CN100440593C - Iron lithium phosphate material used for lithium ion battery and its manufacturing method - Google Patents
Iron lithium phosphate material used for lithium ion battery and its manufacturing method Download PDFInfo
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- CN100440593C CN100440593C CNB2004100720704A CN200410072070A CN100440593C CN 100440593 C CN100440593 C CN 100440593C CN B2004100720704 A CNB2004100720704 A CN B2004100720704A CN 200410072070 A CN200410072070 A CN 200410072070A CN 100440593 C CN100440593 C CN 100440593C
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Abstract
The present invention relates to lithium iron phosphate materials used for a lithium ion battery and a manufacture method of the lithium iron phosphate materials. The lithium iron phosphate materials are manufactured by adopting the method that the diameter of the carbon or the metal fibre is controlled to 100 to 300 nm in raw materials composed of lithium, a compound doped with ions, ferric iron, phosphate radical, carbon materials, carbon or metal fibre, length is controlled to 10 to 20 mu m, the lithium bit doping valence of lithium iron phosphate is larger than +2-+4 of the lithium bit doping valence of the ions, and the content of the carbon materials in the manufactured lithium iron phosphate is reduced greatly under a precondition that electronic conductivity is not reduced; because the specific surface area of the carbon materials is selected from 30 to 80m<2>/g, the tap density of the materials is effectively improved, and great convenience is brought for the subsequent processing of an electrode smear. The lithium iron phosphate materials prepared by the present invention have the advantages of low cost and simple technological operation and are easy to magnify production.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries technical field, particularly relate to a kind of iron lithium phosphate material used for lithium ion battery manufacture method.
Background technology
At present, lithium-ions battery generally is subjected to people and welcomes because of it has the good characteristics of high-energy-density, high-specific-power and high-temperature behavior.Commercial anode material for lithium-ion batteries adopts cobalt acid lithium more than 90%, but high and safety issue has limited its application in capacity and high power lithium ion cell greatly because of its price.In recent years, a kind of new type lithium ion battery positive electrode-LiFePO4 because it can overcome above-mentioned deficiency, and is extensively developed.
Application No. US 2003/0077514 A1 discloses a kind of LiFePO4 manufacture method, this method is raw material with the trivalent iron salt, at iron position doped metal ion, in raw material, mix material with carbon element, has excellent high power charging-discharging characteristic, but make tap density on the low side because of having added more carbon black in this material, bring difficulty for the electrode processing that will make.
Summary of the invention
The present invention provides a kind of iron lithium phosphate material used for lithium ion battery manufacture method for solving problems of the prior art.
The purpose of this invention is to provide that a kind of carbon content is low, tap density is big, make electrode be easy to process and have a kind of iron lithium phosphate material used for lithium ion battery manufacture method of excellent electrical.
The present invention adopts following technical scheme:
The iron lithium phosphate material used for lithium ion battery manufacture method, comprise the lithium source, the compound of dopant ion, the ferric iron source that contains ferric iron compound, the phosphoric acid root of phosphoric acid radical compound, material with carbon element, carbon or metallic fiber mix the back and constitute raw material, described lithium source, the dopant ion compound, ferric iron source, phosphoric acid root atomic concentration is than counting Li by 100% purity: M: Fe: P=0.9-0.99: 0.01-0.1: 1: 1, described M is the dopant ion compound of chemical valence+2-+4, described material with carbon element addition adds 6.6-9g by 1 mole of ferric iron source to be calculated, and described material with carbon element specific area is 30-80m
2/ g; The diameter of described carbon or metallic fiber is that 100-300nm, length are 10-20 μ m, and its content is characterized in comprising following technical process for generating the 1-5% of LiFePO4 weight:
(1) is that the absolute ethyl alcohol of 5-15% dissolves in deionized water with volume ratio, makes the absolute ethyl alcohol aqueous solution;
(2) described lithium source, chemical valence are put into the described absolute ethyl alcohol aqueous solution respectively for dopant ion compound, ferric iron source, phosphoric acid root, material with carbon element, carbon or the metallic fiber of+2-+4, with organic acid it are transferred to into the mixed liquor that the pH value is 4-6;
(3) under 20-50 ℃ of temperature, the compound, ferric iron source, phosphoric acid root, material with carbon element, carbon or the metallic fiber that stir lithium source, dopant ion make its compound dissolving;
(4) in whipping process, temperature is risen to 50-100 ℃, until the solution evaporate to dryness;
(5) with the atomic concentration of 100% purity meter behind the evaporate to dryness than being Li: M: Fe: P=0.9-0.99: 0.01-0.1: 1: 1 described lithium source, the compound of dopant ion, ferric iron source, phosphoric acid root, add by 1 mole of ferric iron source that 6.6-9g calculates and specific area is 30-80m
2The material with carbon element of/g, the carbon or the metallic fiber that generate the 1-5% of LiFePO4 weight mix the back grinding, put into inert atmosphere, with the speed of 1-5 ℃/min, rise to 300-500 ℃ earlier, in this temperature range, kept 2-8 hour, rise to 700-850 ℃ with identical speed again, and in this temperature range, be incubated 2-10 hour, and reduce to normal temperature with identical speed at last, taking-up promptly becomes iron lithium phosphate material used for lithium ion battery after grinding.
