CN104466177A - Nickel coated carbon fluoride positive electrode material and preparation method thereof - Google Patents
Nickel coated carbon fluoride positive electrode material and preparation method thereof Download PDFInfo
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- 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
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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
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- H01M4/06—Electrodes for primary cells
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- H—ELECTRICITY
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- 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
Abstract
The invention discloses a nickel coated carbon fluoride positive electrode material and a preparation method of the nickel coated carbon fluoride positive electrode material. The positive electrode material is prepared by coating the surface of carbon fluoride particles with a nickel-plating layer. The preparation method comprises the steps that the carbon fluoride particles are sequentially sensitized, activated and reduced under a function of dispersing agents and the nickel-plating layer is plated; the carbon fluoride particles coated with the nickel-plating layer are subjected to thermal treatment to obtain the nickel coated carbon fluoride positive electrode material. The preparation method is easy to operate, mild in process conditions and low in cost; the prepared nickel coated carbon fluoride positive electrode material is uniform in coating of nickel-plating layer, stable in structure, and can be used for preparing a lithium carbon fluoride battery with high conductivity, high specific capacity and high power density.
Description
Technical field
The present invention relates to a kind of nickel coated fluorocarbons positive electrode and preparation method thereof, belong to cell positive material, particularly primary cell positive electrode field.
Background technology
Nearly ten years, it is swift and violent that China's mancarried electronic aid, aerostatics, Aero-Space and organism are implanted into the development of the field such as power supply, therefore to height ratio capacity, high power and light-weighted primary cell demand is urgent.
Lithium fluorocarbon battery is the primary cell that current theoretical specific energy (2180Wh/kg) is maximum, and there is environment friendly and pollution-free, the advantage such as fail safe is high, temperature range wide (-30 ~ 80 DEG C), stable operating voltage, there is good application prospect.Be used in the advanced fields such as military project, Aero-Space, accurate medical treatment in a large number by the advanced country such as the U.S., Japan at present.
At present, China's lithium fluorocarbon battery applications is less, and main cause has the following aspects: (1) fluorocarbons costly, causes lithium fluorocarbon battery price high; (2) fluorocarbons poorly conductive, causes lithium fluorocarbon cell discharge efficiency low; (3) fluorocarbons surface energy is low, and cause fluorocarbons positive electrode to disperse uneven, electrolyte affinity is poor, and fluorocarbons electrode produces serious polarization, and battery performance declines greatly (voltage is lower than 3.0V).People have attempted the method for a lot of improvement fluorocarbons battery performance.The people such as A.Hamwi are oxidized fluorographite (CFx), prepared fluorine oxide graphite (GFO), to a certain degree improve the hydrophily of fluorographite, but it sacrifices the discharge voltage of lithium fluorocarbon battery.The people such as Q.Zhang have carried out material with carbon-coated surface to CFx, and to improve its conductivity, prepared lithium fluorocarbon cell voltage slightly improves, and battery multiplying power discharging property makes moderate progress.The people such as H.Groult carry out coated with the polypyrrole (PPy) that can conduct electricity to CFx, to a certain degree improve the high rate performance of lithium fluorocarbon battery.Above-mentioned improving one's methods has certain help to raising lithium fluorocarbon battery performance, but due to effect obvious not, thus do not apply in lithium-fluorocarbons production technology temporarily.
Summary of the invention
The object of the invention is to be to provide a kind of nickel coating evenly coated, Stability Analysis of Structures, can be used for the nickel coated fluorocarbons positive electrode preparing good conductivity, specific capacity is high, power density is large lithium fluorocarbon battery.
Another object of the present invention is the method for the fluorocarbons positive electrode that there are provided a kind of simple to operate, process conditions are gentle, cost is low nickel coated described in preparation.
The invention provides a kind of nickel coated fluorocarbons positive electrode, this nickel coated fluorocarbons positive electrode is made up of the coated one deck nickel coating of fluorocarbons particle surface.
Nickel coated fluorocarbons positive electrode of the present invention also comprises following preferred version:
In preferred nickel coated fluorocarbons positive electrode, nickel coating thickness is 0.1 ~ 1.0 μm.
In preferred nickel coated fluorocarbons positive electrode, nickel coating is the nickel-phosphorus alloy of phosphorus mass percentage < 8%.
In preferred nickel coated fluorocarbons positive electrode, fluorocarbons particle is fluoridize one or more in coke, fluorographite, fluorinated graphene, fluorinated carbon fiber, carbon fluoride nano-tube granular materials.
