CN106684353A - Preparation method for carbon-coated potassium vanadium phosphate and application of carbon-coated potassium vanadium phosphate - Google Patents
Preparation method for carbon-coated potassium vanadium phosphate and application of carbon-coated potassium vanadium phosphate Download PDFInfo
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- CN106684353A CN106684353A CN201611229524.3A CN201611229524A CN106684353A CN 106684353 A CN106684353 A CN 106684353A CN 201611229524 A CN201611229524 A CN 201611229524A CN 106684353 A CN106684353 A CN 106684353A
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- vanadium phosphate
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method for carbon-coated potassium vanadium phosphate. The preparation method comprises the following steps of S1 adding ammonium metavanadate, citric acid and monopotassium phosphate into deionized water and uniformly stirring to obtain mixed solution; S2 freezing and drying the mixed solution to obtain a precursor; and S3 calcining the precursor in mixed gas of argon and hydrogen at the calcination temperature of 500-1200 DEG C to obtain a black solid, namely carbon-coated potassium vanadium phosphate. The preparation method for the carbon-coated potassium vanadium phosphate, which is provided by the invention, is easy to operate and cannot produce harmful gas and cause pollution, and the prepared carbon-coated potassium vanadium phosphate has uniform morphology and single phase. The invention also discloses application of the carbon-coated potassium vanadium phosphate to a positive electrode material of a potassium battery material.
Description
Technical field
The present invention relates to battery material technical field, specifically, is related to a kind of preparation side of the vanadium phosphate potassium of carbon coating
Method and the application on battery material.
Background technology
Energy resource consumption is the key character of modern social development, and efficient energy-storage system be then regenerative resource industry,
The core pillar of consumer electronics industry, transportation industry.In many energy storage modes, lithium ion battery with light weight, capacity it is high and
The advantages of memory-less effect, in current energy storage industry core status are occupied.Due to lithium ion battery high-energy-density and good
Cycle performance so as to expand to electric automobile and mixed power electric car using from portable electric appts.However, lithium resource
Rare and skewness, adding growing consumption makes its cost constantly rise, so as to limit its extensive big rule
Mould application.
It is reported that careful professor in Tokyo university of science coltfoal field et al. is in the research and development of kalium ion battery technology of new generation
Breach is have found, research worker is successfully realized multiple discharge and recharge in the case where performance is not reduced, makes using graphite electrode
It is expected to improve 10 times than the charge/discharge rates of lithium ion battery with the novel battery of the technology, and high-intensity currrent can be corresponded to,
The bigger electric power of output.
With going deep into for research, phosphate system electrode material not only low cost is gradually found, and with storage well
Sodium performance, is the preferable sodium-ion battery positive electrode material of a class.But phosphate material is led due to the inducing action of phosphate radical
Cause its electric conductivity poor so as to have high power capacity to be but difficult to bring into play completely on foot, it is necessary to which we are by the original position of conductive materials
Cladding, to improve its electronic conductivity, improves its chemical property.Phosphoric acid vanadium lithium and vanadium phosphate sodium are respectively as lithium ion and sodium
The electrode material of ion battery has been widely studied, and vanadium phosphate potassium with both have close ratio and structure, and due to
Potassium ion it is embedded, directly increase the ion diffusion admittance of the material, thus in theory its as kalium ion battery positive electrical
Pole material should have larger potentiality.
The content of the invention
One purpose of the present invention is a kind of preparation method of the vanadium phosphate potassium for providing carbon coating.
The technical scheme that the preparation method of the vanadium phosphate potassium of carbon coating disclosed by the invention is adopted is：
A kind of preparation method of the vanadium phosphate potassium of carbon coating, comprises the following steps：
S1 adds ammonium metavanadate, citric acid, potassium dihydrogen phosphate into deionized water, is uniformly mixing to obtain mixed solution；
Mixed solution lyophilization is obtained presoma by S2；
S3 presomas are calcined in argon, the mixed gas of hydrogen, and calcining heat is 500 to 1200 DEG C, and obtaining black solid is
The vanadium phosphate potassium of carbon coating.
Preferably, in step sl, the mol ratio of the ammonium metavanadate, citric acid and potassium dihydrogen phosphate is 1：（1
~5）：（1~5）, the mole (mol) of the ammonium metavanadate is 1 with the ratio of the volume (L) of deionized water：（1~5）.
Preferably, in step sl, the mol ratio of the ammonium metavanadate, citric acid and potassium dihydrogen phosphate is 1：1：
1.5, the mole (mol) of the ammonium metavanadate is 1 with the ratio of the volume (L) of deionized water：4.
Preferably, in step s 2, mixed solution lyophilization 12~72 hours.
Preferably, in step s 2, mixed solution lyophilization 48 hours.
Preferably, in step s3, the calcination time of presoma is 3~48 hours.
Preferably, in step s3, the calcining heat of presoma is 900 DEG C, and calcination time is 12 hours.
