CN101645504A - Method for preparing lithium iron phosphate of anode material of lithium ion battery - Google Patents
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Abstract
The invention relates to a method for preparing lithium iron phosphate of an anode material of a lithium ion battery. The method synthesizes a reactive precursor under the liquid-phase condition and calcines the precursor at high temperature to prepare the lithium iron phosphate of the anode material of the lithium ion battery, and comprises the following steps: dissolving a lithium source, a phosphorus source compound and a doped element compound in deionized water; adjusting the pH value of the mixture between 2 and 4; and after carrying out sufficient reaction, adding the conductive organicprecursor and an iron source compound into the reacted mixture and stirring and mixing the obtained mixture evenly to obtain a mixture containing lithium, iron and phosphorus and doped metal elements, and then calcining the mixture to obtain the lithium iron phosphate of the anode material of the lithium ion battery. Compared with the prior art, the method has reasonable process and simple operation, well controls the chemical composition of the material and the shape and size of granules through simple process steps, improves the electrical conductivity and the lithium-ion diffusion rate ofthe material, greatly improves the magnification charge-discharge and cycle performance of the synthesized material, and is suitable for industrialized production.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries, relate in particular to a kind of preparation method of lithium ion battery anode material lithium iron phosphate.
Background technology
Since Padhi etc. has reported phosphoric acid iron lithium (LiFePO
4) can be used as anode material for lithium-ion batteries after, because this new material has advantages such as theoretical specific capacity height (170mAh/g), voltage moderate (3.4V), environmental friendliness, security performance are good, cheap, the focus that this material has become the strong competitor of positive electrode of new generation and studied in the world.Yet shortcoming has hindered its development and large-scale application because pure phase LiFePO4 conductance is low and the lithium ion migration rate is low etc.LiFePO
4Industrialization must possess following 3 points: (1) developing low-cost, be suitable for the preparation method of large-scale production; (2) increase substantially LiFePO
4Conductivity; (3) control LiFePO effectively
4Particle size distribution and product pattern, improve its tap density, thereby improve the volume energy density of material.Present conductivity of usually in building-up process, coming reinforcing material by carbon dope or doped metal ion at its shortcoming; What also have is exactly by the control synthesis technique, obtain shortening the evolving path of lithium ion than small particle diameter and the granular materials that is evenly distributed, thus the high rate charge-discharge performance of raising material.
At present, in the synthetic method commonly used, solid phase method is the technology of comparative maturity.But existing solid phase method synthesis temperature height, energy consumption is big, the random pattern of product, particle size distribution is wide, and tap density is low, the processing step complex operation, the cost of material height is difficult to realize industrialization.Though other synthetic methods can obtain the little and equally distributed particle of particle, owing to the equipment requirements height, yield poorly, step control difficulty is difficult to produce on a large scale.How, optimize synthetic route, reduce cost, and the lithium ion anode material that obtains function admirable will be the inexorable trend of a research by improving production technology.
Summary of the invention
Purpose of the present invention is exactly to provide the preparation method that a kind of technology is reasonable, simple to operate, be fit to the lithium ion battery anode material lithium iron phosphate of suitability for industrialized production for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of lithium ion battery anode material lithium iron phosphate is characterized in that, this method adopts synthetic reaction presoma under liquid-phase condition, carries out high-temperature calcination again and prepares lithium ion battery anode material lithium iron phosphate, may further comprise the steps:
(1) presoma preparation: the stoichiometric proportion according to lithium, iron, phosphorus and doped metallic elements is (0.9～1.2): 1: 1: the ratio of (0～0.1) took by weighing lithium source, source of iron, P source compound and doped metallic elements compound, Li source compound, P source compound and doped metallic elements compound are dissolved in the deionized water, regulate pH=2～4 then, fully after the reaction, add the conductive organic matter presoma, dissolving fully, add Fe source compound, mix, obtain containing the precursor mixture of lithium, iron, phosphorus and doped metallic elements after the drying;
(2) calcination processing: the precursor mixture that obtains is changed in the tube furnace, under inert atmosphere,,, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling at 500～900 ℃ of calcining at constant temperature 5～48h with the heating of 1～30 ℃/min heating rate.
Regulate pH=2～4 in the described step (1), fully after the reaction, adding the conductive organic matter presoma, dissolving fully, dry back adds Fe source compound, mixes, and obtains containing the precursor mixture of lithium, iron, phosphorus and doped metallic elements.
Also can be between described step (1) and the step (2) through preliminary treatment, this preliminary treatment is specially: with precursor mixture 200～450 ℃ of low temperature presintering 4～15h under inert atmosphere that step (1) obtains, ball milling 2～8h behind the natural cooling.