In preferred nickel coated fluorocarbons positive electrode, fluorocarbons particle size distribution is between 2 ~ 20 μm, and fluorine carbon atom number ratio is 0.8 ~ 1.2.
Present invention also offers the preparation method of described nickel coated fluorocarbons positive electrode, this preparation method is after fluorocarbons particle is adopted the washing of alcohol water mixed solvent, carry out sensitization, activation and reduction pretreatment successively, pretreated fluorocarbons particle is dispersed in the mixing plating solution of sulfur acid nickel, inferior sodium phosphate, natrium citricum and ammonium chloride and carries out chemical nickel plating coating under dispersant effect; Again the fluorocarbons particle having plated nickel coating is heat-treated, to obtain final product.
The preparation method of nickel coated fluorocarbons positive electrode of the present invention also comprises following preferred version:
Mixing plating solution pH in preferred preparation method is 8 ~ 8.5, and in often liter of mixing plating solution, solute is composed of the following components: nickelous sulfate 20 ~ 60g, inferior sodium phosphate 15 ~ 30g, natrium citricum 30 ~ 60g, ammonium chloride 30 ~ 70g, dispersant 0.2 ~ 2mL.
Mixing plating solution solvent in preferred preparation method is water.
In preferred preparation method, dispersant is one or more in OP-10, sucrose ester, polysorbate.
In preferred preparation method, heat treatment the fluorocarbons particle having plated nickel coating is 100 ~ 200 DEG C in temperature be incubated 1 ~ 4 hour.
In preferred preparation method alcohol water mixed solvent be second alcohol and water by volume 1:2 ~ 3:1 composition mixed solvent.
In preferred preparation method, fluorocarbons particulate material is managed use amount in step throughout and is no more than 30g/L (solution).
In preferred preparation method, washing is washed under frequency is the ultrasonic wave added of 20 ~ 40kHz, and the time is 1 ~ 30min.
In preferred preparation method, sensitization is that hydrochloric acid solution fluorocarbons particle being placed in the sub-tin of chloride containing stirs; Wherein, in the hydrochloric acid solution of the sub-tin of often liter of chloride containing, solute is composed of the following components: stannous chloride 2 ~ 8g, concentrated hydrochloric acid HCl 2 ~ 6mL, dispersant 0.2 ~ 2mL; Solvent is water.
In preferred preparation method activation be by sensitized treatment after the fluorocarbons particle hydrochloric acid solution that is placed in chloride containing palladium stir; Wherein, in the hydrochloric acid solution of often liter of chloride containing palladium, solute is composed of the following components: palladium bichloride 0.1 ~ 1g, concentrated hydrochloric acid HCl 4 ~ 10mL, dispersant 0.2 ~ 2mL; Solvent is water.
In preferred preparation method reduction be by activation processing after fluorocarbons particle be placed in ortho phosphorous acid sodium solution and stir; Described ortho phosphorous acid sodium solution is composed of the following components: inferior sodium phosphate 1 ~ 5wt%, dispersant 0.2 ~ 2mL/L, and solvent is water.
The preparation method of nickel coated fluorocarbons positive electrode of the present invention comprises following concrete steps:
Step 1: washing
Fluorocarbons particle is placed in second alcohol and water by volume 1:2 ~ 3:1 composition mixed solvent, take mechanical agitation, mixing speed is 50 ~ 500 revs/min, temperature is 15 ~ 40 DEG C, be wash 1 ~ 30min, centrifugation under the ultrasonic wave added of 20 ~ 40kHz in frequency, water washing for several times;
Step 2: sensitization
Step 1 gained fluorocarbons particle is placed in the hydrochloric acid solution that temperature is the sub-tin of chloride containing of 15 ~ 40 DEG C, and take mechanical agitation, stir 1 ~ 10min, centrifugation with the speed of 50 ~ 500 revs/min, water washing for several times; The hydrochloric acid solution of the sub-tin of described chloride containing is composed of the following components: stannous chloride 2 ~ 8g/L, concentrated hydrochloric acid HCl2 ~ 6mL/L, dispersant 0.2 ~ 2mL/L, and solvent is water;
Step 3: activation
Fluorocarbons particle after the sensitized treatment of step 2 is placed in the hydrochloric acid solution that temperature is the chloride containing palladium of 15 ~ 40 DEG C, takes mechanical agitation, stirs carry out activation processing 1 ~ 10min, centrifugation with the speed of 50 ~ 500 revs/min, and water washing for several times; The hydrochloric acid solution of described chloride containing palladium is composed of the following components: palladium bichloride 0.1 ~ 1g/L, concentrated hydrochloric acid HCl 4 ~ 10mL/L, dispersant 0.2 ~ 2mL/L, and solvent is water;
