battery, and the multiplying power property of battery is relatively poor.That is to say that battery is when high current charge-discharge, battery capacity obviously reduces (for example, less than 70%) when charging and discharging with respect to little electric current.
In order to address this problem, obtain positive electrode than highly electron conductive, at document 1:Zhaohui Chen, and J.R.Dahn.Reducing Carbon in LiFePO 4/ C CompositeElectrodes to Maximize Specific Energy, Vo1umetric Energy, andTap Density.J.Electrochem.Soc., 149 (9), A1184-A1189 discloses at LiFePO in (2002) 4The method of coated with carbon or plated metal has been improved the electronics contact between the particle, thereby has improved the electronic conductivity of material.As document 2:Sung-yoon chung, Jasont.Bloking and Yet-ming Chiang.Electronically conductivephospho-olivines as lithium storage electrodes.Nature material, 2, described in the 123-128 (2002), also can adopt the intrinsic electronic conductance that improves material in the method for Li position doping high valence ion.After but the lithium position is substituted by high valence ion, the diffusion admittance of lithium ion will be blocked, and make ionic conductivity lower.The inventor has proposed a kind of chemical formula in application number is the Chinese patent application of 200410031151.x be Li xA yM mN nT tPO 4(M=Fe, Mn), have a material of olivine structural, it is at the ion of Li position doping monovalence with at the ion of Fe position doping monovalence or divalence, and, when Fe position doping monovalent ion, whenever substitute 1 mole Fe atom for the consideration of charge balance, adopt 2 moles substitution atoms, for example LiFe 1-xNa 2xPO 4Thereby, by introducing the intrinsic conductivity that impurity energy level has improved material.
Though these improve the multiplying power property of having improved material really, but in the practical application of battery, particularly in the application of high power battery, for example, when surpassing the discharging and recharging of 5C (roughly be equivalent to 12 minutes batteries fill entirely entirely put), require the high rate performance of material very high, capability retention needs more than 80%, this requires electrode material to have higher intrinsic electronic conductance and ionic conductance simultaneously, and keep electronics contact between the good active material particle, interface stability and transport property are the demands that can not satisfy high-power battery like this and adopt the capability retention of the above-mentioned material that obtains of improving one's methods.
Summary of the invention
The objective of the invention is in order to overcome existing LiFePO 4The class material during as the positive electrode of serondary lithium battery electronic conductivity and ionic conductivity low, adopt carbon to coat and to improve body phase electronic conductance, high valence ion mixes in the lithium position and can not effectively improve the shortcoming of electronic conductance and ionic conductance, increases substantially the material electronics electricity and leads lithium iron phosphate positive material with the oxygen-containing vacancy that is used for serondary lithium battery of ionic conductance by introduce the oxygen room in material thereby provide a kind of.
Another object of the present invention is to provide the purposes of the lithium iron phosphate positive material of the described oxygen-containing vacancy that is used for serondary lithium battery.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of lithium iron phosphate positive material that is used for the oxygen-containing vacancy of serondary lithium battery, its chemical formula is
LiFe 1-xM xPO 4-yN z，
Wherein, M is Li, Na, K, Ag, Cu;
0≤x≤0.1,0＜y≤1,0≤z≤0.5, and x, y, z can not be 0 simultaneously, and satisfy following condition simultaneously:
1) work as x=0, during z=0,0＜y≤1;
2) work as x=0, z ≠ 0 o'clock, y 〉=3z/2;
3) work as z=0, x ≠ 0 o'clock, y 〉=x/2;
4) when x ≠ 0, z ≠ 0 o'clock, y 〉=x/2+3z/2.