The precursor mixture that described step (1) obtains also can carry out subsequent step again behind ball milling 1～10h.
Lithium source in the described step (1) and P source compound comprise the compound of lithium, P elements coexistence.
Li source compound in the described step (1) is selected from a kind of in lithium carbonate, lithium oxalate, lithium hydroxide, lithium phosphate, lithium acetate, lithium sulfate, the lithium nitrate; P source compound in the described step (1) is selected from a kind of in phosphoric acid, lithium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
Fe source compound in the described step (1) is selected from a kind of in ferrous oxalate, ferrous acetate, ferrous sulfate, ferric nitrate, ferrous oxide, the di-iron trioxide; Doped metallic elements compound in the described step (1) is selected from a kind of in titanium dioxide, aluminium oxide, aluminium acetate, magnesium hydroxide, magnesium carbonate, magnesium acetate, nickel acetate, zirconium dioxide, zirconium carbonate, zirconium acetate, niobium oxide, cobalt oxide, manganese carbonate, manganese oxide, the nickel nitrate.
The consumption of the deionized water in the described step (1) is lithium source, three kinds of compound gross masses of source of iron and phosphorus source 1～6 times; The used reagent of adjusting pH value is selected from one or more in oxalic acid, acetic acid, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor, the urea in the described step (1).
Conductive organic matter presoma in the described step (1) is selected from a kind of in glucose, epoxy resin, carboxymethyl cellulose, hydroxyethylcellulose, sucrose, polyvinyl alcohol, polypropylene, carbon gel, carbon nano-tube, citric acid, the phenolic resins; Be that 1wt%～15wt% adds the conductive organic matter presoma according to theoretical carbon content in the end-product in the described step (1).
Inert gas in described step (2) and the preliminary treatment is selected from one or more in nitrogen, argon gas, hydrogen, carbon monoxide, methane, ethene, the acetylene.
The present invention has following characteristics:
1. the present invention's synthetic reaction presoma under liquid-phase condition, P elements, elemental lithium and doped metallic elements are formed a kind of compound, even lithium, iron, phosphorus and doped metallic elements all mixed at liquid phase state next time, mixing of materials is even, the simple and easy operating of preparation section.
The present invention avoided using in the conventional solid-state method ammonium dihydrogen phosphate or diammonium hydrogen phosphate as raw material directly calcining produces ammonia, cause gas forming amount greatly or the problem that produces because of the ammonia contaminated environment.Synthetic reaction precursor body contacts, activity is higher relatively, has the reaction time weak point, characteristics such as the easy control of process, and the LiFePO4 purity height of preparation, chemical property and physical property are good.
3. the organic precursor by doped metallic elements and carbon containing in raw material, make the carbon in the synthetic material coat more even, prevent the reunion of particle, effectively controlled the particle diameter (average grain diameter is 200nm) of product, helped improving LiFePO4 conductivity and lithium ion diffusion coefficient.
4. He Cheng LiFePO 4 material charge/discharge capacity height, large current discharging capability is strong, the cycle performance excellence.Synthetic material and metal lithium sheet are formed button cell, and with the 0.1C rate charge-discharge, voltage range is at 2.5～4.2V, and discharge capacity reaches 165mAh/g, and the 1C discharge capacity is 133mAh/g, and the 2C discharge capacity reaches 121mAh/g.
Compared with prior art, technology of the present invention is reasonable, employing is the synthetic reaction presoma under liquid-phase condition, and the synthetic metal-doped carbon-coated LiFePO 4 for lithium ion batteries positive electrode of high-temperature calcination, simple to operate, controlled the chemical composition and the granule-morphology size of material well by simple process steps, improved the conductivity and the lithium ion diffusion rate of material, synthetic material multiplying power charges and discharge with cycle performance and has all obtained bigger improvement, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the synthetic LiFePO4 of embodiment 1～embodiment 3, and wherein: a is the X ray diffracting spectrum of embodiment 1; B is the X ray diffracting spectrum of embodiment 2; C is the X ray diffracting spectrum of embodiment 3;
Fig. 2 is the first charge-discharge curve of embodiment 1 under different multiplying, and wherein: charge-discharge magnification is respectively 0.1C, 0.5C, 1C, 2C;
Fig. 3 is embodiment 2 cycle performance curves, and wherein: charge-discharge magnification is 0.1C, and voltage range is at 2.5～4.2V;
Fig. 4 is the first charge-discharge curve of embodiment 3 under different multiplying, and wherein: charge-discharge magnification is respectively 0.1C, 0.2C, 0.5C, 1C;
Fig. 5 is the sem photograph of the embodiment of the invention 1 LiFePO4.
