CN104600301A - Spherical cobaltous fluoride for battery positive material and preparation method of spherical cobaltous fluoride - Google Patents
Spherical cobaltous fluoride for battery positive material and preparation method of spherical cobaltous fluoride Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 title abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 abstract 3
- 239000013049 sediment Substances 0.000 abstract 2
- 238000000227 grinding Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/582—Halogenides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a spherical cobaltous fluoride for a battery positive material. The spherical cobaltous fluoride is synthesized by ammonium fluoride as a fluorine source, cobalt nitrate hexahydrate as a cobalt source, and ethylene glycol as a solvent by adopting a hydrothermal method, and is spherical CoF2 with the particle sizes are 100-500nm and formed by stacking small nano particles. The invention further discloses a preparation method of the spherical cobaltous fluoride. The method comprises the following steps: weighing cobalt nitrate hexahydrate, ammonium fluoride and urea according to a molar ratio of 1 to (3-4) to (4-5), stirring for dissolving into ethylene glycol, and then transferring into a reaction kettle of which an lining is made from polytetrafluoroethylene; reacting at 120-200 DEG C for 2-40 hours, centrifuging, washing and collecting sediments; and drying the sediments and grinding to form the spherical CoF2. The preparation process disclosed by the invention is simple; the cost is reduced; the preparation cycle is shortened; the efficiency is improved; the volume change for stripping/embedding lithium-ions in the charge and discharge processes is overcome by the spherical CoF2; the specific capacitance of the spherical cobaltous fluoride as the positive material is greatly improved; and the cycle life is greatly prolonged.
Description
Technical field
Embodiments of the present invention relate to lithium battery energy field, and more specifically, embodiments of the present invention relate to a kind of for cell positive material, particularly a kind of spherical CoF by Hydrothermal Synthesis
2and preparation method thereof.
Background technology
In recent years, lithium ion battery as a kind of novel, can the energy storage equipment of discharge and recharge, the portable electric appts such as household electrical appliance, notebook computer and mobile phone are widely used.And in the electrode material of lithium ion battery use, negative material finds after extensive and deep research, positive electrode also plays key effect for the raising of whole battery performance, wherein metal fluoride becomes one of latest model, most potential positive electrode due to its higher theoretical capacity, and the parent being subject to various countries researcher looks at.But this kind of material, due to itself larger band gap and Lithium-ion embeding/deviate from the high megohmite insulant LiF formed in process, causes its conductivity extreme difference, hinder its application in cell positive material field.Therefore, for addressing these problems, researcher proposes a lot of measure improving material.
As far as we know, the nanometer materials designing a kind of three-dimensional structure a kind ofly the most effectively solve one of strategy of problem above.Mainly come from this three-dimensional structure there is the large and ion of contact area, electrical conductivity is fast, in battery charge and discharge process, provide buffer area to avoid larger stereomutation, thus alleviate electrode material pulverizing, finally reach raising chemical property.Up to the present, the research report about negative material is a lot, is also mainly to improve lithium ion storage lithium performance by the structural design of electrode material, as: nano wire/rod, nano particle/crystal, nano flower-like or more complicated structure etc.And for the cobaltous fluoride of positive electrode, adopt green simple synthetic method, design a kind of three-dimensional structure of uniqueness, improving its chemical property, is focus of greatest concern at present.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, the execution mode of a kind of spherical cohalt difluoride for cell positive material and preparation method thereof is provided, to expect can obtain the good material of a kind of chemical property as positive electrode, obtain a kind of simple preparation method simultaneously.
For solving above-mentioned technical problem, one embodiment of the present invention by the following technical solutions:
For a spherical cohalt difluoride for cell positive material, it is fluorine source with ammonium fluoride, and being cobalt source with cobalt nitrate hexahydrate, take ethylene glycol as solvent, spherical CoF that adopt water heat transfer, that take the particle diameter that nanometer granule is stacking as 100 ~ 500nm
2.
