CN103956486A - Preparation method of nano-fibrous lithium cobalt phosphate positive electrode material - Google Patents
Preparation method of nano-fibrous lithium cobalt phosphate positive electrode material Download PDFInfo
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- CN103956486A CN103956486A CN201410124539.8A CN201410124539A CN103956486A CN 103956486 A CN103956486 A CN 103956486A CN 201410124539 A CN201410124539 A CN 201410124539A CN 103956486 A CN103956486 A CN 103956486A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention relates to a preparation method of a nano-fibrous lithium cobalt phosphate positive electrode material, and belongs to the technical field of chemical industry electrode material preparation technologies. The preparation method comprises the following steps: dissolving cobalt salt, lithium salt, phosphate and a high-molecular polymer in deionized water, uniformly stirring the obtained solution, and allowing the solution to stand until the solution is clear; carrying out electrostatic spinning; and calcining the obtained spinning products in inert atmosphere, cooling the obtained material to room temperature after the calcining reaction, and removing the obtained products to obtain the lithium cobalt phosphate positive electrode materials with a nano-fibrous morphology. The method has the advantages of simplicity, easy operation, and strong controllability of preparation parameters; the obtained product has a nano-fibrous morphology, so the contact of the positive electrode material with an electrolyte contact is increased, and it is in favor of the transmission of lithium ions; and the positive electrode material and carbon form a composite structure, so the conductivity of the positive electrode material is improved, and the positive electrode material has a good electrochemical performance, and is expected to become a high-voltage positive electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer fibrous cobalt phosphate lithium positive electrode, belong to chemical industry electrode material manufacturing process technology field.
Background technology
Lithium ion battery is since successfully developing the beginning of the nineties in last century, just high with its specific energy, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, the unique advantage such as pollution-free and receiving much attention, and extensive use in the small portable electronic products such as mobile phone, digital camera, notebook computer.In recent years, for reply auto industry fast development bring such as negative effects such as environmental pollution, petroleum resources sharply consume, the countries such as the U.S., Japan, China are all actively developing the employing electric automobile EV of clean energy resource and the R&D work of hybrid electric vehicle HEV.And lithium ion battery is as the topmost candidate's electrical source of power of following electric automobile, there is feature with low cost, excellent performance, become the main study hotspot in international electrokinetic cell field, be wherein the emphasis of research as the exploitation of the function admirable electrode material that improves one of key factor of performance of lithium ion battery always.
At present, the main positive electrode of applying in lithium ion battery is LiFePO4, cobalt acid lithium, element material, wherein LiFePO4 material with carbon element, environmental friendliness safe with material itself, aboundresources, cyclical stability advantages of higher are paid attention to widely, and obtain good business application.But along with science and technology and the development in epoch, people have higher requirement to lithium ion battery, and especially the fail safe to material and energy density are especially paid attention to.Under this trend, theoretical energy density only has the LiFePO4 of 586Wh/kg also more and more can not meet the expectation of people to lithium ion battery high-energy-density.Cobalt phosphate lithium due to have with LiFePO4 same crystal structure not only compatible the high security of polyanion structure, its higher theoretical energy density (802Wh/kg) also makes it be expected to become alternative LiFePO4 becomes anode material for lithium-ion batteries of future generation, has good prospect and potentiality.
Recent study personnel have carried out a series of research to cobalt phosphate lithium positive electrode, but cobalt phosphate lithium positive electrode synthetic also exists very large problem and difficult point, such as the more difficult control of synthesis technique, calcining heat interval are narrower, material property is poor etc.
Summary of the invention
The object of the invention is in order to solve existing lithium ion battery cobalt phosphate lithium positive electrode ion, electron conduction is poor, the problem of synthesis condition harshness, to improve the chemical property of lithium ion battery cobalt phosphate lithium positive electrode, provide a kind of preparation method of nanometer fibrous cobalt phosphate lithium positive electrode.
The object of the invention is to be achieved through the following technical solutions.
The preparation method of a kind of nanometer fibrous cobalt phosphate lithium positive electrode of the present invention, concrete steps are:
1) lithium salts, phosphate, the cobalt salt that are 1:1:1 by mol ratio are successively dissolved in deionized water; Subsequently high molecular polymer is added to gained solution and stir after leave standstill to clarification;
2) solution is carried out to electrostatic spinning;
3) by step 2) in the spinning product that obtains under inert atmosphere, calcine, after calcination reaction finishes, treat that material cooled is to room temperature, take out product and obtain having the cobalt phosphate lithium positive electrode of nanofibrous structures.
Above-mentioned steps 1) in cobalt salt be cobaltous sulfate, cobalt nitrate, cobalt acetate; Lithium salts is lithium hydroxide, lithium nitrate, lithium acetate, lithium dihydrogen phosphate; Phosphate is phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate; High molecular polymer is polyvinylpyrrolidone, polyvinyl alcohol.Wherein the addition of lithium salts, phosphate, cobalt salt is 6～12mmol, and the addition of high molecular polymer is 600～1000mg, and the addition of deionized water is 10～12ml.