Embodiment
The invention will be further described for the contrast drawings and the specific embodiments below.
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method comprises:
With lithium, iron, phosphorus and magnesium according to mol ratio 1.05: 1: 1: 0.05 metering score another name is got a hydronium(ion) oxidation lithium, ferrous oxalate, phosphoric acid and magnesium hydroxide, measure the deionized water of 5 times of a hydronium(ion) oxidation lithium, ferrous oxalate and phosphoric acid weight, one hydronium(ion) oxidation lithium and magnesium hydroxide are joined in the deionized water, add phosphoric acid and mix, regulate pH=3.2 by adding oxalic acid and ammoniacal liquor.Add corresponding sucrose according to theoretical carbon content 3wt% in the end-product, make its whole dissolvings, mix, the adding ferrous oxalate mixes and obtains mixed slurry, and rapid draing obtains the reaction precursor body;
Behind ball milling 2h on the planetary ball mill, change in the tube furnace at 95v%Ar+5v%H
2In the atmosphere, with 250 ℃ of pre-burning 5h of presoma, ball milling 4h obtains dusty material behind the natural cooling;
Be warming up to 700 ℃ of calcining at constant temperature 10h with 10 ℃/min again, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling.
The XRD of product as shown in Figure 1, adopts the method to prepare the olivine-type lithium iron phosphate positive material of pure phase, free from admixture peak in this product shown in a curve among Fig. 1.
With the lithium sheet is negative pole, the product of gained is assembled into Experimental cell, first charge-discharge curve under the different multiplying is shown in Figure 2, as shown in Figure 2, with the 0.1C rate charge-discharge, voltage range is at 2.5～4.2V, and discharge capacity reaches 165mAh/g, the 1C discharge capacity is 133mAh/g, and the 2C discharge capacity reaches 121mAh/g.
The sem photograph of the LiFePO4 of present embodiment as shown in Figure 5.
Embodiment 2
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method comprises:
Lithium, iron, phosphorus are got lithium acetate, ferrous acetate, phosphoric acid according to 1: 1: 1 metering score of mol ratio another name, with the deionized water dilution of phosphoric acid with 1 times of lithium acetate, ferrous acetate and phosphoric acid weight, under condition of stirring, add lithium acetate then, by dripping acetic acid and urea regulator solution pH=3.2, treat that solution system is stable after, add corresponding epoxy resin according to carbon content 6wt%, make its whole dissolvings, mix, rapid draing obtains containing the compound of lithium, phosphorus;
Gained compound powder and ferrous acetate are mixed, obtain presoma, behind the ball milling 4h, change in the tube furnace at N
2In the atmosphere, with 350 ℃ of pre-burning 10h of presoma, ball milling 2h obtains dusty material behind the natural cooling;
Be warming up to 600 ℃ of calcining at constant temperature 18h with 20 ℃/min again, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling.
The XRD of product as shown in Figure 1, adopts the method to prepare the rhombic system olivine-type lithium iron phosphate positive material of pure phase, free from admixture peak in this product shown in b curve among Fig. 1.
With the lithium sheet is negative pole, the product of gained is assembled into Experimental cell, its cycle performance of constant current test, as shown in Figure 3, as shown in Figure 3, with the 0.1C rate charge-discharge, voltage range is at 2.5～4.2V, and the discharge capacity after battery is stable reaches 150mAh/g, after 50 weeks of circulating, capacity remains unchanged substantially, has embodied excellent cycle performance.
Embodiment 3
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method comprises:
With lithium, iron, phosphorus and zirconium were according to mol ratio 1: 1: 1: 0.1 metering score another name is got lithium hydroxide, di-iron trioxide, ammonium dihydrogen phosphate and zirconium acetate, ammonium dihydrogen phosphate and two kinds of raw materials of lithium hydroxide are dissolved in lithium hydroxide respectively, di-iron trioxide, in the deionized water that ammonium dihydrogen phosphate weight is 6 times, then two kinds of solution are slowly mixed, add zirconium acetate, regulate pH=3.5 by adding oxalic acid, 15wt% adds corresponding polyvinyl alcohol according to the end-product carbon content, make its whole dissolvings, after mixing, add di-iron trioxide and obtain uniform slurries, utilize rapid dry process to obtain lithium, iron, the equally distributed reaction precursor body of three kinds of elements of phosphorus.