Step 4: reduction
Fluorocarbons particle after step 3 activation processing is placed in the ortho phosphorous acid sodium solution that temperature is 15 ~ 40 DEG C, takes mechanical agitation, stirs carry out reduction treatment 0.5 ~ 5min, centrifugation with the speed of 50 ~ 500 revs/min; Described ortho phosphorous acid sodium solution is composed of the following components: inferior sodium phosphate 1 ~ 5wt%, dispersant 0.2 ~ 2mL/L, and solvent is water;
Step 5: chemical nickel plating
Fluorocarbons particle after step 4 reduction treatment is placed in the plating solution that pH is 8 ~ 8.5, under 70 ~ 90 DEG C of temperature conditions, takes mechanical agitation, stirs carry out chemical nickel plating 0.5 ~ 10min, centrifugation with the speed of 50 ~ 500 revs/min, and water washing for several times; Described plating solution is composed of the following components: nickelous sulfate 20 ~ 60g/L, inferior sodium phosphate 15 ~ 30g/L, natrium citricum 30 ~ 60g/L, ammonium chloride 30 ~ 70g/L, dispersant 0.2 ~ 2mL/L, and solvent is water;
Step 6: heat treatment
Under fluorocarbons particle after step 5 chemical nickel plating is placed at the temperature environment of 100 ~ 200 DEG C, is incubated 1 ~ 4 hour, obtains nickel coated fluorocarbons positive electrode.
Beneficial effect of the present invention: it is good that the present invention adopts nickel coated carbon fluoride powder particle to obtain a kind of conductivity performance first, constitutionally stable nickel coated fluorocarbons positive electrode, can be used for the lithium fluorocarbon battery preparing height ratio capacity and high power density.The advantage that technical solution of the present invention is outstanding is: 1, the present invention is to the coated nickel of carbon fluoride powder particle surface, can improve the conductivity of positive electrode on the one hand, be beneficial to electron transmission, fast reaction speed, effectively improves the discharge power of lithium fluorocarbon battery; On the other hand can the amphipathic property of reinforcing material, be conducive to material surface solution and exchange and ion transport, reduce electrode polarization, promote cell discharge voltage platform, improve cell power conversion efficiency.2, nickel coated carbon fluoride powder granular materials conductivity obtained after the present invention adopts nickel coated fluorocarbons improves greatly, when making fluorocarbons electrode, can reduce and uses or do not use carbonaceous conductive agent.3, preparation method of the present invention, all use dispersant in whole preparation technology, can fluorocarbons particle is effectively dispersed in solution, more be conducive to sensitization, activation, reduction and nickel process, so that it is evenly coated to obtain coating, constitutionally stable nickel coated fluorocarbons positive electrode.4, preparation technology of the present invention is simple to operate, and process conditions are gentle, and production cost is low, meets suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is the structural representation of nickel coated fluorocarbons particle: 1 represents fluorocarbons particle; 2 represent nickel coating.
The scanning electron microscope (SEM) photograph of the nickel coated fluorocarbons particle that [Fig. 2] obtains for embodiment 1.
The battery discharge specific capacity comparison diagram that [Fig. 3] makes for the obtained nickel coated fluorocarbons positive electrode of embodiment 1 and fluorocarbons positive electrode.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Embodiment 1
Get the fluorographite particle 5g that fluorine carbon atomic ratio is 1.03, granular size is 5 ~ 10 μm, carries out chemical nickel plating process, and the technique of chemical nickel plating is:
(1) clean
Above-mentioned fluorocarbons is added alcohol and water volume ratio is 1:1, cumulative volume is in the alcohol water blend of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, ultrasonic oscillation, and concussion frequency 30kHz, the time is 5min.
By fluorocarbons centrifugation, and with deionized water rinsing repeatedly.
(2) sensitization
It is stannous chloride (SnCl that fluorocarbons after cleaning is added composition
22H
2o) 4g/L, 37%HCl 4mL/L, OP-101mL/L, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, and the time is 2min.
By fluorocarbons centrifugation, and be 7 with deionized water rinsing to pH.
(3) activate
Fluorocarbons after sensitization being added composition is palladium bichloride (PdCl
2) 0.4g/L, 37%HCl 8mL/L, OP-101mL/L, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, and the time is 2min.
By fluorocarbons centrifugation, and be 7 with deionized water rinsing to pH.
