CN1773751A - Production of olivine structural lithium ferric phospate lithium battery anode material by solution method - Google Patents
Production of olivine structural lithium ferric phospate lithium battery anode material by solution method Download PDFInfo
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- CN1773751A CN1773751A CNA2004100946378A CN200410094637A CN1773751A CN 1773751 A CN1773751 A CN 1773751A CN A2004100946378 A CNA2004100946378 A CN A2004100946378A CN 200410094637 A CN200410094637 A CN 200410094637A CN 1773751 A CN1773751 A CN 1773751A
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Abstract
A method for preparing lithium cell positive electrode material of lithium-iron phosphate in olivine structure by solution process includes dissolving Fe power, Li salt and phosphate radical compound in organic acid aqueous solution to form mixed solution with mole ratio of L:+ : Fe2+ : PO43- as I+X : I+ Y : I ;agitating and drying mixed solution to obtain solid power then heating solid power up to 500 DEG C for carrying out heat treatment on solid powder.
Description
Technical field
The invention relates to a kind of preparation method of positive electrode, refer to a kind of Li especially
1+xFe
1+yPO
4The preparation method of positive electrode.
Background technology
Because Portable, wireless, consumer products market that weight is light and handy is flourish, expands just rapidly as the secondary cell market of its power supply.No matter be that electronics, information, communication apparatus or living doctor's equipment all have urgent demand to secondary cell.Common small-sized secondary batteries has nickel-cadmium cell, Ni-MH battery, lithium ion battery or the like at present.Wherein, lithium rechargeable battery is owing to have high volumetric capacitance, pollution-free, advantage such as the cycle charge discharge characteristic is good, and meets the compact requirement of modern electronic product, significantly is applied to various small-sized portable type 3C Products.
And positive electrode is the critical material of decision lithium rechargeable battery characteristic.Iron lithium phosphate (the LiFePO of olivine structural wherein
4) positive electrode is owing to having high theoretical capacitance, low pollute, coming into one's own as the safe and low cost of material of positive electrode.Though the LiFePO of olivine structural
4Be present in the natural crystal, however the iron lithium phosphate (LiFePO in the natural olivine ore
4) purity is very low.Therefore, general olivine structural iron lithium phosphate (LiFePO as positive electrode
4) mostly be artificial synthetic.Existing olivine structural iron lithium phosphate (LiFePO
4) synthetic method think ferric iron as synthesis material, for example ferric sulfate, ferric nitrate, ferric acetate more ... or the like, with reducing process ferric iron is reduced into two valency iron, easily generate and contain ferric impurity.Though its raw material sources are obtained easily, its unit price is still higher, is difficult for when producing in a large number reducing cost.Moreover, existing olivine structural iron lithium phosphate (LiFePO
4) synthetic method many carry out with solid state reaction, after also being about to lithium salts, molysite and ammonium phosphate salt and carrying out the ground and mixed powdered to scale, heat treatment again.Yet solid state reaction needs high temperature, long-time, and particle big (50 μ m) can cause electrical conductivity relatively poor.In addition, solid state reaction is easily because mixed grinding causes by other element pollution, and the also more also control of the composition of each composition.
Summary of the invention
The invention relates to a kind of Li
1+xFe
1+yPO
4The preparation method of powder, wherein-0.2≤x≤0.2 ,-0.2≤y≤0.2 may further comprise the steps: (A) iron powder, lithium salts and phosphate compound are dissolved in the aqueous solutions of organic acids to form a mixed solution, wherein Li
+: Fe
2+: PO
4 3-Mole ratio be 1+x: 1+y: 1; (B) stir this mixed solution; (C) dry this mixed solution is to obtain pressed powder; And (D) heat more than this pressed powder to 500 ℃, with this pressed powder of heat treatment.Because the price of iron powder is very cheap, therefore the preparation method of olivine structural positive electrode of the present invention can significantly reduce cost, and is beneficial to the application of industry.
Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein dry this aqueous solution of can the be any existing drying means of step (C) is preferably this mixed solution of convection drying or spray drying.Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein step (D) can place pressed powder any existing inert gas to heat, and is preferably and places nitrogen or argon gas atmosphere.Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein lithium salts can be any existing lithium salts, is preferably lithium nitrate, lithium acetate, lithium hydroxide, lithium hydrogen phosphate or lithium phosphate.Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein the phosphate compound can be any existing phosphate compound, is preferably ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate, ammonium phosphate lithium or phosphoric acid.Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein organic acid can be any existing organic acid, is preferably acetic acid, citric acid, oxalic acid, tartaric acid, propionic acid, butyric acid or its mixture.The preparation method of olivine structural positive electrode of the present invention, wherein step (A) can optionally add carbohydrate, and sucrose for example be coated on Li with the carbon that utilizes carbohydrate can cracking when the heat treatment to produce trace
1+xFe
1+yPO
4Powder surface, the electrical conductivity of increase positive electrode, wherein the content of this carbohydrate is Li
1+xFe
1+yPO
4Between 5% to 25% percentage by weight of powder is preferable.Li of the present invention
1+xFe
1+yPO
4The preparation method of powder, wherein the heat treatment time of step (D) was preferably more than 6 hours.