The above-mentioned lithium iron phosphate positive material that is used for the oxygen-containing vacancy of serondary lithium battery provided by the invention, can introduce the oxygen room by following several approach:
(1) at LiFePO 4In, introduce the position formation nitrogen phosphate that the N element replaces O, can obtain LiFePO 4-yN z, y=3z/2;
(2) replace with monovalent ion in the Fe position, obtain LiFe 1-xM xPO 4-y, y=x/2;
(3) adopt above-mentioned two kinds of methods of introducing the oxygen room simultaneously, obtain LiFe 1-xM xPO 4-yN z, y=x/2+3z/2;
(4) also can be with LiFePO 4And above-mentioned three kinds of material LiFePO 4-yN z, y=3z/2; LiFe 1-xM xPO 4-y, y=x/2 or LiFe 1-xM xPO 4-yN z, y=x/2+3z/2 is suitably handling under the reducing atmosphere, obtains the material LiFe of oxygen-containing vacancy 1-xM xPO 4-yN z, 0≤x≤0.1,0＜y≤1,0≤z≤1.Work as x=0, during z=0, expression directly obtains the LiFePO of oxygen-containing vacancy 4-y, 0＜y≤1; Work as x=0, z ≠ 0, expression obtains LiFePO 4-yN z, y＞3z/2; When x ≠ 0, z ≠ 0 o'clock, expression obtains LiFe 1-xM xPO 4-yN z, y＞x/2+3z/2.
In semi-conducting material, introduce the oxygen room, will cause the enhancing of electronic conductance in the material, present n type electricity and lead.In LiFePO4, transporting of lithium ion is at PO 4Transport in the passage that tetrahedron is formed, the migration of lithium is subjected to the interactional influence of O.Work as PO 4In the oxygen excalation after, the Coulomb attraction that lithium is subjected to reduces, thereby the mobility of lithium ion in lattice can improve, thus ionic conductivity also can improve.Approach (1) as the aforementioned is when at LiFePO 4The middle N element of introducing, part replaces LiMPO 4Middle PO 4Behind the O element in the group,, after replacing two oxygen atoms, two N atoms will introduce an oxygen room because the valence state of N is more negative than oxygen.Approach (2) as the aforementioned, after the Fe position replaces with equimolar monovalent atom, because charge balance, will there be oxygen defect in the O position.Two monovalent atoms replace two Fe atoms, will produce an oxygen room.Approach (3) can take Fe position monovalent atom to replace and the replacement of O position N atom simultaneously as the aforementioned, introduces more oxygen room.In addition, suitably handling under the reducing atmosphere, oxide material can form the material of anoxic, with pure LiFePO 4Under reducing atmosphere, handle, can obtain LiFePO 4-y, 0＜y≤1.Approach (4) is handled the above-mentioned material of handling through approach (1-3) under reducing atmosphere as the aforementioned, can obtain the more material of oxygen-containing vacancy, the unified LiFe that is expressed as 1-xM xPO 4-yN z, y＞x/2+3z/2.
Because oxygen-containing vacancy in the positive electrode of research, as previously mentioned, the electronic conductivity of material and ionic conductivity can significantly improve, and when using as electrode material in battery, compare existing system, and its high rate capability is excellence more.
In fact, also can be on the basis of the lithium iron phosphate positive material of oxygen-containing vacancy provided by the invention, carry out the coating of carbon handles on the lithium iron phosphate positive material surface of oxygen-containing vacancy provided by the invention, can improve electrically contacting between the particle, further improve the chemical property of material of the present invention in lithium ion battery.
The invention provides the purposes that a kind of lithium iron phosphate positive material with oxygen-containing vacancy is used for serondary lithium battery, make the positive pole of serondary lithium battery, with negative pole, the electrolyte of routine, barrier film is formed serondary lithium battery.Carbon, conducting metal oxide or metal that the conductive additive that uses in the positive pole uses as routine; But the employed active material of negative pole comprises material with carbon element, lithium transition-metal nitride or the lithium ulvospinel of lithium metal, lithium alloy removal lithium embedded; For being full of the barrier film of electrolyte, perhaps be solid or colloidal electrolyte between positive pole and the negative pole, positive pole is burn-on respectively to go between with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.
The LiFePO4 that adopts oxygen-containing vacancy of the present invention is applicable to that as the serondary lithium battery of positive electrode various mobile electronic devices maybe need the equipment of mobile driven by energy, mobile phone for example, notebook computer, portable video recorder, electronic toy, electric tool, electric automobile, hybrid vehicle, electric topedo, fields such as accumulation power supply, and be not limited to this.
