CN102992295A - Manufacturing method of high-activity lithium iron phosphate positive pole material - Google Patents
Manufacturing method of high-activity lithium iron phosphate positive pole material Download PDFInfo
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- CN102992295A CN102992295A CN2011102808527A CN201110280852A CN102992295A CN 102992295 A CN102992295 A CN 102992295A CN 2011102808527 A CN2011102808527 A CN 2011102808527A CN 201110280852 A CN201110280852 A CN 201110280852A CN 102992295 A CN102992295 A CN 102992295A
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Abstract
The invention provides a manufacturing method of a high-activity lithium iron phosphate positive pole material, which comprises the following steps: carrying out solid-phase mixing and grinding on soluble iron salt solid with crystalline water, lithium salt and phosphorus source; carrying out wet-process ball milling on the mixture and carbon source, and drying to obtain a precursor mixture containing organic carbon source; and calcining the precursor mixture in a weak reducing atmosphere at 500-700 DEG C to obtain black nano lithium iron phosphate powder. The invention has the following advantages: 1. the synthetic material has uniform granules and uniform activity, and the battery has favorable consistency, favorable loop stability and greatly improved low-temperature discharging property; 2. the energy consumption is low; 3. the production cost is obviously lowered; and 4. the technique is simple and easy to implement, and is suitable for industrial production.
Description
Technical field: the present invention relates to the making method of its anode material for lithium-ion batteries in a kind of energy storage material and the electrochemical field, particularly a kind of making method of high reactivity lithium iron phosphate positive material.
Background technology: existing anode material for lithium-ion batteries mainly contains LiCoO2, LiMn2O4 and LiFePO4, although LiCoO2 in occupation of most of market, LiFePO4 (iron lithium phosphate, as follows) as a kind of higher capacity and the relatively low product of cost, larger advantage is arranged.Existing method of making lithium iron phosphate positive material comprises solid phase method, coprecipitation method, sol-gel method.Rear two kinds of methods are because of its complicated operation, and cost is high, now seldom use; Solid phase method is simple because of technique, cost is low, the user is more.Its making flow process is: first molysite, lithium salts and phosphoric acid salt are prepared precursor mixture by solid phase mixing, then by the dry moisture of removing, after again precursor mixture is carried out high-temperature calcination.Because ferrous iron at high temperature is oxidized to ferric iron easily, therefore in the middle of reducing atmosphere, carry out solid state reaction.The deficiency that the method in use exists is: 1, its synthetic material granule is inhomogeneous, the seed activity size of material has certain difference, so that the active substance of large granule interior is not fully utilized, especially under the relatively large condition of current density, the consistence of battery will be had a strong impact on; 2, power consumption is large, not only wants the dry moisture of removing in its work flow, and needs 700-800 ℃ high-temperature calcination, and these all need to consume a large amount of energy; 3, production cost is high, and this has relatively high expectations to raw-material in being to make, so that bid is high, power consumption has also increased greatly the expenditure of production cost in addition.
Summary of the invention: the object of the invention is to, the deficiency that in use exists for existing its making method of lithium ion battery anode material lithium iron phosphate, and a kind of uniform particles of synthetic materials, the making method of high reactivity lithium iron phosphate positive material that active size high conformity, power consumption and production cost identical, battery is low are proposed.
Can realize the object of the invention by following technical proposals, a kind of making method of high reactivity lithium iron phosphate positive material is characterized in that, it is made of following steps:
(1), with solubility with molysite solid, lithium salts and the phosphorus source of crystal water according to element mol ratio Li: Fe: P=0.96～1.1: 0.96～1.1: 0.96～1.1 are carried out solid phase mixing and were ground 1～5 hour, fully react; For removing other negatively charged ion, with deionized water and ethanol it is washed; Carry out vacuum-drying and grinding, after obtain green precursor powder.
