CN100336247C - Method for preparing phosphate positive-pole material of lithium-ion cell - Google Patents

Method for preparing phosphate positive-pole material of lithium-ion cell Download PDF

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CN100336247C
CN100336247C CNB2004100034771A CN200410003477A CN100336247C CN 100336247 C CN100336247 C CN 100336247C CN B2004100034771 A CNB2004100034771 A CN B2004100034771A CN 200410003477 A CN200410003477 A CN 200410003477A CN 100336247 C CN100336247 C CN 100336247C
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ion battery
lithium ion
cathode material
phosphate cathode
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CN1677718A (en
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王德宇
黄学杰
陈立泉
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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

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Abstract

The present invention relates to a preparation method of positive electrode material of the phosphate system of a secondary lithium ion battery, which comprises: lithium salt, ferric salt or a precursor of vandic salt and phosphate is uniformly mixed according to stoichiometric proportion, and then the mixture is pretreated at temperature of 200 to 500 DEG C; finally, sintering reaction is carried out at temperature of 400 to 1200 DEG C, and the positive electrode material of the phosphate of a lithium ion battery is obtained. The lithium salt is lithium halide. The method also comprises: the positive electrode material of the phosphate of a lithium ion battery is coated with carbon. The carbon coating material is carbohydrate, acetylene black or graphite; the carbon coating material can be added when the precursor is mixed, or is added when the sintering reaction is carried out, or is added after the sintering reaction is carried out, and sintering is carried out again. The method has simple technology, Li3PO4 can be aovided, and obtained material has high actual capacity.

Description

A kind of preparation method of phosphate cathode material of lithium ion battery
Technical field
The present invention relates to a kind of preparation method of cell positive material, particularly relate to a kind of preparation method of phosphate system positive electrode of secondary lithium battery.
Background technology
The current phosphate system positive electrode that is usually used in secondary lithium battery mainly contains LiFePO 4And Li 3V 2(PO 4) 3Propose LiFePO in patent USA 5,910,382 at J.B.Goodenough in 1997 etc. 4Positive electrode as novel lithium ion battery, this material feedstock is cheap, free from environmental pollution, security performance is good and theoretical capacity higher (170mAhg-1), but the electrical conductivity of this material is very low simultaneously, high rate performance is poor, so in application limitation is arranged, never is widely used.After the 196th the electrochemistry meeting of holding in Hawaii in 1999, M.Armand etc. publish an article and claim carbon to coat can to improve the performance of material greatly, thereby make LiFePO 4Become the focus of research once more.
At present, LiFePO 4And Li 3V 2(PO 4) 3The preparation method mainly be high temperature solid-state method, the lithium salts of its use mostly is Li 2CO 3But, use Li 2CO 3As feedstock production LiFePO 4, technological requirement is very harsh, is difficult to obtain gratifying result; And use Li 2CO 3Be easy to form Li as raw material 3PO 4, and Li 3PO 4The inevitable actual capacity that reduce material greatly of formation, make the actual capacity of battery only be 120mAhg -1About.
Summary of the invention
The objective of the invention is to overcome prior art and prepare LiFePO 4And Li 3V 2(PO 4) 3The time technological requirement very harsh, form Li easily 3PO 4, the defective that the actual capacity of battery material is low, thus provide a kind of technology simple, can avoid forming Li 3PO 4, material the preparation method of phosphate cathode material of the high lithium ion battery of actual capacity.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of preparation method of phosphate cathode material of lithium ion battery, comprise following step:
1) mixes presoma: lithium salts, molysite or vanadic salts, phosphate are mixed by stoichiometric proportion;
2) preliminary treatment: the presoma that step 1) is mixed is handled 0.5～24h in 200～500 ℃ in protective atmosphere, grind behind the natural cooling, obtains dusty material;
3) sintering reaction: will be through step 2) pretreated dusty material is handled 4～48h in 400～1200 ℃ in protective atmosphere, obtains the phosphate cathode material of lithium ion battery.