The present invention is oxidized to effective two valency iron (Fe with organic acid or mixed organic acid with iron
2+), therefore any with acid solution brown iron oxide or iron, generate stable or be situated between and stablize Fe
2+, with preparation Li
1+xFe
1+yPO
4The method of powder promptly belongs to Li of the present invention
1+xFe
1+yPO
4The preparation method of powder.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates of one embodiment of the invention;
Fig. 2 is the cycle charge discharge electrograph of one embodiment of the invention;
Fig. 3 is the X-ray diffraction collection of illustrative plates of another embodiment of the present invention;
Fig. 4 is the cycle charge discharge electrograph of another embodiment of the present invention.
Embodiment
Among the preparation method of olivine structural positive electrode of the present invention, Li
+, Fe
2+, PO
4 3-Metering than for can be any existing metering ratio, be 1: 1: 1 mole ratio of employing in present embodiment.
Embodiment one: prepare olivine structural iron lithium phosphate (LiFePO by direct drying method
4)
With the iron powder of 0.1mole, the LiNO of 0.1mole
3(the NH of solution and 0.1mole
4)
2HPO
4, add 200ml and contain in the 0.1mole lemon aqueous acid, form a mixed solution.Li in this mixed solution
+, Fe
2+, PO
4 3-Mole ratio be 1: 1: 1.And the sucrose of adding 1.8g.Treat iron powder, LiNO
3Solution and (NH
4)
2HPO
4After mixing fully, directly improve temperature and make water evaporates (direct drying method).Can obtain LiFePO after the oven dry
4Forerunner's powder.With this LiFePO
4Forerunner's powder place blanket of nitrogen, with 700 ℃ of heat treatments 12 hours, can obtain the LiFePO of 18g tool olivine crystalline phase
4The positive powder powder material.
Test result
The a.X-ray diffraction analysis
At first see also Fig. 1, be the LiFePO of present embodiment
4The X-ray diffraction collection of illustrative plates of powder.Owing to only show the diffraction peak collection of illustrative plates of typical olivine crystalline phase among Fig. 1, as can be known the LiFePO of present embodiment
4Have only olivine to generate mutually in the powder, there is no other two second phase.That is to say the olivine structural LiFePO of present embodiment
4The preparation method, can prepare the LiFePO of the high pure olivine phase of purity really
4Powder.
Iron lithium phosphate (the LiFePO of existing pure olivine phase
4) powder all is with ferric iron, for example ferric sulfate or ferric nitrate etc. are as the LiFePO of olivine phase
4Synthetic raw material.And, ferric iron is reduced to ferrous iron carries out synthetic reaction by by method of reducing.And preparation method of the present invention is as olivine phase iron lithium phosphate (LiFePO with cheap and handy iron powder
4) synthesis material.Compared to existing technology, the present invention is that the method with oxidation is a ferrous iron with oxidation of iron powder, and is different with existing method.And because the price of iron powder is very cheap, therefore preparation method of the present invention can save cost greatly, and can prepare highly purified olivine phase iron lithium phosphate (LiFePO equally
4) powder, have tangible progressive.
Then, again with the iron lithium phosphate (LiFePO of the olivine phase of present embodiment
4) powder is used as the positive electrode of battery, to test its charge-discharge characteristic.
B. cycle charge discharge electrical testing
Olivine phase iron lithium phosphate (LiFePO with present embodiment
4) powder and acetylene carbon black and polyvinylidene fluoride (PVDF) be 83: 10: 7 ratio according to weight ratio, (NMP N-methylpyrollidone) is mixed into slurry, evenly coats on the aluminium foil again with solvent N-methyl nafoxidine ketone.After the drying, make suitable anodal test piece, and be assembled into button cell, to carry out the cycle charge discharge electrical testing.