The beneficial effect of the preparation method of the vanadium phosphate potassium of carbon coating disclosed by the invention is：It is easy to operate, course of reaction
It is middle to produce without harmful gass, do not result in pollution, and the vanadium phosphate potassium of the carbon coating for producing has uniform morphology, thing is mutually single.
Another object of the present invention is to a kind of new opplication of the vanadium phosphate potassium of carbon coating is provided, as kalium ion battery
Positive electrode, with good capacity retention energy.
Description of the drawings
Fig. 1 be the vanadium phosphate potassium of carbon coating of the present invention preparation method made by carbon coating vanadium phosphate potassium scanning electron microscope
Figure；
Fig. 2 be the vanadium phosphate potassium of carbon coating of the present invention preparation method made by carbon coating vanadium phosphate potassium X-ray diffractogram
Spectrum；
Fig. 3 be carbon coating vanadium phosphate potassium made by electrode slice under the voltage window of 2.5~4.3 V with 0.2 mV s-1's
Sweep CV curves under speed；
Fig. 4 be carbon coating vanadium phosphate potassium made by electrode slice under the voltage window of 2.5~4.3V with 20 mA/g electric current densities
The charging and discharging curve of different number of turns during test；
Fig. 5 be carbon coating vanadium phosphate potassium made by electrode slice under the voltage window of 2.5~4.3V with 20 mA/g electric current densities
Cycle performance during test.
Specific embodiment
The present invention is further elaborated with reference to specific embodiment and is illustrated：
A kind of preparation method of the vanadium phosphate potassium of carbon coating, comprises the following steps：
S1 is by ammonium metavanadate, citric acid, potassium dihydrogen phosphate with mol ratio as 1：（1~5）：（1~5）Mixed, by metavanadic acid
The mole of ammonium（mol）With the volume of deionized water（L）Ratio be 1：（1~5）, by ammonium metavanadate, citric acid, potassium dihydrogen phosphate
Add into deionized water, be uniformly mixing to obtain mixed solution；
Mixed solution lyophilization is obtained presoma in 12~72 hours by S2；
S3 is 92 in volume ratio：In 8 argon and the mixed gas of hydrogen, presoma is entered with calcining heat as 500 to 1200 DEG C
Row calcining, calcination time is 3~48 hours, obtains the vanadium phosphate potassium that black solid is carbon coating.
Embodiment
Ammonium metavanadate, the citric acid of 0.01mol, the potassium dihydrogen phosphate of 0.015mol of 0.01mol are weighed, adds 40mL's
In deionized water, mixed solution is uniformly mixing to obtain, mixed solution lyophilization is obtained into presoma in 48 hours, in hydrogen volume
Fraction is in 8% hydrogen and the mixed gas of argon, with 900 DEG C of temperature calcining 12 hours to be carried out, and obtains black solid, as
The vanadium phosphate potassium of carbon coating.
Refer to the scanning electron microscope (SEM) photograph of the vanadium phosphate potassium of the carbon coating of the above-mentioned preparations of Fig. 1, it is seen then that the vanadium phosphate potassium of carbon coating
Pattern with three-dimensional porous knot.The X ray diffracting spectrum of the vanadium phosphate potassium of the carbon coating of the above-mentioned preparations of Fig. 2 is refer to, by Fig. 2
Can be seen that, can fit like a glove with standard card, without obvious miscellaneous peak, thing is mutually pure.
By the vanadium phosphate potassium of products therefrom carbon coating and conductive acetylene is black, binding agent PVDF in mass ratio 80:10:10 mix
Close, add a certain amount of 1-Methyl-2-Pyrrolidone（NMP）, pasty state is fully ground into, it is uniformly coated on the mm of diameter 14, thickness
On about 9 μm of Copper Foil, then Copper Foil is vacuum dried 12 hours under 120 DEG C of temperature conditionss, after cooling, taking-up is fabricated to electricity
It is extremely standby；Upper step electrode slice is transferred in the glove box full of argon, using CR2025 type button cell shells, diameter 16mm
Metallic potassium piece is dissolved with the EC and DEC of 1 M KPF6 as negative electrode, the type polypropylene films of Celgard 2325 as barrier film
（Volume ratio 1:1）Mixed liquor as electrolyte, the battery standing 10h being completed is to be measured；Performance test is in Land tests system
Carry out on system.Electrode slice made by the vanadium phosphate potassium of Fig. 3 carbon coatings be refer under the voltage window of 2.5~4.3 V with 0.2
mV s-1Sweep CV curves under speed, as can be seen from Figure, CV curves have obvious redox peaks.Refer to Fig. 4 carbon coatings
Different number of turns when electrode slice made by vanadium phosphate potassium is tested under the voltage window of 2.5~4.3V with 20 mA/g electric current densities
Charging and discharging curve, as seen from Figure 4, the discharge capacity of the vanadium phosphate potassium first circle of carbon coating is 55 mAh g-1, 3.88V with
3.60 V or so have obvious discharge platform.Electrode slice made by the vanadium phosphate potassium of Fig. 5 carbon coatings be refer to 2.5~4.3V's
Cycle performance when being tested with 20 mA/g electric current densities under voltage window, still has good circulation steady after the circle of circulation 200
It is qualitative.