Lithium salts in the described step 1) is a lithium halide, comprises LiF, LiCl, LiBr and LiI.
Described step 1) molysite in is FeC 2O 4NH 2O, Fe 2(C 2O 4) 3NH 2O, Fe 3(PO 4) 2NH 2O, FePO 4NH 2O, FeO, Fe 2O 3, Fe 3O 4Or Fe (NO 3) 3NH 2O.
Described step 1) phosphate in is NH 4H 2PO 4Or (NH 4) 2HPO 4, (NH 4) 3PO 4Or P 2O 5
Described step 1) vanadic salts in is V 2O 5, VO 2, V 2O 3Or NH 4VO 3
Described step 2) and 3) protective atmosphere be non-oxidizing gas, comprise CO 2, N 2, Ar, H 2, Ar-H 2(volume ratio is 92: 8) gaseous mixture.
Described step 3) sintering LiFePO 4Temperature be 400～900 ℃.
Described step 3) sintering Li 3V 2(PO 4) 3Temperature be 600～1200 ℃.
The invention provides the preparation method of the phosphate cathode material of another kind of lithium ion battery, as stated above, in step 1), also add carbon encapsulated material, the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight, obtains the phosphate cathode material of the lithium ion battery of carbon coating then through preliminary treatment, sintering reaction.
Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
The invention provides also a kind of preparation method of phosphate cathode material of lithium ion battery, as stated above, will be before step 3) through step 2) pretreated material adds carbon encapsulated material, the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight, obtains the phosphate cathode material of the lithium ion battery of carbon coating then through sintering reaction.
Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
The invention provides the preparation method of the phosphate cathode material of another lithium ion battery; as stated above; after step 3), add carbon encapsulated material; the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight; in protective atmosphere, handle 2～20h in 400～900 ℃ then, obtain the phosphate cathode material of lithium ion battery.
Described protective atmosphere is a non-oxidizing gas, comprises CO 2, N 2, Ar, H 2, Ar-H 2(volume ratio is 92: 8) gaseous mixture.
Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
The preparation method of the phosphate cathode material of lithium ion battery provided by the invention compared with the prior art, its advantage is: adopt lithium halide to prepare LiFePO for the lithium source 4And Li 3V 2(PO 4) 3, process conditions are relatively simple, and can avoid Li 3PO 4The formation of dephasign is easy to obtain pure phase LiFePO 4And Li 3V 2(PO 4) 3Thereby the actual capacity height of the material that obtains is shown in example 1,3,6,7.
Description of drawings
Fig. 1 is the 2nd all charging and discharging curves of the embodiment of the invention 1;
Fig. 2 is the 20th all charging and discharging curves of the embodiment of the invention 2;
Fig. 3 is the 2nd all charging and discharging curves of the embodiment of the invention 3;
Fig. 4 is the 2nd all charging and discharging curves of the embodiment of the invention 4;
Fig. 5 is the 2nd all charging and discharging curves of the embodiment of the invention 5;
Fig. 6 is the cycle performance curve of the embodiment of the invention 1,2,3,4,5; Wherein: " ■-" is the cycle performance curve of embodiment 1; "-▲-" be the cycle performance curve of embodiment 1; "-◆-" be the cycle performance curve of embodiment 1; " ★-" is the cycle performance curve of embodiment 1; "-●-" be the cycle performance curve of embodiment 1.
Embodiment
Embodiment 1,
With LiF, FeC 2O 42H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon shield, 200 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At argon shield, 700 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of lithium ion battery 4
This LiFePO 4The charging and discharging curve in the 2nd week see Fig. 1, cyclicity is seen Fig. 6, charging and discharging currents is 10mA/g.