(2), above-mentioned green precursor powder and carbon source are carried out the precursor mixture that wet ball grinding, drying obtain containing organic carbon source according to mass ratio 100: 5～20;
(3), with above-mentioned precursor mixture under weak reducing atmosphere protection, through 500 ℃ of-700 ℃ of temperature calcinings, time 4-24 hour, temperature rise rate was 1-10 ℃/min, rate of temperature fall is 1-5 ℃/min, obtains the nano-scale lithium iron phosphate powder of black after the calcining.
Solubility is a kind of in iron vitriol, four water iron protochlorides and the six ferrous sulfate hydrate ammoniums with the molysite solid of crystal water; Lithium salts is lithium nitrate or monohydrate lithium hydroxide; The phosphorus source is the phosphoric acid of concentration 50-85%.
Describedly with deionized water and ethanol it is washed, refer to deionized water and dehydrated alcohol it be carried out washing more than 2 times.
Described carbon source is selected one or more in glucose, sucrose, polyvinyl alcohol, cellulose acetate, Mierocrystalline cellulose, vitamins C acid, resol, Sorbic Acid, oleic acid, the dodecyl sodium sulfonate.
Described weak reducing atmosphere refers to a kind of in nitrogen, nitrogen and hydrogen mixture (3-5% hydrogen, volume ratio) or the argon gas.
Effect of the present invention is: 1, the uniform particles of synthetic materials, active size is identical, the high conformity of battery, and has good stable circulation performance, its low temperature discharge property is greatly improved, this is that mainly this making method used the Room Temperature Solid State reaction, selected solubility to substitute the molysite solid without crystal water used in the existing method with molysite solid that is the solubility ferrous iron of crystal water, because of solubility with the molysite solid of crystal water in solid phase mixing is ground, physical change not only occurs, the more important thing is, it and lithium salts generation chemical transformation, produce the throw out of solvable water, so that its grain diameter little (0.5-0.8 micron) and even, the specific surface area of final product is less than 10m2/g, the product granularity is about 80 nanometers, reach more than the 150mAh/g with 0.1C rate charge-discharge reversible specific capacity, and show good cycle performance; 2, power consumption is low, and this is because this making method has adopted the Room Temperature Solid State reaction, and its calcining has 500 ℃ of-700 ℃ of temperature to get final product, and far below calcining temperature of the prior art, comparable prior art is saved energy; 3, significantly reduce production costs, this is that the used starting material of present method all can be technical grade, and in its cost ratio prior art the price of raw materials is low, and the reduction of power consumption also so that production cost reduce; 4, simple for process, suitability for industrialized production.
The invention will be further described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is the XRD figure of the prepared iron phosphate powder of embodiment 1;
Fig. 2 is the SEM figure of the prepared iron phosphate powder of embodiment 1;
Fig. 3 is the charging and discharging curve figure of the prepared iron phosphate powder of embodiment 1.
Embodiment:
Embodiment 1: referring to accompanying drawing 1,2,3, a kind of making method of high reactivity lithium iron phosphate positive material, it is made of following steps: (1), take 1.726 kilograms of lithium nitrates, 6.96 kilograms of iron vitriols and the 5.09 kilograms of solubility phosphoric acid as 85% as raw material, ground 3 hours, with deionized water it is washed three times, use again absolute ethanol washing three times, obtain green presoma through 80 ℃ of vacuum dryings.(2), 2 kilograms of above-mentioned green presomas carried out wet ball grinding with 0.2 kilogram of sucrose mixed in 8 hours, take ethanol as dispersion agent, the mixture paste that ball milling is complete is carried out vacuum-drying and is obtained the precursor powder.(3) the precursor powder that drying is good carries out high-temperature calcination in the box-type furnace of nitrogen (99.999%) protection, and temperature is 650 ℃, and calcination time is 5 hours, and temperature rise rate is 5 ℃/min, and rate of temperature fall is 2 ℃/min, obtains the grey black product.
The XRD figure show sample of prepared iron phosphate powder is consistent with olivine structure lithium iron phosphate, without other dephasign; The SEM figure show sample primary particle size of prepared iron phosphate powder is in 100 nanometers; The charging and discharging curve figure show sample specific discharge capacity of prepared iron phosphate powder is 156mAh/g, discharging voltage balance.