Embodiment
The lithium iron phosphate positive material LiFePO of embodiment 1, preparation oxygen-containing vacancy of the present invention 3.998
Positive electrode LiFePO 3.998Can prepare by following steps.At first, take by weighing LiF, FeC at 1: 1: 1 according to mol ratio 2O 42H 2O and NH 4H 2PO 4, behind the mechanical ball milling (rotating speed is 500 rev/mins, 3 hours), with this mixture at high-purity Ar gas/H 2Gas gaseous mixture (H 2The gas volume ratio accounts for 8%) (heat treated step is: be warming up to 400 ℃ with 1 hour from room temperature to protect heat treatment down; at 400 ℃ of constant temperature after 4 hours; with dropping to room temperature in two hours); (rotating speed is 500 rev/mins to ball milling once more; 1 hour) after; mixture once more sintering (sintering step is: be warming up to 600 ℃ with 2 hours from room temperature, at 600 ℃ of constant temperature after 8 hours, with dropping to room temperature in 3 hours.
LiFePO with the grey black that obtains 3.998Positive electrode mixes the formation slurry (wherein at normal temperatures and pressures with the cyclohexane solution of acetylene black and 10% Kynoar (PVDF), active material: acetylene black: the PVDF weight part ratio is 75: 15: 10), evenly be coated on the aluminum substrates, about 2～20 μ m of the film thickness of gained are as the positive pole of simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF 6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The multiplying power testing procedure of simulated battery: at first charge to 4.2V with 30mA/g, the multiplying power current discharge is to 2.0V then, and the capacity of being emitted is the discharge capacity under this multiplying power, and discharge is discharged to 2.0V with 30mA/g after finishing again.Carry out the test of next multiplying power then.The test result of this simulated battery is listed in table 1.
Embodiment 2, the preparation lithium iron phosphate positive material LiFePO that is used for the oxygen-containing vacancy of serondary lithium battery of the present invention 3.7
Method by embodiment 1 prepares the lithium iron phosphate positive material LiFePO that is used for the oxygen-containing vacancy of serondary lithium battery of the present invention 3.7, different is, 400 ℃ of constant temperature 8 hours, 600 ℃ of constant temperature 12 hours.All the other preparation processes are identical with embodiment 1.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFePO of embodiment 3, preparation oxygen-containing vacancy of the present invention 3.5
The lithium iron phosphate positive material LiFePO for preparing oxygen-containing vacancy of the present invention by the method for embodiment 1 3.5, different is, 400 ℃ of constant temperature 12 hours, 600 ℃ of constant temperature 24 hours.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFePO of embodiment 4, preparation oxygen-containing vacancy of the present invention 3.97N 0.02
The lithium iron phosphate positive material LiFePO of oxygen-containing vacancy 3.97N 0.02Can prepare by following steps.At first, according to mol ratio 1: 1: 1: 0.02 takes by weighing LiF, FeC 2O 42H 2O, NH 4H 2PO 4, Li 3N is filling high-purity N 2In the sealing ball grinder of gas behind the mechanical ball milling (rotating speed is 500 rev/mins, 3 hours), with this mixture in high-purity N 2(heat treated step is: be warming up to 400 ℃ with 1 hour from room temperature in heat treatment under the gas shiled; at 400 ℃ of constant temperature after 4 hours; with dropping to room temperature in two hours); (rotating speed is 500 rev/mins to ball milling once more; 1 hour) after; mixture once more sintering (sintering step is: be warming up to 600 ℃ with 2 hours from room temperature, at 600 ℃ of constant temperature after 12 hours, with dropping to room temperature in 3 hours.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFePO of embodiment 5, preparation oxygen-containing vacancy of the present invention 3.25N 0.5
The lithium iron phosphate positive material LiFePO for preparing oxygen-containing vacancy of the present invention by the method for embodiment 4 3.25N 0.5, different is Li in presoma 3The ratio of N is brought up to 0.5M.All the other preparation processes are identical with embodiment 4.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFePO of embodiment 6, preparation oxygen-containing vacancy of the present invention 3N 0.5