Embodiment 2,
With LiF, FeC 2O 42H 2O and (NH 4) 2HPO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 26g sucrose, mixture is mixed;
Under argon shield, 400 ℃, carry out preliminary treatment 8h then, behind the natural cooling, grind again;
At argon shield, 700 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The charging and discharging curve in the 20th week see Fig. 2, cyclicity is seen Fig. 6, charging and discharging currents is 10mA/g.
Embodiment 3,
With LiF, Fe 3(PO 4) 25H 2O and (NH 4) 3PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon shield, 500 ℃, carry out preliminary treatment 0.5h then, behind the natural cooling, grind again;
At argon shield, 600 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material LiFePO of lithium ion battery 4
This LiFePO 4The charging and discharging curve in the 2nd week see Fig. 3, cyclicity is seen Fig. 6, charging and discharging currents is 10mA/g.
Embodiment 4,
With LiF, Fe 3(PO 4) 25H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 50g sucrose, mixture is mixed;
Under argon shield, 500 ℃, carry out preliminary treatment 0.5h then, behind the natural cooling, grind again;
At argon shield, 600 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The charging and discharging curve in the 2nd week see Fig. 4, cyclicity is seen Fig. 6, charging and discharging currents is 10mA/g.
Embodiment 5,
With LiF, V 2O 5And NH 4H 2PO 4By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under hydrogen shield, 300 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At hydrogen shield, 850 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material Li of lithium ion battery 3V 2(PO 4) 3
This Li 3V 2(PO 4) 3The 2nd all charging and discharging curves see Fig. 5, cyclicity is seen Fig. 6, charging and discharging currents is 12mA/g.
Embodiment 6,
With LiF, Fe 2(C 2O 4) 35H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 1g starch, mixture is ground 4h in high-energy ball milling, mix;
Under argon shield, 200 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At argon shield, 500 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 7,
With LiF, Fe 3(PO 4) 25H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 15g acetylene black, mixture is ground 4h in high-energy ball milling, mix;
Under argon shield, 200 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At argon shield, 400 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 8,
With LiCl, Fe 2O 3And P 2O 5By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 0.1g sucrose, mixture is mixed;
Under argon shield, 400 ℃, carry out preliminary treatment 8h then, behind the natural cooling, grind again;
At argon shield, 500 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 9,
With LiBr, FeO and (NH 4) 3PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 2g acetylene black, mixture is ground 4h in high-energy ball milling, mix;
Under argon shield, 450 ℃, carry out preliminary treatment 1h then, behind the natural cooling, grind again;
At argon shield, 900 ℃ of lower sintering 4h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 10,
With LiF, Fe 3O 4And NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 10g acetylene black, mixture is mixed;
Under nitrogen protection, 400 ℃, carry out preliminary treatment 5h then, behind the natural cooling, grind again;
At nitrogen protection, 900 ℃ of lower sintering 8h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 11,
With LiI3H 2O, FePO 45H 2O and (NH 4) 2HPO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 5g graphite, mixture is mixed;
Under carbon-dioxide protecting, 400 ℃, carry out preliminary treatment 6h then, behind the natural cooling, grind again;
At carbon-dioxide protecting, 600 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 12,
With LiF, Fe 3O 4And NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, every mole of LiFePO 4Add 15g glucose, mixture is mixed;
Under argon shield, 400 ℃, carry out preliminary treatment 6h then, behind the natural cooling, grind again;
At argon shield, 700 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 13,
With LiCl, Fe 3(PO 4) 25H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon hydrogen gaseous mixture (volume ratio is 92: 8) protection, 400 ℃, carry out preliminary treatment 8h then, behind the natural cooling, grind again;
At argon hydrogen gaseous mixture (volume ratio is 92: 8) protection, 700 ℃ of lower sintering 24h, cooling obtains LiFePO naturally at last 4