The iron lithium phosphate material used for lithium ion battery manufacture method can also adopt following technical measures to realize:
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: the compound of described dopant ion be mix in the compound of chemical valence+2-+4 ion, described (5) material that grinds the back and pH value for the organic acid of 4-6 by wet mixing or do to drift along or through and synthesize solid matter; Grinding in described (5) is for being 20-5 with mass ratio: 1 agate ball and described solid matter are inserted container, are to carry out ball milling under the 130-250rpm condition in dry air atmosphere and rotating speed, and the described ball milling time is 0.5-10 hour;
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described material with carbon element is a carbon black.
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described lithium source is selected from lithium chloride, lithium fluoride, lithium sulfide, lithium carbonate, lithium nitrate, lithium phosphate, lithium acetate or lithium hydroxide.
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described phosphoric acid root is selected from ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described ferric iron source is selected from ferric oxalate or di-iron trioxide.
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described dopant ion is selected from B
3+, Al
3+, Mg
2+, Ca
2+, Ba
2+, Zn
2+, Ti
4+, Cr
3+Or V
3+, and be entrained on the lithium position.
The iron lithium phosphate material used for lithium ion battery manufacture method is characterized in: described metallic fiber is nickel, copper, iron or zinc fiber.
The manufacture method of iron lithium phosphate material used for lithium ion battery is characterized in: described inert atmosphere is nitrogen or argon gas.
Advantage and good effect that the present invention has are: owing to added nano-scale carbon or metallic fiber, while is at the ion of the lithium position doping chemical valence+2-+4 of LiFePO4, under the prerequisite that does not reduce electronic conductivity, greatly reduce the content of material with carbon element in the LiFePO4 that makes; Owing to found out the specific area of the material with carbon element that plays the reducing agent effect and the OK range of addition, avoided working as the material with carbon element specific area less than 30m
2During/g, reduction effect is relatively poor, greater than 80m
2During/g, the problem that the material that makes is bulk has improved the tap density of material effectively, for the processing of subsequent electrode smear has brought very big convenience.Contrast with Application No. US2003/0077514A1 disclosed method, in the anode thin film electrode made from LiFePO4, conductive agent and bonding agent, the weight ratio of carbon class conductive agent has dropped to below 6.5% from 15%, but first discharge capacity from less than 150mAh/g to greater than 150mAh/g, improved electrical property.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, enumerate following examples now:
Embodiment 1: a kind of manufacture method of iron lithium phosphate material used for lithium ion battery, lithium source, source of iron, phosphoric acid root and dopant oxidation magnesium are all by 100% purity meter, and weighing the 0.98mol molecular formula is CH
3COOLi.2H
2Lithium acetate 99.902 grams of O, molecular formula are 0.02mol magnesium oxide 0.806 gram of MgO, and molecular formula is Fe
2(C
2O
4)
3.5H
20.5mol ferric oxalate 232.92 grams of O, molecular formula is (NH
4)
2HPO
41.0mol diammonium hydrogen phosphate 132.06 gram; Carbon black 7.5 grams; diameter is 150nm; long carbon fiber 6.332 grams for 10-20 μ m; put into the absolute ethyl alcohol deionized water that 600ml accounts for aqueous solution cumulative volume 10% respectively; add the acetum of 10% weight ratio and transfer solution PH to 5; be stirred well to the lithium source in 40 ℃; source of iron; phosphoric acid root and the dissolving of magnesium source compound; then under 80 ℃ with aqueous solution evaporate to dryness; with the lithium source behind the evaporate to dryness; the phosphoric acid root; ferric iron source; the magnesium source; material with carbon element; carbon fiber mixes the back and grinds; put into the high-purity argon gas protection; speed with 2 ℃/min; rise to 450 ℃ earlier; and under this temperature, kept 6 hours, rise to 750 ℃ with identical speed again, and under this temperature, be incubated 8 hours; reduce to normal temperature with identical speed at last; promptly become iron lithium phosphate material used for lithium ion battery after taking out grinding, this material is through the weightlessness analysis, and wherein the weight ratio of carbon containing is 4.2%.