The cycle charge discharge electrical test results of present embodiment is with different charge-discharge velocities (between the 2C to C/10) as shown in Figure 2, carries out 30 times charge-discharge test result between cut-ff voltage 2.5V to 4.5V.Fig. 2 shows, with the olivine phase LiFePO of present embodiment
4Powder is as the button cell of positive electrode, at room temperature and charge-discharge velocity C/10 (0.06mA/cm
2) situation under, accessible specific capacitance just is 165mAh/g, still has 150mAh/g through specific capacitance behind the 30 circle cycle charge-discharges.As seen the olivine phase LiFePO of present embodiment
4Powder is during as positive electrode, and battery is under slower charge-discharge velocity C/10, and the specific capacitance decline is little, and the cycle charge discharge electrical characteristics are good.Then, continue to test with charge-discharge velocity (C/5, C/3,1C and 2C) faster.Test result shows, under charge-discharge velocity fast, the battery of present embodiment still has the favorable charge-discharge characteristic.Up to 2C (1mA/cm
2) the speed of charge and discharge cycles fast under, its just specific capacity still have 123mAh/g, through specific capacitance behind the 30 circle cycle charge-discharges 115mAh/g is arranged still.Demonstration is with present embodiment olivine phase LiFePO
4Powder still demonstrates good characteristic and capacitance as the battery of positive electrode under high charge-discharge speed.
This shows the olivine phase iron lithium phosphate (LiFePO of present embodiment
4) not only cost of manufacture is cheap for powder, and it is electrical to have a good cycle charge discharge, is beneficial to a large amount of productions.Be applied to lithium rechargeable battery and have good industry applications.
Embodiment two: by the LiFePO of spray drying method for preparation olivine structural
4Powder
With the iron powder of 0.1mole, the LiNO of 0.1mole
3(the NH of solution and 0.1mole
4)
2HPO
4Add 200ml and contain in the 0.1mole lemon aqueous acid, make the Li in the solution
+, Fe
2+, PO
4 3-The metering ratio be 1: 1: 1.And the sucrose of adding 1.8g.Treat iron powder, LiNO
3(or LiOAc) solution and (NH
4)
2HPO
4After mixing fully, with (spray drying process) of this solution spray drying.Can obtain LiFePO
4The precursor powder.With this LiFePO
4The precursor powder place blanket of nitrogen, with 700 ℃ of heat treatments 12 hours, can obtain the LiFePO of the tool olivine crystalline phase of 18g
4The positive powder powder material.
Test result
The a.X-ray diffraction analysis
Iron lithium phosphate (the LiFePO of present embodiment
4) powder is with the spray-on process drying, its X-ray diffraction analysis figure is similarly a typical olivine crystalline phase figure as shown in Figure 3, and does not have other secondary and generate mutually.
Therefore, olivine structural iron lithium phosphate (LiFePO of the present invention
4) in the manufacture method, as long as preparation is mixed with the aqueous solutions of organic acids of iron powder, lithium salts and ammonium phosphate salt, promptly available any existing drying means and heat treatment can obtain the iron lithium phosphate (LiFePO of olivine crystalline phase
4).
Iron lithium phosphate (the LiFePO that present embodiment obtains with spray drying
4) powder, to observe by the SEM photo, its particle diameter is about about 2 μ m.Be with, can obtain the little iron lithium phosphate (LiFePO of particle diameter with spray drying process
4) powder.
B. cycle charge discharge electrical testing
The button cell manufacture method of present embodiment is with embodiment one.Fig. 4 is the iron lithium phosphate (LiFePO with present embodiment
4) powder is the button cell that positive electrode is formed, at room temperature with 1C (0.51mA/cm
2) charge-discharge velocity, be the cycle charge discharge electrical test results that records between 2.5V and 4.5V charging and discharging cut-ff voltage.Fig. 4 shows that the initial capacitance of the button cell of present embodiment is about 125mAh/g, and through after the discharging and recharging of three circles, capacitance can tend to be steady and maintain about 138mAh/g.Even through behind the cycle charge-discharge, specific capacitance still maintains about 138mAh/g, does not have the decline of tangible specific capacitance.
The present invention and existing olivine be iron lithium phosphate (LiFePO mutually
4) anodal powder, the sizable progressive of tool with regard to manufacture method.At first, as material, its cost is cheap far beyond existing trivalent iron salt with iron powder in the present invention.In addition, the present invention is to be ferrous iron with mode of oxidizing with oxidation of iron powder, with existing fully different.Moreover the present invention finishes olivine structural Li with solwution method
1+xFe
1+yPO
4Synthetic, its processing procedure is simple, and can obtain the tiny iron lithium phosphate (LiFePO of particle diameter
4) powder, shorten Li
+Diffusion length, have preferable conductivity.And existing major part is to prepare iron lithium phosphate (LiFePO with solid state reaction
4), need high temperature, long heat treatment, and make powder particle big (50 μ m), cause electrical conductivity relatively poor.In addition, solid state reaction causes by other element pollution because of mixed grinding easily, and the also more also control of the composition of each composition.