The lithium iron phosphate positive material LiFePO for preparing oxygen-containing vacancy of the present invention by the method for embodiment 5 3N 0.5, different is, and in the time lengthening to 8 of 400 ℃ of constant temperature hour, 600 ℃ of constant temperature extend to 24 hours, and used carrier gas is a high-purity N 2Gas/H 2Gas gaseous mixture (H 2The gas volume ratio accounts for 8%), all the other preparation processes are identical with embodiment 5.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 7, preparation oxygen-containing vacancy of the present invention 0.9Na 0.1PO 3.95
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 4 0.9Na 0.1PO 3.95, different is, in presoma, adds NaF, LiF wherein, FeC 2O 42H 2O, NaF, NH 4H 2PO 4Mol ratio is 1: 0.9: 0.1: 1.Carrier gas is a high-purity Ar gas.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 8, preparation oxygen-containing vacancy of the present invention 0.97Li 0.03PO 3.98
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 7 0.97Li 0.03PO 3.98, different is, in presoma, and LiF, FeC 2O 42H 2O, NH 4H 2PO 4Mol ratio is 1: 03: 0.97: 1.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 9, preparation oxygen-containing vacancy of the present invention 0.95K 0.05PO 3.97
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 7 0.95K 0.05PO 3.97, different is, in presoma, adds KF, LiF wherein, FeC 2O 42H 2O, KF, NH 4H 2PO 4Mol ratio is 1: 0.95: 0.05: 1.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 10, preparation oxygen-containing vacancy of the present invention 0.9Cu 0.1PO 3.95
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 7 0.9Cu 0.1PO 3.95, different is, in presoma, adds CuF, LiF wherein, FeC 2O 42H 2O, CuF, NH 4H 2PO 4Mol ratio is 1: 0.9: 0.1: 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 11, preparation oxygen-containing vacancy of the present invention 0.95Na 0.05PO 3.825N 0.1
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 1 0.95Na 0.05PO 3.825N 0.1, different is, 400 ℃ of constant temperature 12 hours, 600 ℃ of constant temperature 24 hours.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 12, preparation oxygen-containing vacancy of the present invention 0.9Cu 0.1PO 3.1N 0.5
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 1 0.9Cu 0.1PO 3.1N 0.5, different is, in presoma, adds CuF, LiF wherein, FeC 2O 42H 2O, CuF, NH 4H 2PO 4Mol ratio is 1: 0.9: 0.1: 1.Carrier gas is a high-purity N 2Gas/H 2Gas gaseous mixture (H 2The gas volume ratio accounts for 8%).400 ℃ of constant temperature 12 hours, 600 ℃ of constant temperature 24 hours.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LiFe of embodiment 13, preparation oxygen-containing vacancy of the present invention 0.9Ag 0.1PO 3.6N 0.2
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 12 0.9Ag 0.1PO 3.6N 0.2, different is, in the presoma, adds AgF, LiF wherein, FeC 2O 42H 2O, AgF, NH 4H 2PO 4Mol ratio is 1: 0.9: 0.1: 1.400 ℃ of constant temperature 6 hours, 600 ℃ of constant temperature 12 hours.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material of embodiment 14, preparation oxygen-containing vacancy of the present invention
LiFe 0.97Na 0.03PO 3.8N 0.1
The lithium iron phosphate positive material LiFe for preparing oxygen-containing vacancy of the present invention by the method for embodiment 13 0.97Na 0.03PO 3.8N 0.1, different is, in the presoma, adds NaF, LiF wherein, FeC 2O 42H 2O, NaF, NH 4H 2PO 4Mol ratio is 1: 0.97: 0.03: 1.400 ℃ of constant temperature 6 hours, 600 ℃ of constant temperature 8 hours.All the other preparation processes are identical with embodiment 1.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The lithium iron phosphate positive material LIFe of the oxygen-containing vacancy of embodiment 15, preparation coated with carbon of the present invention 0.97Na 0.03PO 3.95