For a preparation method for the spherical cohalt difluoride of cell positive material, it comprises the following steps:
(1) get ammonium fluoride, cobalt nitrate hexahydrate and urea according to mol ratio 1:3 ~ 4:4 ~ 5, then stirring and dissolving is in ethylene glycol, obtains pink solution;
(2) described pink solution being proceeded to liner is in the reactor of polytetrafluoroethylene, reacts 2 ~ 40 hours at temperature 120 ~ 200 DEG C, after having reacted, centrifugal, washing, collecting precipitation;
(3) grind after described precipitation being dried, obtain pink powder shape finished product.
Preferably, the mol ratio of described ammonium fluoride, cobalt nitrate hexahydrate and urea is 1:3:5.
Preferably, described pink solution reaction temperature is in a kettle. 200 DEG C, and the reaction time is 20 hours.
Further technical scheme is: it is 3.0 ~ 6.0mg/mL that described cobalt nitrate hexahydrate is dissolved in the concentration after ethylene glycol.
Further technical scheme is: the method for described washing washs 3 times respectively with deionized water and absolute ethanol washing successively.
Further technical scheme is: the method for described drying adopts air dry oven to dry.
Further technical scheme is: the temperature of described drying is 50 ~ 80 DEG C, and the dry time is 6 ~ 12 hours.
Compared with prior art, one of beneficial effect of the present invention is: (1) preparation technology's cheap and simple, spherical CoF
2the preparation of positive electrode is obtained by one pot of water heat transfer, and reduce cost, it also avoid loaded down with trivial details synthesis technique simultaneously, shorten manufacturing cycle, efficiency is high; Use nontoxic green reagent ammonium fluoride as the synthesis of fluorine source, avoid and use severe corrosive HF, reduce potential safety hazard; (2) the spherical CoF prepared
2the design feature of positive electrode is to overcome the change in volume that lithium ion in charge and discharge process is deviate from/embedded by the spheroid of 100 ~ 500nm particle diameter that nanometer granule is stacking; (3) by spherical CoF prepared by this simple method
2specific capacitance and the cycle life of positive electrode improve a lot, we adopt use the same method prepared different temperatures scope under synthesize CoF
2and the CoF under different time condition
2, we find that hydrothermal temperature is 200 DEG C, and the hydro-thermal time is the CoF synthesized under 20h condition
2structure is the most stable, at current density 20mAg
-1under first discharge capacity be 567.6mAh/g, the capacitance after 30 times that circulates still can be maintained 131.2mAh/g; The spherical CoF of (4) one pots of water heat transfer
2positive electrode is the very promising lithium battery material of one.
Accompanying drawing explanation
Fig. 1 is spherical CoF of the present invention
2sEM figure.
Fig. 2 is spherical CoF of the present invention
2the XRD figure of condition of different temperatures.
Fig. 3 is spherical CoF of the present invention
2cycle life figure.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Take cobalt nitrate hexahydrate 0.29g, ammonium fluoride 0.12g, and urea 0.3g, the mol ratio of cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:3:5, be uniformly mixed in 50mL ethylene glycol solution, it is 5.8mg/mL that cobalt nitrate hexahydrate is dissolved in the concentration after ethylene glycol, obtains pink homogeneous mixed solution; Then, mixed solution is proceeded in teflon-lined reactor, at 200 DEG C, react 20h; After having reacted, centrifugal, collecting precipitation material, adopts absolute ethyl alcohol and deionized water respectively to wash 3 times respectively, with air dry oven at 50 DEG C dry 12 hours, grinds, obtains pink powder sample.The SEM figure of sample as shown in Figure 1, illustrates that this sample is spherical CoF
2, form by nanometer granule is stacking, particle diameter is 100 ~ 500nm.
The spherical cohalt difluoride powder of above-mentioned acquisition, conductive black, bonding agent (PVDF) are mixed according to the ratio of 80:10:10, slurry is applied on Al paper tinsel, 70 DEG C of dryings, take out pole piece roll extrusion on twin rollers, be cut into the disk that diameter is 8mm, put into vacuum tank 100 DEG C of dried overnight, weigh and write down the quality of spherical cohalt difluoride, under water and oxygen content are less than 1ppm, be assembled into button battery, wherein electrolyte is 1MLiPF
6(solvent is DMC:EC=1:1, volume ratio).Survey its cyclic voltammetry curve (CV), the chemical properties such as electrochemical impedance spectroscopy (EIS) and charging and discharging curve.