According to every mole of LiFePO 4The ratio of 10g acetylene black adds acetylene black the LiFePO of gained 4In;
At argon hydrogen gaseous mixture (volume ratio is 92: 8) protection, 700 ℃ of lower sintering 6h, naturally cool off, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 14,
With LiBrH 2O, Fe (NO 3) 39H 2O and (NH 4) 3PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon shield, 200 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At argon shield, 700 ℃ of lower sintering 24h, cooling obtains LiFePO naturally at last 4
According to every mole of LiFePO 4The ratio of 30g graphite adds graphite the LiFePO of gained 4In;
At argon hydrogen gaseous mixture (volume ratio is 92: 8) protection, 400 ℃ of lower sintering 20h, naturally cool off, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 15,
With LiIH 2O, Fe (NO 3) 35H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon shield, 400 ℃, carry out preliminary treatment 8h then, behind the natural cooling, grind again;
At argon shield, 750 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
According to every mole of LiFePO 4The ratio of 30g sucrose adds sucrose the LiFePO of gained 4In;
At argon hydrogen gaseous mixture (volume ratio is 92: 8) protection, 900 ℃ of lower sintering 2h, naturally cool off, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 16,
With LiF, FePO 42H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and mixture is ground 30min in agate mortar, mixes;
Under argon shield, 300 ℃, carry out preliminary treatment 20h then, naturally after the cooling, by every mole of LiFePO 4Add 15g starch, grind again;
At argon shield, 800 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of the lithium ion battery of carbon coating 4
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 17,
With LiF, FePO 42H 2O and (NH 4) 2HPO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and mixture is ground 30min in agate mortar, mixes;
Under argon shield, 400 ℃, carry out preliminary treatment 16h then, behind the natural cooling, grind again;
According to every mole of LiFePO 4Add 1g sucrose, mixture is mixed;
At argon shield, 750 ℃ of following sintering 20h, natural cooling,
This carbon coats LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Embodiment 18,
With LiF, V 2O 5(NH 4) 2HPO 4By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under hydrogen shield, 200 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At hydrogen shield, 600 ℃ of lower 48h that process, naturally cooling obtains the nature cooling, obtains the phosphate cathode material Li of lithium ion battery at last 3V 2(PO 4) 3
This Li 3V 2(PO 4) 3The 1st week and the discharge capacity in the 20th week list in table 1.
Embodiment 19,
With LiCl, NH 4VO 3(NH 4) 3PO 4By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Carry out preliminary treatment 0.5h argon shield, 500 ℃ then, behind the natural cooling, grind again;
At argon shield, 1200 ℃ of lower sintering 4h, naturally cool off at last, obtain the phosphate cathode material Li of lithium ion battery 3V 2(PO 4) 3
This Li 3V 2(PO 4) 3The 1st week and the discharge capacity in the 20th week list in table 1, charging and discharging currents is 12mA/g.
Embodiment 20,
With LiBrH 2O, VO 2And P 2O 5By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Carry out preliminary treatment 12h argon shield, 350 ℃ then, behind the natural cooling, grind again;
At argon shield, 850 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material Li of lithium ion battery 3V 2(PO 4) 3
This Li 3V 2(PO 4) 3The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 12mA/g.
Embodiment 21,
With LiI3H 2O, V 2O 3And NH 4H 2PO 4By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Carry out preliminary treatment 24h nitrogen protection, 200 ℃ then, behind the natural cooling, grind again;
At nitrogen protection, 1000 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material Li of lithium ion battery 3V 2(PO 4) 3
This Li 3V 2(PO 4) 3The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 12mA/g.
Table 1
Material 2 nd (mAh/g) 10 th (mAh/g) Material 2 nd (mAh/g) 10 th (mAh/g)
Comparative example 1 118.6 115.5 Embodiment 13 155.7 154.6
Comparative example 2 78.6 72.1 Embodiment 14 158.2 157.8
Embodiment 6 155.9 154.1 Embodiment 15 160.5 161.1
Embodiment 7 148.7 147.9 Embodiment 16 161.1 161.5
Embodiment 8 142.7 134.6 Embodiment 17 161.0 161.3
Embodiment 9 145.2 144.6 Embodiment 18 124.5 125.4
Embodiment 10 147.8 145.6 Embodiment 19 125.2 125.5
Embodiment 11 160.6 159.8 Embodiment 20 120.4 123.5.