The lithium iron phosphate positive material LiFe for preparing the oxygen-containing vacancy of coated with carbon of the present invention by the method for embodiment 7 0.97Na 0.03PO 3.95Different is LiF in the presoma, FeC 2O 42H 2O, NaF, NH 4H 2PO 4Mol ratio is 1: 0.97: 0.03: 1.All the other preparation processes are identical with embodiment 7.Obtaining LiFe 0.97Na 0.03PO 3.95After, with itself and sucrose mechanical mixture (weight ratio is 20: 1), at N 2(heat treated step is down heat treatment of protection: be warming up to 600 ℃ with 3 hours from room temperature, at 600 ℃ of constant temperature after 4 hours, with dropping to room temperature in two hours.Obtain the LiFe of coated with carbon 0.97Na 0.03PO 3.95The percentage by weight of carbon in compound is 1%.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.The lithium iron phosphate positive material LIFe of the oxygen-containing vacancy of embodiment 16, preparation coated with carbon of the present invention 0.97Na 0.03PO 3.95
The lithium iron phosphate positive material LiFe for preparing the oxygen-containing vacancy of coated with carbon of the present invention by the method for embodiment 15 0.97Na 0.03PO 3.95Different is LiFe 0.97Na 0.03PO 3.95The weight ratio of mixing with sucrose is 1: 1, and all the other preparation processes are identical with embodiment 15.Obtain the LiFe of coated with carbon 0.97Na 0.03PO 3.95The percentage by weight of carbon in compound is 20%.The positive pole of simulated battery, negative pole, electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
Table 1, positive electrode LiFe 1-xM xPO 4-yN zComposition and the test result of simulated battery
Embodiment The positive electrode chemical formula LiFe 1-xM xPO 4-yN 2 Discharge capacity
x y z 0.2C 1C 3C 10C
1 LiFePO 3.998 0 0.00 2 0 145 135 120 110
2 LiFePO 3.7· 0 0.3 0 140 130 120 105
3 LiFePO 3.5 0 0.5 0 135 130 125 105
4 LiFePO 3.97N 0.02 0 0.03 0.02 145 130 125 100
5 LiFePO 3.25N 0.5 0 0.75 0.5 142 132 120 98
6 LiFePO 3N 0.5 0 1 0.5 150 140 110 95
7 LiFe 0.9Na 0.1PO 3.95 0.1 0.05 0 150 142 125 102
8 LiFe 0.97Li 0.03PO 3.98 0.03 0.02 0 150 141 130 105
9 LiFe 0.95K 0.05PO 3.97 0.05 0.03 0 145 135 120 100
10 LiFe 0.9Cu 0.1PO 3.95 0.1 0.05 0 142 130 115 105
11 LiFe 0.95Na 0.05PO 3.825N 0.1 0.05 0.17 5 0.1 148 138 124 122
12 LiFe 0.9Cu 0.1PO 3.1N 0.5 0.01 0.9 0.5 160 152 132 120
13 LiFe 0.9Ag 0.1PO 3.6N 0.2 0.1 0.4 0.2 158 140 135 125
14 LiFe 0.97Na 0.03PO 3.8N 0.1 0.03 0.2 0.1 165 150 135 125
15 LiFe 0.97Na 0.03PO 3.95 0.03 0.05 0 160 150 140 130
16 LiFe 0.97Na 0.03PO 3.95 0.03 0.05 0 140 135 120 115
According to the result of table 1 as can be seen, the lithium iron phosphate positive material that is used for the oxygen-containing vacancy of serondary lithium battery of the present invention has all shown the multiplying power property that higher lithium storage content is become reconciled, the LiFePO of general pure phase 4Under the 3C multiplying power, have only 60% raw capacity (90mAh/g), under the multiplying power of 10C, have only the capacity of 70mAh/g.This explanation is by our material design, and the electronic conductance and the ionic conductivity of material improve really.Reality confirms also that to the measurement of the electronic conductance of some material oneself is increased to 10 the electronic conductance of these materials -5～10 -4S/cm is than pure LiFePO 4(10 -10～10 -9S/cm) high several magnitude.

Claims (3)

1, a kind of lithium iron phosphate positive material that is used for the oxygen-containing vacancy of serondary lithium battery, its chemical formula is
LiFe 1-xM xPO 4-yN z，
Wherein, M is Li, Na, K, Ag, Cu;
0≤x≤0.1,0＜y≤1,0≤z≤0.5, and x, y, z can not be 0 simultaneously, and satisfy following condition simultaneously:
1) work as x=0, during z=0,0＜y≤1;
2) work as x=0, z ≠ 0 o'clock, y 〉=3z/2;
3) work as z=0, x ≠ 0 o'clock, y 〉=x/2;
4) when x ≠ 0, z ≠ 0 o'clock, y 〉=x/2+3z/2.
2, the lithium iron phosphate positive material that is used for the oxygen-containing vacancy of serondary lithium battery as claimed in claim 1 is characterized in that, also being included in described chemical formula is LiFe 1-xM xPO 4-yN zThe lithium iron phosphate positive material surface carry out the material that carbon coat to be handled.
3, the purposes of the lithium iron phosphate positive material of a kind of claim 1 or the 2 described oxygen-containing vacancies that are used for serondary lithium battery.
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