Embodiment 2
Take cobalt nitrate hexahydrate 0.29g, ammonium fluoride 0.12g and urea 0.3g, the mol ratio of cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:3:5, is uniformly mixed in 100mL ethylene glycol solution, it is 2.9mg/mL that cobalt nitrate hexahydrate is dissolved in the concentration after ethylene glycol, obtains pink homogeneous mixed solution; Then, mixed solution is proceeded in teflon-lined reactor, at 180 DEG C, react 20h; After having reacted, centrifugal, collecting precipitation material, adopts absolute ethyl alcohol and deionized water to wash 3 times respectively, with air dry oven at 80 DEG C dry 6 hours, grinds, obtains pink powder sample.SEM figure and the similar shown in Fig. 1 of sample, illustrate that this sample is spherical CoF
2, form by nanometer granule is stacking, particle diameter is 100 ~ 500nm.
The spherical cohalt difluoride powder of above-mentioned acquisition, conductive black, bonding agent (PVDF) are mixed according to the ratio of 80:10:10, slurry is applied on Al paper tinsel, 70 DEG C of dryings, take out pole piece roll extrusion on twin rollers, be cut into the disk that diameter is 8mm, put into vacuum tank 100 DEG C of dried overnight, weigh and write down the quality of spherical cohalt difluoride, under water and oxygen content are less than 1ppm, be assembled into button battery, wherein electrolyte is 1MLiPF
6(solvent is DMC:EC=1:1, volume ratio).Survey its cyclic voltammetry curve (CV), the chemical properties such as electrochemical impedance spectroscopy (EIS) and charging and discharging curve.
Embodiment 3
Take cobalt nitrate hexahydrate 0.29g, ammonium fluoride 0.12g and urea 0.3g, the mol ratio of cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:3:5, is uniformly mixed in 80mL ethylene glycol solution, it is 3.6mg/mL that cobalt nitrate hexahydrate is dissolved in the concentration after ethylene glycol, obtains pink homogeneous mixed solution; Then, mixed solution is proceeded in teflon-lined reactor, at 140 DEG C, react 20h; After having reacted, centrifugal, collecting precipitation material, adopts absolute ethyl alcohol and deionized water to wash 3 times respectively, with air dry oven at 70 DEG C dry 7 hours, grinds, obtains pink powder sample.
The spherical cohalt difluoride powder of above-mentioned acquisition, conductive black, bonding agent (PVDF) are mixed according to the ratio of 80:10:10, slurry is applied on Al paper tinsel, 70 DEG C of dryings, take out pole piece roll extrusion on twin rollers, be cut into the disk that diameter is 8mm, put into vacuum tank 100 DEG C of dried overnight, weigh and write down the quality of spherical cohalt difluoride, under water and oxygen content are less than 1ppm, be assembled into button battery, wherein electrolyte is 1MLiPF
6(solvent is DMC:EC=1:1, volume ratio).Survey its cyclic voltammetry curve (CV), the chemical properties such as electrochemical impedance spectroscopy (EIS) and charging and discharging curve.
Fig. 2 is spherical CoF of the present invention
2the XRD figure of condition of different temperatures, Fig. 3 is spherical CoF
2cycle life figure.Adopt spherical CoF prepared by the inventive method
2specific capacitance and the cycle life of positive electrode improve a lot, we adopt use the same method prepared different temperatures scope under synthesize CoF
2and the CoF under different time condition
2, we find that hydrothermal temperature is 200 DEG C, and the hydro-thermal time is the CoF synthesized under 20h condition
2structure is the most stable, at current density 20mAg
-1under first discharge capacity be 567.6mAh/g, the capacitance after 30 times that circulates still can be maintained 131.2mAh/g.
Embodiment 4
Take cobalt nitrate hexahydrate 0.29g, ammonium fluoride 0.12g and urea 0.24g, the mol ratio of cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:3:4, is uniformly mixed in 48mL ethylene glycol solution, cobalt nitrate hexahydrate is dissolved in the concentration 6.0mg/mL after ethylene glycol, obtains pink homogeneous mixed solution; Then, mixed solution is proceeded in teflon-lined reactor, at 120 DEG C, react 40h; After having reacted, centrifugal, collecting precipitation material, adopts absolute ethyl alcohol and deionized water to wash 3 times respectively, with air dry oven at 80 DEG C dry 7 hours, grinds, obtains pink powder sample.