Embodiment 2: a kind of manufacture method of iron lithium phosphate material used for lithium ion battery, weighing the 0.98mol molecular formula is CH
3COOLi.2H
2Lithium acetate 99.902 grams of O, molecular formula are 0.02mol magnesium oxide 0.806 gram of MgO, and molecular formula is Fe
2(C
2O
4)
3.5H
20.5mol ferric oxalate 232.92 grams of O, molecular formula is (NH
4)
2HPO
41.0mol diammonium hydrogen phosphate 132.06 gram; carbon black 7.5 grams; diameter is 150nm; long carbon fiber 6.332 grams for 10-20 μ m; ethanedioic acid 15 grams and 4800 gram agate balls are put into the agate jar in the lump; under dry air, mixed 4 hours with 150rpm rotating speed ball milling; mixture is put into the corundum boat; under the high-purity argon gas protection, be warming up to 450 ℃ with 2 ℃/min; and under this temperature, kept 6 hours; be warming up to 750 ℃ with identical speed again, and under this temperature, kept 8 hours, be cooled to room temperature with identical speed at last.Take out material, after the hand lapping, promptly become the lithium-ions battery LiFePO 4 material, this material is through the weightlessness analysis, and wherein the weight ratio of carbon containing is 4.4%.
The iron lithium phosphate material used for lithium ion battery that above-mentioned two kinds of methods are made, button 2430 type batteries are adopted in its electrical property evaluation, negative pole is that diameter is 20mm, the metal lithium sheet of thick 1mm, anodal LiFePO4 and the bonding agent Kynoar that is made by embodiment 1 or embodiment 2 formed, their mass ratio is 95: 5, the manufacturing process of anode thin film electrode is: the n-methlpyrrolidone solution that the LiFePO4 that makes and weight ratio are 7.5% Kynoar is made slurry, be coated on the aluminum foil current collector and dry, roll extrusion, make the thick positive plate that is about 110 μ m, be the positive pole of the disk of 20mm from wherein taking out diameter then as button 2430 type batteries, barrier film Celgard 2400, EC in the electrolyte: 1: 1 1M LiPF6+EC/DMC of DMC volume ratio, be assembled into behind the lithium battery at 3-4.2V with 0.3mA constant current impulse electricity, the discharge capacity representative value reaches 155mAh/g first, and circulating after 10 times is 150mAh/g.
Claims (9)
1. iron lithium phosphate material used for lithium ion battery manufacture method, comprise the lithium source, the compound of dopant ion, the ferric iron source that contains ferric iron compound, the phosphoric acid root of phosphoric acid radical compound, material with carbon element, carbon or metallic fiber mix the back and constitute raw material, described lithium source, the dopant ion compound, ferric iron source, phosphoric acid root atomic concentration is than counting Li by 100% purity: M: Fe: P=0.9-0.99: 0.01-0.1: 1: 1, described M is the dopant ion compound of chemical valence+2-+4, described material with carbon element addition adds 6.6-9g by 1 mole of ferric iron source to be calculated, and described material with carbon element specific area is 30-80m
2/ g; The diameter of described carbon or metallic fiber is that 100-300nm, length are 10-20 μ m, and its content is characterized in that comprising following technical process for generating the 1-5% of LiFePO4 weight:
(1) is that the absolute ethyl alcohol of 5-15% dissolves in deionized water with volume ratio, makes the absolute ethyl alcohol aqueous solution;
(2) described lithium source, chemical valence are put into the described absolute ethyl alcohol aqueous solution respectively for dopant ion compound, ferric iron source, phosphoric acid root, material with carbon element, carbon or the metallic fiber of+2-+4, with organic acid it are transferred to into the mixed liquor that the pH value is 4-6;
(3) under 20-50 ℃ of temperature, the compound, ferric iron source, phosphoric acid root, material with carbon element, carbon or the metallic fiber that stir lithium source, dopant ion make its compound dissolving;
(4) in whipping process, temperature is risen to 50-100 ℃, until the solution evaporate to dryness;
(5) with the atomic concentration of 100% purity meter behind the evaporate to dryness than being Li: M: Fe: P=0.9-0.99: 0.01-0.1: 1: 1 described lithium source, the compound of dopant ion, ferric iron source, phosphoric acid root, add by 1 mole of ferric iron source that 6.6-9g calculates and specific area is 30-80m
2The material with carbon element of/g, the carbon or the metallic fiber that generate the 1-5% of LiFePO4 weight mix the back grinding, put into inert atmosphere, with the speed of 1-5 ℃/min, rise to 300-500 ℃ earlier, in this temperature range, kept 2-8 hour, rise to 700-850 ℃ with identical speed again, and in this temperature range, be incubated 2-10 hour, and reduce to normal temperature with identical speed at last, taking-up promptly becomes iron lithium phosphate material used for lithium ion battery after grinding.
2. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that:
The compound of described dopant ion be mix in the compound of chemical valence+2-+4 ion, described (5) material that grinds the back and pH value for the organic acid of 4-6 by wet mixing or do to drift along or through and synthesize solid matter;
Grinding in described (5) is for being 20-5 with mass ratio: 1 agate ball and described solid matter are inserted container, are to carry out ball milling under the 130-250rpm condition in dry air atmosphere and rotating speed, and the described ball milling time is 0.5-10 hour.
3. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described material with carbon element is a carbon black.
4. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described lithium source is selected from lithium chloride, lithium fluoride, lithium sulfide, lithium carbonate, lithium nitrate, lithium phosphate, lithium acetate or lithium hydroxide.
5. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described phosphoric acid root is selected from ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
6. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described ferric iron source is selected from ferric oxalate or di-iron trioxide.
7. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described dopant ion is selected from B
3+, Al
3+, Mg
2+, Ca
2+, Ba
2+, Zn
2+, Ti
4+, Cr
3+Or V
3+, and be entrained on the lithium position.
8. iron lithium phosphate material used for lithium ion battery manufacture method according to claim 1 is characterized in that: described metallic fiber is nickel, copper, iron or zinc fiber.
9. the manufacture method of iron lithium phosphate material used for lithium ion battery according to claim 1, it is characterized in that: described inert atmosphere is nitrogen or argon gas.
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|---|---|---|---|
| CNB2004100720704A CN100440593C (en) | 2004-09-24 | 2004-09-24 | Iron lithium phosphate material used for lithium ion battery and its manufacturing method |
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| CNB2004100720704A CN100440593C (en) | 2004-09-24 | 2004-09-24 | Iron lithium phosphate material used for lithium ion battery and its manufacturing method |
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| CN100440593C true CN100440593C (en) | 2008-12-03 |
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| CN100491239C (en) * | 2006-11-24 | 2009-05-27 | 横店集团东磁股份有限公司 | Preparation method of lithium iron phosphate as lithium ion battery anode material and product thereof |
| CN101364643B (en) * | 2008-07-18 | 2010-06-02 | 杭州赛诺索欧电池有限公司 | Boron containing lithium iron phosphate/carbon composite material and preparation thereof |
| CN102013489B (en) * | 2010-10-28 | 2013-01-02 | 河北工业大学 | Metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof |
| CN102275891A (en) * | 2011-07-19 | 2011-12-14 | 彩虹集团公司 | Method for preparing ferrous-phosphate-based lithium salt material through high-pressure liquid phase preparation |
| CN102522552A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Preparation method for doping lithium iron phosphate at lithium position |
| CN106252644A (en) * | 2016-08-26 | 2016-12-21 | 浙江长兴金太阳电源有限公司 | A kind of preparation method of lithium ion battery thulium doped titanic acid lithium anode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004001881A2 (en) * | 2002-06-21 | 2003-12-31 | Umicore | Carbon-coated li-containing powders and process for production thereof |
| JP2004031131A (en) * | 2002-06-26 | 2004-01-29 | Sony Corp | Nonaqueous electrolyte liquid secondary battery |
| CN1511352A (en) * | 2001-05-23 | 2004-07-07 | ƶ��� | Lithium transition-metal phosphate powder for rechargeable batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511352A (en) * | 2001-05-23 | 2004-07-07 | ƶ��� | Lithium transition-metal phosphate powder for rechargeable batteries |
| WO2004001881A2 (en) * | 2002-06-21 | 2003-12-31 | Umicore | Carbon-coated li-containing powders and process for production thereof |
| JP2004031131A (en) * | 2002-06-26 | 2004-01-29 | Sony Corp | Nonaqueous electrolyte liquid secondary battery |
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