A kind of carbon of anode material for lithium-ion batteries coats presoma and preparation method thereof
Technical field
The invention belongs to the lithium ion battery material field, particularly a kind of carbon of anode material for lithium-ion batteries coats presoma and preparation method thereof.
Background technology
Lithium ion battery has obtained develop rapidly since the commercialization of the early 1990s in last century, become the main power supply equipment of portable products such as mobile communication, notebook computer, video camera such as mobile phone, proposition along with new forms of energy concept and new forms of energy car, power-type lithium ion battery becomes now and the main direction of future development, and is also more and more higher to the requirement of battery material simultaneously.Olivine structural phosphoric acid based material serves as typical case's representative with LiFePO4 (LiFePO4) wherein, and it is safe, good cycling stability, advantages such as material is abundant, cheap and easy to get, and charge and discharge platform obviously, stable and capacity is moderate become one of main positive electrode of power-type lithium ion battery.But such material electronics conductivity is extremely low, is seriously limiting its application in lithium dynamical battery, the particularly application in high power battery.It is a kind ofly the most simply, relatively effectively to improve its conductivity that carbon coats, thereby improves the method for its chemical property, but the selection of carbon coated presoma and method for coating thereof are the difficult points of this process.
In order to the carbon matrix precursor that coats glucose, sucrose, starch are arranged at present, polymer alcohol, olefin(e) acid and acid amides etc., but, because these carbon matrix precursors formed carbon graphite degree under the material sintering is temperature required is low, so the material electric conductivity of its preparation is difficult to be improved by a relatively large margin.
Summary of the invention
The carbon that the purpose of this invention is to provide a kind of anode material for lithium-ion batteries coats presoma.
Concrete technical scheme is as follows:
A kind of carbon of anode material for lithium-ion batteries coats presoma, comprise lithium source, source of iron, source of phosphoric acid and coating carbon source phenolic resins, wherein the mole proportioning of lithium source, source of iron, source of phosphoric acid is: 1~1.1: 1: 1, the consumption of described phenolic resins was 4~10g/1mol lithium source.
Preferably, described phenolic resins is resol resin or part bakelite.
Preferably, described lithium source is lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate, lithium nitrate or lithium fluoride.
Preferably, described source of iron is ferric oxalate, ferrous oxalate, iron oxide, tri-iron tetroxide, ferrous sulfate, ferrous nitrate or frerrous chloride.
Preferably, described source of phosphoric acid is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.
Another object of the present invention provides the preparation method that above-mentioned carbon coats presoma.
Concrete technical scheme is as follows:
A kind of above-mentioned carbon coats the preparation method of presoma, comprises the steps:
(1) in planetary ball mill, add solvent, take by weighing lithium source, source of iron and source of phosphoric acid by the mole proportion speed and place planetary ball mill, the ball milling mixing, the consumption of described solvent is as the criterion soaking into raw material fully;
(2) phenolic resins is dissolved in the identical solvent of step (1), is mixed with the solution that concentration is 15-25%, join then in the planetary ball mill in the step (1), continue the ball milling mixing;
(3) step (2) is obtained mixture oven dry and vacuumize, dried mixture in pure argon atmosphere, is calcined 3-5h under 300-500 ℃ of condition, the carbon that namely gets described anode material for lithium-ion batteries behind the cooling ball milling coats presoma.
Preferably, described solvent is one or more in water, acetone, the ethanol.
Another object of the present invention provides a kind of anode material for lithium-ion batteries.
Concrete technical scheme is as follows:
A kind ofly coat presoma by above-mentioned carbon and prepare anode material for lithium-ion batteries.
Another object of the present invention provides the preparation method of above-mentioned anode material for lithium-ion batteries.
Concrete technical scheme is as follows:
A kind of preparation method of anode material for lithium-ion batteries comprises following steps: the carbon that method for preparing is obtained coats presoma in pure argon atmosphere, calcines 5-10h under the 650-900 ℃ of condition, namely.
Advantage of the present invention is:
The present invention is directed to present phosphoric acid is the electrode material electric conductivity difference, thereby causes the problem of serious polarization, provides a kind of material to be easy to get, simple to operate, is fit to large-scale production, and the carbon that can effectively improve material conductivity coats presoma and preparation method thereof.
Carbon of the present invention coats presoma and adds phenolic resins and use carbon source as coating, and carries out the planetary ball mill certain hour in solvent, after the desolventizing in inert atmosphere synthesizing lithium ion cell positive cell polar material.This method is to contain Sp at high proportion
2Carbon is carbon source, improves the degree of graphitization of carbon, thereby more effective reduction material is because the serious polarization that poorly conductive causes, simultaneously the reproducibility that has of phenolic resins has prevented the unfavorable oxidation of transition metal, and raw material is cheap, be easy to get, process is simple, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is first three circle charging and discharging curve of LiFePO4/C positive electrode (embodiment 1 method prepares);
The AC impedance figure (wherein the upper left corner is the match equivalent circuit diagram) of LiFePO4/C (LFP/C-G) positive electrode that Fig. 2 prepares for prepared LiFePO4/C (LFP/C-R) positive electrode of the embodiment of the invention 2 methods with glucose conventional bag coating method.
Embodiment
The used phenolic resins of the embodiment of the invention is according to " Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas " (J.AM.CHEM.SOC.2006,128,11652-11662) the synthetic gained of the method for document record.