Without ball milling, directly change in the tube furnace, at 90v%N
2+ 10v%C
2H
2In the atmosphere, presoma is warming up to 450 ℃ of pre-burning 15h, ball milling 8h obtains dusty material behind the natural cooling;
Be warming up to 800 ℃ of calcining at constant temperature 7h with 20 ℃/min again, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling.
The XRD of product as shown in Figure 1, adopts the method to prepare the rhombic system olivine-type lithium iron phosphate positive material of pure phase, free from admixture peak in this product shown in c curve among Fig. 1.
With the lithium sheet is negative pole, the product of gained is assembled into Experimental cell, first charge-discharge curve under the different multiplying as shown in Figure 4, as shown in Figure 4, with the 0.1C rate charge-discharge, voltage range is at 2.5～4.2V, and discharge capacity reaches 130.7mAh/g, 0.5C discharge capacity reaches 123.4mAh/g, the 1C discharge capacity reaches 118.4mAh/g.
Embodiment 4
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method adopts synthetic reaction presoma under liquid-phase condition, carries out high-temperature calcination again and prepares lithium ion battery anode material lithium iron phosphate, may further comprise the steps:
(1) presoma preparation: the stoichiometric proportion according to lithium, iron, phosphorus and manganese is 0.9: 1: 1: 0.07 ratio takes by weighing lithium phosphate, ferric nitrate, phosphoric acid and manganese carbonate, lithium phosphate, manganese carbonate are dissolved in the deionized water of 3 times of lithium phosphates, ferric nitrate, phosphoric acid weight, add phosphoric acid, regulate pH=2 with acetic acid and ammonium carbonate then, fully after the reaction, add carboxymethyl cellulose according to end-product carbon content 1wt%, dissolving fully, adding ferric nitrate mixes, after the drying, ball milling 1h obtains containing the precursor mixture of lithium, iron, phosphorus and manganese;
(2) preliminary treatment: with precursor mixture 200 ℃ of low temperature presintering 15h under 10v%CO+90v%Ar atmosphere that step (1) obtains, ball milling 6h obtains dusty material behind the natural cooling;
(3) calcination processing: the dusty material that step (2) is obtained changes in the tube furnace, under the inert atmosphere identical, heat with 1 ℃/min heating rate with step (2), at 550 ℃ of calcining at constant temperature 48h, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling.
Embodiment 5
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method adopts synthetic reaction presoma under liquid-phase condition, carries out high-temperature calcination again and prepares lithium ion battery anode material lithium iron phosphate, may further comprise the steps:
(1) presoma preparation: according to lithium, iron, the stoichiometric proportion of phosphorus and nickel is 1.2: 1: 1: 0.09 ratio takes by weighing lithium nitrate, ferrous oxalate, ammonium phosphate and nickel nitrate, ammonium phosphate is dissolved in lithium nitrate, ferrous oxalate, in the deionized water that ammonium phosphate weight is 4 times, add lithium nitrate, nickel nitrate, regulate pH=4 with oxalic acid and carbonic hydroammonium then, fully after the reaction, add citric acid according to end-product carbon content 10wt%, dissolving fully, after the rapid draing, adding ferrous oxalate mixes, ball milling 10h obtains containing lithium, iron, the precursor mixture of phosphorus and nickel;
(2) preliminary treatment: the precursor mixture that step (1) is obtained is at 10v%CH
4The following 400 ℃ of low temperature presintering 4h of+90v%Ar atmosphere, ball milling 4h obtains dusty material behind the natural cooling;
(3) calcination processing: the dusty material that step (2) is obtained changes in the tube furnace, under the inert atmosphere identical, heat with 30 ℃/min heating rate with step (2), at 820 ℃ of calcining at constant temperature 5h, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling.
Embodiment 6
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, this method comprises:
With lithium, iron, phosphorus and magnesium according to mol ratio 1.05: 1: 1: 0.05 metering score another name is got lithium hydroxide, ferrous oxalate, phosphoric acid and magnesium acetate, measure the deionized water of 5 times of lithium hydroxide, ferrous oxalate and phosphoric acid weight, one hydronium(ion) oxidation lithium and magnesium acetate are joined in the deionized water, add phosphoric acid and mix, regulate pH=3.2 by adding oxalic acid and ammoniacal liquor.Add corresponding sucrose according to theoretical carbon content 3wt% in the end-product, make its whole dissolvings, mix, the adding ferrous oxalate mixes and obtains mixed slurry, and rapid draing obtains the reaction precursor body;
Behind ball milling 2h on the planetary ball mill, change in the tube furnace at 95v%Ar+5v%H
2In the atmosphere, be warming up to 700 ℃ of calcining at constant temperature 15h, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling with 25 ℃/min.