Embodiment 12 160.8 161.0 Embodiment 21 120.6 123.8
Comparative example 1
With Li 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4By Li: Fe: P=1: 1: 1 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under argon shield, 400 ℃, carry out preliminary treatment 8h then, behind the natural cooling, grind again;
At argon shield, 600 ℃ of lower sintering 24h, naturally cool off at last, obtain the phosphate cathode material LiFePO of lithium ion battery 4
This material LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 10mA/g.
Comparative example 2
With Li 2CO 3, V 2O 5And NH 4H 2PO 4By Li: V: P=3: 2: 3 stoichiometric proportion takes by weighing, and grinds 30min in agate mortar, mixes;
Under hydrogen shield, 300 ℃, carry out preliminary treatment 24h then, behind the natural cooling, grind again;
At hydrogen shield, 850 ℃ of lower sintering 48h, naturally cool off at last, obtain the phosphate cathode material Li of lithium ion battery 3V 2(PO 4) 3
This material LiFePO 4The 2nd, 10 all discharge capacities list in table 1, charging and discharging currents is 12mA/g.
Can be found by above-described embodiment and comparative example, when using lithium halide to prepare LiFePO 4And Li 3V 2(PO 4) 3The time, the actual capacity of resulting materials does not form lithium phosphate far above the material that uses the lithium carbonate preparation when its reason is used lithium halide exactly.

Claims (10)

1, a kind of preparation method of phosphate cathode material of lithium ion battery comprises following step:
1) mixes presoma: LiF, molysite or vanadic salts, phosphate are mixed by stoichiometric proportion;
2) preliminary treatment: the presoma that step 1) is mixed is handled 0.5～24h in 200～500 ℃ in protective atmosphere, grind behind the natural cooling, obtains dusty material;
3) sintering reaction: will be through step 2) pretreated dusty material is handled 4～48h in 400～1200 ℃ in protective atmosphere, obtains the phosphate cathode material of lithium ion battery.
2, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: the molysite described step 1) is FeC 2O 4NH 2O, Fe 2(C 2O 4) 3NH 2O, Fe 3(PO 4) 2NH 2O, FePO 4NH 2O, FeO, Fe 2O 3, Fe 3O 4Or Fe (NO 3) 3NH 2O.
3, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: the phosphate described step 1) is NH 4H 2PO 4, (NH 4) 2HPO 4, (NH 4) 3PO 4Or P 2O 5
4, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: the vanadic salts described step 1) is V 2O 5, VO 2, V 2O 3Or NH 4VO 3
5, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: described step 2) and 3) protective atmosphere be non-oxidizing gas, comprise CO 2, N 2, Ar, H 2, Ar-H 2Gaseous mixture.
6, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: described step 3) sintering LiFePO 4Temperature be 400～900 ℃.
7, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1 is characterized in that: described step 3) sintering Li 3V 2(PO 4) 3Temperature be 600～1200 ℃.
8, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, also comprise: also add carbon encapsulated material in described step 1), the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight; Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
9, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, will be before described step 3) through step 2) pretreated material adds carbon encapsulated material, and the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight; Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
10, the preparation method of the phosphate cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, after described step 3), add carbon encapsulated material, the addition of carbon encapsulated material is 0.01～20wt% that the amount of carbon accounts for the positive electrode gross weight, in protective atmosphere, handle 2～20h in 400～900 ℃ then, obtain the phosphate cathode material of lithium ion battery;
Described protective atmosphere is a non-oxidizing gas, comprises CO 2, N 2, Ar, H 2, Ar-H 2Gaseous mixture;
Described carbon encapsulated material is carbohydrate, acetylene black or graphite.
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