Embodiment 1
The carbon of the described anode material for lithium-ion batteries of present embodiment coats presoma, comprises LiOH (lithium source), FeC
2O
4.2H
2O (source of iron), HN
4H
2P0
4(source of phosphoric acid) and coating carbon source phenolic resins, wherein the mole proportioning of lithium source, source of iron, source of phosphoric acid is: 1: 1: 1, be respectively 0.02mol.
Above-mentioned carbon coats the preparation method of presoma, comprises the steps:
(1) in planetary ball mill, adds 40ml ethanol, take by weighing lithium source, source of iron and source of phosphoric acid by the mole proportion speed and place planetary ball mill, the ball milling mixing;
(2) phenolic resins is dissolved in the ethanol, is mixed with concentration and is 20% solution, splash into the above-mentioned solution of 0.8247g in the planetary ball mill in the step (1) then, continue the ball milling mixing;
(3) step (2) is obtained 80 ℃ in mixture oven dry and in 120 ℃ of vacuumize 6h, with dried mixture in pure argon atmosphere, calcine 4h under 450 ℃ of conditions, the carbon that namely gets the described anode material for lithium-ion batteries of present embodiment behind the cooling ball milling coats presoma.
The carbon that method for preparing is obtained coats presoma, continues to calcine 10h under 700 ℃ of conditions in pure argon atmosphere, namely gets the described anode material for lithium-ion batteries of present embodiment after the cooling.
Embodiment 2
The carbon of the described anode material for lithium-ion batteries of present embodiment coats presoma, comprise lithium carbonate (lithium source), frerrous chloride (source of iron), phosphoric acid (source of phosphoric acid) and coat carbon source phenolic resins, wherein the mole proportioning of lithium source, source of iron, source of phosphoric acid is: 1.05: 1: 1, be respectively 0.021mol, 0.020mol, 0.020mol.
Above-mentioned carbon coats the preparation method of presoma, comprises the steps:
(1) in planetary ball mill, adds 40ml acetone, take by weighing lithium source, source of iron and source of phosphoric acid by the mole proportion speed and place planetary ball mill, the ball milling mixing;
(2) phenolic resins is dissolved in the ethanol, is mixed with concentration and is 15% solution, splash into the above-mentioned solution of 1.0996g in the planetary ball mill in the step (1) then, continue the ball milling mixing;
(3) step (2) is obtained 80 ℃ in mixture oven dry and in 120 ℃ of vacuumize 6h, with dried mixture in pure argon atmosphere, calcine 4h under 500 ℃ of conditions, the carbon that namely gets the described anode material for lithium-ion batteries of present embodiment behind the cooling ball milling coats presoma.
The carbon that method for preparing is obtained coats presoma, continues to calcine 8h under 800 ℃ of conditions in pure argon atmosphere, namely gets the described anode material for lithium-ion batteries of present embodiment after the cooling.
Embodiment 3
The carbon of the described anode material for lithium-ion batteries of present embodiment coats presoma, comprise lithium nitrate (lithium source), ferrous sulfate (source of iron), diammonium hydrogen phosphate (source of phosphoric acid) and coat carbon source phenolic resins, wherein the mole proportioning of lithium source, source of iron, source of phosphoric acid is: 1.1: 1: 1, be respectively 0.022mol, 0.020mol, 0.020mol.
Above-mentioned carbon coats the preparation method of presoma, comprises the steps:
(1) in planetary ball mill, adds 40ml water, take by weighing lithium source, source of iron and source of phosphoric acid by the mole proportion speed and place planetary ball mill, the ball milling mixing;
(2) phenolic resins is dissolved in the ethanol, is mixed with concentration and is 25% solution, splash into the above-mentioned solution of 0.65976g in the planetary ball mill in the step (1) then, continue the ball milling mixing;
(3) step (2) is obtained 80 ℃ in mixture oven dry and in 120 ℃ of vacuumize 6h, with dried mixture in pure argon atmosphere, calcine 4h under 350 ℃ of conditions, the carbon that namely gets the described anode material for lithium-ion batteries of present embodiment behind the cooling ball milling coats presoma.
The carbon that method for preparing is obtained coats presoma, continues to calcine 5h under 900 ℃ of conditions in pure argon atmosphere, namely gets the described anode material for lithium-ion batteries of present embodiment after the cooling.
Embodiment 4 application experiments
The application experiment of the LiFePO4/C positive electrode that embodiment 1 and 2 methods prepare is shown in Fig. 1-2.
Fig. 1 is with the prepared LiFePO of the embodiment of the invention 1
4First three circle charging and discharging curve figure of/C material, as can be seen from the figure, along with the intensification of preceding two circle electrolyte infiltration degrees, when arriving the 3rd circle, the charging and discharging curve terrace part accounts for the absolute major part of curve and does not have polarization substantially, and discharge capacity reaches 168.89mAhg under 0.1c charge-discharge magnification condition
-1, be almost LiFePO
4Theoretical capacity 170mAhg
-1
Fig. 2 is the material (LFP-C/G) that adopts carbon source that the present invention tells to coat gained material (LFP-C/R) and adopt traditional glucose to coat as carbon source, do electrode with lithium, the AC impedance comparison diagram that 2032 button cells are tested and equivalent circuit diagram thereof (upper left insertion portion among the figure), as can be seen from the figure the charge transfer resistance of LFP-C/R (Rct) is littler than LFP-C/G, illustrate that carbon source that the present invention tells coats LiFePO4 and can effectively reduce material resistance, reduce the polarization phenomena of material.
More than be at the specifying of possible embodiments of the present invention, but this embodiment is not in order to limiting claim of the present invention, does not allly break away from the equivalence that skill spirit of the present invention does and implement or change, all should be contained in the claim of the present invention.