Finally it should be noted that above example is only illustrating technical scheme, rather than to present invention guarantor
The restriction of shield scope, although having made to explain to the present invention with reference to preferred embodiment, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent, without deviating from the reality of technical solution of the present invention
Matter and scope.
Claims (8)
1. the preparation method of the vanadium phosphate potassium of a kind of carbon coating, it is characterised in that comprise the following steps：
S1 adds ammonium metavanadate, citric acid, potassium dihydrogen phosphate into deionized water, is uniformly mixing to obtain mixed solution；
Mixed solution lyophilization is obtained presoma by S2；
S3 presomas are calcined in argon, the mixed gas of hydrogen, and calcining heat is 500 to 1200 DEG C, and obtaining black solid is
The vanadium phosphate potassium of carbon coating.
2. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 1, it is characterised in that in step sl, described
The mol ratio of ammonium metavanadate, citric acid and potassium dihydrogen phosphate is 1：（1~5）：（1~5）, the mole of the ammonium metavanadate
(mol) it is 1 with the ratio of the volume (L) of deionized water：（1~5）.
3. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 2, it is characterised in that in step sl, described
The mol ratio of ammonium metavanadate, citric acid and potassium dihydrogen phosphate is 1：1：1.5, the mole (mol) of the ammonium metavanadate with go from
The ratio of the volume (L) of sub- water is 1：4.
4. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 2 or claim 3, it is characterised in that in step s 2, mixes
Close solution lyophilization 12~72 hours.
5. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 4, it is characterised in that in step s 2, mixing
Solution lyophilization 48 hours.
6. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 2 or claim 3, it is characterised in that in step s3, front
The calcination time for driving body is 3~48 hours.
7. the preparation method of the vanadium phosphate potassium of carbon coating as claimed in claim 6, it is characterised in that in step s3, forerunner
The calcining heat of body is 900 DEG C, and calcination time is 12 hours.
8. the vanadium phosphate potassium of carbon coating is applied to the positive electrode of kalium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611229524.3A CN106684353A (en) | 2016-12-27 | 2016-12-27 | Preparation method for carbon-coated potassium vanadium phosphate and application of carbon-coated potassium vanadium phosphate |
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| CN201611229524.3A CN106684353A (en) | 2016-12-27 | 2016-12-27 | Preparation method for carbon-coated potassium vanadium phosphate and application of carbon-coated potassium vanadium phosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258219A (en) * | 2018-01-15 | 2018-07-06 | 桂林理工大学 | A kind of preparation method of kalium ion battery positive pole material fluorophosphoric acid vanadium potassium/carbon |
| CN108365199A (en) * | 2018-02-11 | 2018-08-03 | 西北工业大学 | Carbon-coated fluorophosphoric acid vanadium potassium carbon nano tube compound material and preparation method and application |
| CN113845102A (en) * | 2021-06-15 | 2021-12-28 | 湖南大学 | Method for rapidly preparing high-quality fluorine-containing phosphate polyanion compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102386412A (en) * | 2011-11-11 | 2012-03-21 | 中南大学 | Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof |
| CN104638228A (en) * | 2015-02-04 | 2015-05-20 | 武汉理工大学 | Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire |
| CN105336924A (en) * | 2015-09-25 | 2016-02-17 | 中南大学 | Preparation method of carbon coated vanadium sodium phosphate positive electrode material |
-
2016
- 2016-12-27 CN CN201611229524.3A patent/CN106684353A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102386412A (en) * | 2011-11-11 | 2012-03-21 | 中南大学 | Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof |
| CN104638228A (en) * | 2015-02-04 | 2015-05-20 | 武汉理工大学 | Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire |
| CN105336924A (en) * | 2015-09-25 | 2016-02-17 | 中南大学 | Preparation method of carbon coated vanadium sodium phosphate positive electrode material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258219A (en) * | 2018-01-15 | 2018-07-06 | 桂林理工大学 | A kind of preparation method of kalium ion battery positive pole material fluorophosphoric acid vanadium potassium/carbon |
| CN108365199A (en) * | 2018-02-11 | 2018-08-03 | 西北工业大学 | Carbon-coated fluorophosphoric acid vanadium potassium carbon nano tube compound material and preparation method and application |
| CN113845102A (en) * | 2021-06-15 | 2021-12-28 | 湖南大学 | Method for rapidly preparing high-quality fluorine-containing phosphate polyanion compound |
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Effective date of registration: 20180730 Address after: 518000 Shenzhen, Nanshan District, Guangdong, Guangdong Province, 15 yuan Road, B, Kexing Science Park, 1 units 702 Applicant after: Shenzhen Lu Xing Zhi Agricultural Technology Co., Ltd. Applicant after: Southwest University Address before: 518000 Baoan District, Xixiang, Shenzhen, Guangdong, Xixiang road junction with Shunchang road Shunchang Road, Taihua Indus Industrial Park, 4 story 10B Applicant before: SHENZHEN CHUANMA ELECTRONIC CO., LTD. Applicant before: Southwest University |
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