Embodiment 5
Take cobalt nitrate hexahydrate 0.29g, ammonium fluoride 0.16g and urea 0.3g, the mol ratio of cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:4:5, is uniformly mixed in 96mL ethylene glycol solution, cobalt nitrate hexahydrate is dissolved in the concentration 3.0mg/mL after ethylene glycol, obtains pink homogeneous mixed solution; Then, mixed solution is proceeded in teflon-lined reactor, at 200 DEG C, react 2h; After having reacted, centrifugal, collecting precipitation material, adopts absolute ethyl alcohol and deionized water to wash 3 times respectively, with air dry oven at 80 DEG C dry 7 hours, grinds, obtains pink powder sample.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and execution mode, these amendments and execution mode will drop within spirit disclosed in the present application and spirit.More particularly, in the scope of, accompanying drawing open in the application and claim, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.
Claims (8)
1. the spherical cohalt difluoride for cell positive material, it is characterized in that it is take ammonium fluoride as fluorine source, being cobalt source with cobalt nitrate hexahydrate, take ethylene glycol as solvent, spherical CoF that adopt water heat transfer, that take the particle diameter that nanometer granule is stacking as 100 ~ 500nm
2.
2., for a preparation method for the spherical cohalt difluoride of cell positive material, it is characterized in that it comprises the following steps:
(1) get cobalt nitrate hexahydrate, ammonium fluoride and urea according to mol ratio 1:3 ~ 4:4 ~ 5, then stirring and dissolving is in ethylene glycol, obtains pink solution;
(2) described pink solution being proceeded to liner is in the reactor of polytetrafluoroethylene, reacts 2 ~ 40 hours at temperature 120 ~ 200 DEG C, after having reacted, centrifugal, washing, collecting precipitation;
(3) grind after described precipitation being dried, obtain pink powder shape finished product.
3. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 2, is characterized in that the mol ratio of described cobalt nitrate hexahydrate, ammonium fluoride and urea is 1:3:5.
4. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 2, it is characterized in that described pink solution reaction temperature is in a kettle. 200 DEG C, the reaction time is 20 hours.
5. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 2, it is characterized in that described cobalt nitrate hexahydrate be dissolved in ethylene glycol after concentration be 3.0 ~ 6.0mg/mL.
6. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 2, is characterized in that the method for described washing washs 3 times respectively with deionized water and absolute ethanol washing successively.
7. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 2, is characterized in that the method for described drying adopts air dry oven to dry.
8. the preparation method of the spherical cohalt difluoride for cell positive material according to claim 7, is characterized in that the temperature of described drying is 50 ~ 80 DEG C, and the dry time is 6 ~ 12 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207117A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of nanometer Cobalt difluoride ./C positive electrode material |
| CN106207116A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of method of one-step synthesis method ferrous fluoride/C positive electrode material |
| CN112295563A (en) * | 2020-11-10 | 2021-02-02 | 福州大学 | Co-based catalyst for breaking limitation relation of synthetic ammonia reaction and preparation method and application thereof |
| CN114284475A (en) * | 2021-12-20 | 2022-04-05 | 中南大学 | Preparation method of composite lithium metal cathode with three-dimensional structure and product thereof |
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| 王欣等: "锂二次电池金属氟化物正极材料研究进展", 《电源技术》 * |
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| CN106207117A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of nanometer Cobalt difluoride ./C positive electrode material |
| CN106207116A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of method of one-step synthesis method ferrous fluoride/C positive electrode material |
| CN112295563A (en) * | 2020-11-10 | 2021-02-02 | 福州大学 | Co-based catalyst for breaking limitation relation of synthetic ammonia reaction and preparation method and application thereof |
| CN114284475A (en) * | 2021-12-20 | 2022-04-05 | 中南大学 | Preparation method of composite lithium metal cathode with three-dimensional structure and product thereof |
| CN114284475B (en) * | 2021-12-20 | 2024-01-30 | 中南大学 | Preparation method of three-dimensional structured composite lithium metal anode and product thereof |
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| Publication number | Publication date |
|---|---|
| CN104600301B (en) | 2017-02-01 |
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