Simultaneously, olivine phase Li of the present invention
1+xFe
1+yPO
4Powder not only cost of manufacture is cheap, and has the electrical life-span of good cycle charge discharge, is beneficial to a large amount of productions.Therefore the present invention also is beneficial to the utilization of industry.
The foregoing description only is to give an example for convenience of description, and the interest field that the present invention advocated should be as the criterion so that claim is described certainly, but not only limits to the foregoing description.
Claims (9)
1. Li
1+xFe
1+yPO
4The preparation method of powder, wherein-0.2≤x≤0.2 ,-0.2≤y≤0.2 is characterized in that, may further comprise the steps:
(A) iron powder, lithium salts and phosphate compound are dissolved in the aqueous solutions of organic acids to form a mixed solution, wherein Li
+: Fe
2+: PO
4 3-Mole ratio be 1+x: 1+y: 1;
(B) stir this mixed solution;
(C) dry this mixed solution is to obtain a pressed powder; And
(D) heat more than this pressed powder to 500 ℃, with this pressed powder of heat treatment.
2. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described step (C) is with dry this mixed solution of direct drying.
3. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described step (C) is with this mixed solution of spray drying.
4. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described step (D) is to place nitrogen or argon gas heat hot to handle this pressed powder.
5. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described this lithium salts is lithium nitrate, lithium acetate, lithium chloride, lithium hydroxide, lithium hydrogen phosphate or lithium phosphate.
6. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described this phosphate compound is ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate, ammonium phosphate lithium or phosphoric acid.
7. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described this organic acid is acetic acid, citric acid, oxalic acid, tartaric acid, propionic acid, butyric acid or its mixture.
8. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, described step (A) more comprises adding one carbohydrate, to produce the carbon of trace via high temperature, increases electrical conductivity, and wherein the content of this carbohydrate is Li
1+xFe
1+yPO
4Between the percentage by weight 5% to 25% of powder.
9. Li as claimed in claim 1
1+xFe
1+yPO
4The preparation method of powder is characterized in that, the heat treatment time of described step (D) is more than 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100946378A CN1773751A (en) | 2004-11-11 | 2004-11-11 | Production of olivine structural lithium ferric phospate lithium battery anode material by solution method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100946378A CN1773751A (en) | 2004-11-11 | 2004-11-11 | Production of olivine structural lithium ferric phospate lithium battery anode material by solution method |
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| Publication Number | Publication Date |
|---|---|
| CN1773751A true CN1773751A (en) | 2006-05-17 |
Family
ID=36760586
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008022508A1 (en) * | 2006-08-18 | 2008-02-28 | Henan Huan Yu Group Co. Ltd | Method for preparing lithium iron phosphate through wet process and lithium iron phosphate prepared by the same |
| CN101964419A (en) * | 2010-09-28 | 2011-02-02 | 彩虹集团公司 | Method for synthesizing lithium ion battery anode material LiFePO4 |
| CN101794880B (en) * | 2007-11-14 | 2012-09-12 | 中国科学院理化技术研究所 | Preparation method of positive-electrode porous material used by lithium ion battery |
| CN114188508A (en) * | 2021-10-28 | 2022-03-15 | 厦门理工学院 | Lithium iron phosphate cathode material, preparation method and application |
-
2004
- 2004-11-11 CN CNA2004100946378A patent/CN1773751A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008022508A1 (en) * | 2006-08-18 | 2008-02-28 | Henan Huan Yu Group Co. Ltd | Method for preparing lithium iron phosphate through wet process and lithium iron phosphate prepared by the same |
| CN101794880B (en) * | 2007-11-14 | 2012-09-12 | 中国科学院理化技术研究所 | Preparation method of positive-electrode porous material used by lithium ion battery |
| CN101964419A (en) * | 2010-09-28 | 2011-02-02 | 彩虹集团公司 | Method for synthesizing lithium ion battery anode material LiFePO4 |
| CN101964419B (en) * | 2010-09-28 | 2012-10-24 | 彩虹集团公司 | Method for synthesizing lithium ion battery anode material LiFePO4 |
| CN114188508A (en) * | 2021-10-28 | 2022-03-15 | 厦门理工学院 | Lithium iron phosphate cathode material, preparation method and application |
| CN114188508B (en) * | 2021-10-28 | 2023-02-14 | 厦门理工学院 | Lithium iron phosphate cathode material, preparation method and application |
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