Above-mentioned steps 2) method of described electrostatic spinning is: spinning equipment positive high voltage static is 10～30 kilovolts, and the additional negative high voltage static of receiving terminal is 0～10 kilovolt.
Above-mentioned steps 3) in calcining heat be 650～750 DEG C, the rate of heat addition is 2～5 DEG C/min, calcination time is 6～12h; Inert gas is argon gas or nitrogen.
Beneficial effect
It is of the present invention that preparation is simple, preparation parameter controllability is strong, the cobalt phosphate lithium material of preparing gained has nanofiber pattern, increase the transmission that contact and be conducive to lithium ion of material with electrolyte, the introducing of carbon in material simultaneously, improve the conductivity of material, improved chemical property, be expected to as the high-tension anode material for lithium-ion batteries of one.
The present invention selects comparatively common cobalt salt, lithium salts, phosphate and high molecular polymer, adopts electrostatic spinning process, by the synthetic cobalt phosphate lithium positive electrode of method of one-step calcination, has studied its chemical property.
Brief description of the drawings
Fig. 1 is the ESEM shape appearance figure before the cobalt phosphate lithium positive electrode calcining prepared of embodiment;
Fig. 2 is the ESEM shape appearance figure after the cobalt phosphate lithium positive electrode calcining prepared of embodiment;
Fig. 3 is the X ray diffracting spectrum of the cobalt phosphate lithium positive electrode prepared of embodiment;
Fig. 4 is the charging and discharging curve figure of the cobalt phosphate lithium positive electrode prepared of embodiment under 17mA/g.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated
Embodiment 1
A preparation method for nanometer fibrous cobalt phosphate lithium positive electrode, concrete steps are:
1) first the lithium hydroxide of 8mmol, phosphoric acid are dissolved in to reaction in 12ml deionized water and generate lithium dihydrogen phosphate solution, then add 1g polyvinylpyrrolidone (molecular weight is 1,300,000) to stir, subsequently by extremely clarification of solution left standstill;
2) gained is carried out to electrostatic spinning, positive high voltage is 30kv, and receiving terminal adopts aluminium foil, and negative high voltage is-5kv.The spinning product ESEM shape appearance figure of collecting as shown in Figure 1.
3) above spinning product is calcined under argon gas atmosphere, calcining heat is 750 DEG C, and the rate of heat addition is 5 DEG C/min, and the reaction time is 12h; After having reacted, treat that material temperature is cooled to room temperature, taking-up product obtains having the cobalt phosphate lithium positive electrode of nanofiber pattern, and its ESEM shape appearance figure as shown in Figure 2.
The cobalt phosphate lithium positive electrode obtaining is carried out to X-ray diffraction test, and as shown in Figure 3, the diffraction pattern obtaining and the contrast of standard spectrogram are without assorted peak explanation synthetic material without miscellaneous for result, and the comparatively sharp-pointed illustrative material crystallinity of diffraction maximum is better; To obtain after composite material directly applies to anode material for lithium-ion batteries and carry out charging and discharging capacity test: cobalt phosphate lithium positive electrode will be as work electrode, and lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out to charge-discharge test, and voltage range is 3～5V (vs.Li
+/ Li), current density is 17mA/g.
Test result: when cobalt phosphate lithium positive electrode discharges and recharges under 17mA/g, as shown in Figure 4, its electric discharge (embedding lithium) specific capacity is 49.3mAh/g to specific capacity curve.
Embodiment 2
1) first the lithium dihydrogen phosphate of 12mmol, cobalt nitrate are dissolved in 10ml deionized water, then add 600mg polyvinylpyrrolidone (molecular weight is 1,300,000) to stir, subsequently by extremely clarification of solution left standstill;
2) gained solution is carried out to electrostatic spinning, positive high voltage is 10kv, and receiving terminal adopts aluminium foil, and negative high voltage is-10kv.
3) above spinning product is calcined under argon gas atmosphere, calcining heat is 650 DEG C, and the rate of heat addition is 2 DEG C/min, and the reaction time is 6h; After having reacted, treat that material temperature is cooled to room temperature, take out product and obtain having the cobalt phosphate lithium positive electrode of nanofiber pattern, and it is carried out to electro-chemical test.
The cobalt phosphate lithium positive electrode obtaining is carried out to X-ray diffraction test, and the diffraction pattern obtaining and the contrast of standard spectrogram are without assorted peak explanation synthetic material without miscellaneous, and the comparatively sharp-pointed illustrative material crystallinity of diffraction maximum is better; To obtain after composite material directly applies to anode material for lithium-ion batteries and carry out charging and discharging capacity test: cobalt phosphate lithium positive electrode will be as work electrode, and lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out to charge-discharge test, and voltage range is 3～5V (vs.Li
+/ Li), current density is 17mA/g.
Test result: cobalt phosphate lithium positive electrode (embedding lithium) specific capacity of discharging under 17mA/g is 45.1mAh/g.
Embodiment 3
1) first the lithium dihydrogen phosphate of 6mmol, cobalt nitrate are dissolved in 10ml deionized water, then add 800mg polyvinyl alcohol to be stirred well to dissolving, subsequently by extremely clarification of solution left standstill;
2) gained solution is carried out to electrostatic spinning, positive high voltage is 15kv, and receiving terminal adopts aluminium foil, and negative high voltage is 0kv.