In addition to the implementation, the present invention can also enumerate more embodiment by class by the following technical solutions, as, Li source compound can also be selected from lithium carbonate, lithium oxalate, a kind of in the lithium sulfate, Fe source compound can also be ferrous sulfate, ferrous oxide, P source compound can also be selected from lithium phosphate, a kind of in the diammonium hydrogen phosphate, the doped metallic elements compound can also be selected from titanium dioxide, aluminium oxide, aluminium acetate, magnesium carbonate, nickel acetate, zirconium dioxide, zirconium carbonate, niobium oxide, cobalt oxide, a kind of in the manganese oxide, the conductive organic matter presoma can also be selected from glucose, hydroxyethylcellulose, polypropylene, the carbon gel, carbon nano-tube, a kind of in the phenolic resins, inert gas can also be ethene.
The invention is not restricted to this, any based on replacement of the present invention with modify and all should be included, protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the preparation method of a lithium ion battery anode material lithium iron phosphate is characterized in that, this method adopts synthetic reaction presoma under liquid-phase condition, carries out high-temperature calcination again and prepares lithium ion battery anode material lithium iron phosphate, may further comprise the steps:
(1) presoma preparation: the stoichiometric proportion according to lithium, iron, phosphorus and doped metallic elements is (0.9～1.2): 1: 1: the ratio of (0～0.1) took by weighing lithium source, source of iron, P source compound and doped metallic elements compound, Li source compound, P source compound and doped metallic elements compound are dissolved in the deionized water, regulate pH=2～4 then, fully after the reaction, add the conductive organic matter presoma, dissolving fully, add Fe source compound, mix, obtain containing the precursor mixture of lithium, iron, phosphorus and doped metallic elements after the drying;
(2) calcination processing: the precursor mixture that obtains is changed in the tube furnace, under inert atmosphere,,, obtain lithium ion battery anode material lithium iron phosphate behind the natural cooling at 500～900 ℃ of calcining at constant temperature 5～48h with the heating of 1～30 ℃/min heating rate.
2. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that, regulating pH=2～4 in the described step (1), fully after the reaction, add the conductive organic matter presoma, dissolving fully, dry back adds Fe source compound, mix, obtain containing the precursor mixture of lithium, iron, phosphorus and doped metallic elements.
3. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that, also can be between described step (1) and the step (2) through preliminary treatment, this preliminary treatment is specially: with precursor mixture 200～450 ℃ of low temperature presintering 4～15h under inert atmosphere that step (1) obtains, ball milling 2～8h behind the natural cooling.
4. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that, the precursor mixture that described step (1) obtains also can carry out subsequent step again behind ball milling 1～10h.
5. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that, lithium source in the described step (1) and P source compound comprise the compound of lithium, P elements coexistence.
6. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that the Li source compound in the described step (1) is selected from a kind of in lithium carbonate, lithium oxalate, lithium hydroxide, lithium phosphate, lithium acetate, lithium sulfate, the lithium nitrate; P source compound in the described step (1) is selected from a kind of in phosphoric acid, lithium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
7. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 and 2, it is characterized in that the Fe source compound in the described step (1) is selected from a kind of in ferrous oxalate, ferrous acetate, ferrous sulfate, ferric nitrate, ferrous oxide, the di-iron trioxide; Doped metallic elements compound in the described step (1) is selected from a kind of in titanium dioxide, aluminium oxide, aluminium acetate, magnesium hydroxide, magnesium carbonate, magnesium acetate, nickel acetate, zirconium dioxide, zirconium carbonate, zirconium acetate, niobium oxide, cobalt oxide, manganese carbonate, manganese oxide, the nickel nitrate.
8. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that, the consumption of the deionized water in the described step (1) is lithium source, three kinds of compound gross masses of source of iron and phosphorus source 1～6 times; The used reagent of adjusting pH value is selected from one or more in oxalic acid, acetic acid, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor, the urea in the described step (1).
9. the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that the conductive organic matter presoma in the described step (1) is selected from a kind of in glucose, epoxy resin, carboxymethyl cellulose, hydroxyethylcellulose, sucrose, polyvinyl alcohol, polypropylene, carbon gel, carbon nano-tube, citric acid, the phenolic resins; Be that 1wt%～15wt% adds the conductive organic matter presoma according to theoretical carbon content in the end-product in the described step (1).
10. according to the preparation method of claim 1 or 3 described lithium ion battery anode material lithium iron phosphates, it is characterized in that the inert gas in described step (2) and the preliminary treatment is selected from one or more in nitrogen, argon gas, hydrogen, carbon monoxide, methane, ethene, the acetylene.
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