Claims (5)
1. the making method of a high reactivity lithium iron phosphate positive material is characterized in that, it is made of following steps:
(1), with solubility with molysite solid, lithium salts and the phosphorus source of crystal water according to element mol ratio Li: Fe: P=0.96～1.1: 0.96～1.1: 0.96～1.1 are carried out solid phase mixing and were ground 1～5 hour, fully react; For removing other negatively charged ion, with deionized water and ethanol it is washed; Carry out vacuum-drying and grinding, after obtain green precursor powder.
(2), above-mentioned green precursor powder and carbon source are carried out the precursor mixture that wet ball grinding, drying obtain containing organic carbon source according to mass ratio 100: 5～20;
(3), with above-mentioned precursor mixture under weak reducing atmosphere protection, through 500 ℃ of-700 ℃ of temperature calcinings, time 4-24 hour, temperature rise rate was 1-10 ℃/min, rate of temperature fall is 1-5 ℃/min, obtains the nano-scale lithium iron phosphate powder of black after the calcining.
2. by the making method of high reactivity lithium iron phosphate positive material claimed in claim 1, it is characterized in that solubility is a kind of in iron vitriol, four water iron protochlorides and the six ferrous sulfate hydrate ammoniums with the molysite solid of crystal water; Lithium salts is lithium nitrate or monohydrate lithium hydroxide; The phosphorus source is the phosphoric acid of concentration 50-85%.
3. by the making method of high reactivity lithium iron phosphate positive material claimed in claim 1, it is characterized in that, describedly with deionized water and ethanol it is washed, refer to deionized water and dehydrated alcohol it be carried out washing more than 2 times.
4. press the making method of high reactivity lithium iron phosphate positive material claimed in claim 1, it is characterized in that described carbon source is selected one or more in glucose, sucrose, polyvinyl alcohol, cellulose acetate, Mierocrystalline cellulose, vitamins C acid, resol, Sorbic Acid, oleic acid, the dodecyl sodium sulfonate.
5. by claim 1 or 2 or the making method of 3 or 4 described high reactivity lithium iron phosphate positive materials, it is characterized in that, described weak reducing atmosphere refer to nitrogen, nitrogen and hydrogen mixture wherein hydrogen be a kind of in 3-5% volume ratio or the argon gas.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500832A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method of preparing nanoscale lithium iron phosphate / carbon composite anode material |
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| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | Method for preparing Li Fe PO4 ball shape powder |
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| CN101037195A (en) * | 2007-03-16 | 2007-09-19 | 厦门大学 | LiFePO4 cathode material based on P site doped and preparation method thereof |
| CN101913590A (en) * | 2010-08-09 | 2010-12-15 | 中钢集团安徽天源科技股份有限公司 | Method for preparing iron-lithium phosphate by using high-purity magnet fine mineral powder as iron source |
| CN102034971A (en) * | 2010-10-29 | 2011-04-27 | 华南理工大学 | Lithium-ion battery lithium iron phosphate/polypyrrole pyridine composite anode material and preparation method thereof |
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- 2011-09-09 CN CN2011102808527A patent/CN102992295A/en active Pending
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| JP2000294238A (en) * | 1999-04-06 | 2000-10-20 | Sony Corp | SYNTHESIS OF LiFePO4 AND MANUFACTURE OF NONAQUEOUS ELECTROLYTE BATTERY |
| EP1193784A2 (en) * | 2000-09-29 | 2002-04-03 | Sony Corporation | Method for the preparation of cathode active material and method for the preparation of a non-aqueous electrolyte cell |
| CN1401559A (en) * | 2002-10-18 | 2003-03-12 | 北大先行科技产业有限公司 | Method for preparing ferrous lithium phosphate, and lithium ion cell therewith |
| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | Method for preparing Li Fe PO4 ball shape powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103500832A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method of preparing nanoscale lithium iron phosphate / carbon composite anode material |
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Application publication date: 20130327 |