3) above spinning product is calcined under nitrogen atmosphere, calcining heat is 700 DEG C, and the rate of heat addition is 2 DEG C/min, and the reaction time is 8h; After having reacted, treat that material temperature is cooled to room temperature, take out product and obtain having the cobalt phosphate lithium positive electrode of nanofiber pattern, and it is carried out to electro-chemical test.
The cobalt phosphate lithium positive electrode obtaining is carried out to X-ray diffraction test, and the diffraction pattern obtaining and the contrast of standard spectrogram are without assorted peak explanation synthetic material without miscellaneous, and the comparatively sharp-pointed illustrative material crystallinity of diffraction maximum is better; To obtain after composite material directly applies to anode material for lithium-ion batteries and carry out charging and discharging capacity test: cobalt phosphate lithium positive electrode will be as work electrode, and lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out to charge-discharge test, and voltage range is 3～5V (vs.Li
+/ Li), current density is 17mA/g.
Test result: cobalt phosphate lithium positive electrode (embedding lithium) specific capacity of discharging under 17mA/g is 40.7mAh/g.
Claims (4)
1. a preparation method for nanometer fibrous cobalt phosphate lithium positive electrode, is characterized in that: concrete steps are:
1) lithium salts, phosphate, the cobalt salt that are 1:1:1 by mol ratio are successively dissolved in deionized water; Subsequently high molecular polymer is added to gained solution and stir after leave standstill to clarification;
2) solution is carried out to electrostatic spinning;
3) by step 2) in the spinning product that obtains under inert atmosphere, calcine, after calcination reaction finishes, treat that material cooled is to room temperature, take out product and obtain having the cobalt phosphate lithium positive electrode of nanofibrous structures.
2. the preparation method of a kind of nanometer fibrous cobalt phosphate lithium positive electrode as claimed in claim 1, is characterized in that: in described step 1), cobalt salt is cobaltous sulfate, cobalt nitrate, cobalt acetate; Lithium salts is lithium hydroxide, lithium nitrate, lithium acetate, lithium dihydrogen phosphate; Phosphate is phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate; High molecular polymer is polyvinylpyrrolidone, polyvinyl alcohol; Wherein the addition of lithium salts, phosphate, cobalt salt is 6～12mmol, and the addition of high molecular polymer is 600～1000mg, and the addition of deionized water is 10～12ml.
3. the preparation method of a kind of nanometer fibrous cobalt phosphate lithium positive electrode as claimed in claim 1, it is characterized in that: described step 2) method of described electrostatic spinning is: spinning equipment positive high voltage static is 10～30 kilovolts, and the additional negative high voltage static of receiving terminal is 0～10 kilovolt.
4. the preparation method of a kind of nanometer fibrous cobalt phosphate lithium positive electrode as claimed in claim 1, is characterized in that: in described step 3), calcining heat is 650～750 DEG C, and the rate of heat addition is 2～5 DEG C/min, and calcination time is 6～12h; Inert gas is argon gas or nitrogen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201341A (en) * | 2014-08-26 | 2014-12-10 | 江苏科技大学 | Preparation method of lithium titanate-nickel oxide nanofiber composite material for lithium battery |
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN110931759A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | Al (aluminum)2O3Coated Co-W double-doped LiNiO2Lithium ion battery anode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201030197A (en) * | 2008-12-03 | 2010-08-16 | Elmarco Sro | A method for production of nanofibres and/or nanofibrous structures of phospho-olivines, nanofibres of phospho-olivines and nanofibrous structure formed of nanofibres of phospho-olivines |
| CN102340002A (en) * | 2011-08-29 | 2012-02-01 | 长春理工大学 | Lithium iron phosphate nanofiber as lithium ion battery cathode material and preparation method thereof |
-
2014
- 2014-03-28 CN CN201410124539.8A patent/CN103956486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201030197A (en) * | 2008-12-03 | 2010-08-16 | Elmarco Sro | A method for production of nanofibres and/or nanofibrous structures of phospho-olivines, nanofibres of phospho-olivines and nanofibrous structure formed of nanofibres of phospho-olivines |
| CN102340002A (en) * | 2011-08-29 | 2012-02-01 | 长春理工大学 | Lithium iron phosphate nanofiber as lithium ion battery cathode material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201341A (en) * | 2014-08-26 | 2014-12-10 | 江苏科技大学 | Preparation method of lithium titanate-nickel oxide nanofiber composite material for lithium battery |
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN105803580B (en) * | 2016-04-15 | 2018-05-18 | 东华大学 | A kind of preparation method of phosphatization cobalt hollow Nano fiber in use material |
| CN110931759A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | Al (aluminum)2O3Coated Co-W double-doped LiNiO2Lithium ion battery anode material and preparation method thereof |
| CN110931759B (en) * | 2019-12-19 | 2021-04-27 | 安徽正熹标王新能源有限公司 | Al (aluminum)2O3Coated Co-W double-doped LiNiO2Lithium ion battery anode material and preparation method thereof |
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Application publication date: 20140730 |