(4) reduce
It is inferior sodium phosphate (NaH that fluorocarbons after activation is added composition
2pO
2h
2o) 3% mass fraction, OP-101mL/L, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, and the time is 1min.
By fluorocarbons centrifugation.
(5) chemical nickel plating
It is nickelous sulfate (NiSO46H that fluorocarbons after reduction is added composition
2o) 35g/L, inferior sodium phosphate (NaH
2pO
2h
2o) 20g/L, natrium citricum (C
6h
5na
3o
72H
2o) 45g/L, ammonium chloride (NH
4cl) 50g/L, surfactant 1mL/L, solvent is deionized water, and volume is in the solution of 1L.Be adjusted to pH 8 ~ 8.5 with ammoniacal liquor or citric acid, temperature is 85 DEG C, mixing speed 200 rpms, and the time is 3min.
(6) heat treatment
Fluorocarbons after chemical nickel plating is put into the baking oven of 150 DEG C, be incubated 2 hours.
The fluorocarbons positive electrode of obtained nickel coated, nickel coating thickness is about 0.5 μm, and nickel coating phosphorus content is about 3.5%.
Thickness of coating adopts laser particle analyzer comparative observation coated front and back fluorocarbons particle size to draw.
By the fluorocarbons after coated and PVDF 8:1 in mass ratio, stirring solvent is made even with NMP, electrode is made after coating on aluminium foil, oven dry, cut-parts, 2032 type button lithium batteries are assembled into again in the glove box of argon gas condition, negative pole is lithium sheet, electrolyte solute is the LiPF6 of 1mol/L, and electrolyte solvent is the PC (propene carbonate) of 1:1 and EC (ethylene carbonate), adopts polyethylene diagrams.
The battery that the fluorographite of the not coated nickel of battery embodiment assembled and the same terms makes positive pole carries out discharge test contrast, and discharging current is 100mA/g.Result is illustrated in fig. 3 shown below.From test result, the CFx after the present embodiment nickel coated increases on discharge platform than pure CFx, and specific discharge capacity improves more than 2 times.
Embodiment 2
Get the fluorinated carbon fiber 20g that fluorine carbon atomic ratio is 0.85, granular size is 10 ~ 15 μm, carries out chemical nickel plating process, and the technique of chemical nickel plating is:
(1) clean
Above-mentioned fluorocarbons is added alcohol and water volume ratio is 1:2, cumulative volume is in the alcohol water blend of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, ultrasonic oscillation, and concussion frequency 35kHz, the time is 8min.
By fluorocarbons centrifugation, and with deionized water rinsing repeatedly.
(2) sensitization
It is stannous chloride (SnCl that fluorocarbons after cleaning is added composition
22H
2o) 7g/L, 37%HCl 5mL/L, sucrose ester and each 0.5mL/L of OP-10, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 400 rpms, and the time is 2min.
By fluorocarbons centrifugation, and be 7 with deionized water rinsing to pH.
(3) activate
Fluorocarbons after sensitization being added composition is palladium bichloride (PdCl
2) 0.8g/L, 37%HCl 4mL/L, sucrose ester and each 0.5mL/L of OP-10, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, and the time is 2min.
By fluorocarbons centrifugation, and be 7 with deionized water rinsing to pH.
(4) reduce
It is inferior sodium phosphate (NaH that fluorocarbons after activation is added composition
2pO
2h
2o) 4% mass fraction, sucrose ester and each 0.5mL/L of OP-10, solvent is deionized water, and volume is in the solution of 1L.Temperature is 25 DEG C, mixing speed 200 rpms, and the time is 1min.
By fluorocarbons centrifugation.
(5) chemical nickel plating
It is nickelous sulfate (NiSO that fluorocarbons after reduction is added composition
46H
2o) 50g/L, inferior sodium phosphate (NaH
2pO
2h
2o) 25g/L, natrium citricum (C
6h
5na
3o
72H
2o) 30g/L, ammonium chloride (NH
4cl) 60g/L, sucrose ester and each 0.5mL/L of OP-10, solvent is deionized water, and volume is in the solution of 1L.Be adjusted to pH 8 ~ 8.5 with ammoniacal liquor or citric acid, temperature is 80 DEG C, mixing speed 200 rpms, and the time is 3min.
(6) heat treatment
Fluorocarbons after chemical nickel plating is put into the baking oven of 200 DEG C, be incubated 1 hour.
The fluorocarbons positive electrode of obtained nickel coated, nickel coating thickness is about 0.6 μm, and nickel coating phosphorus content is about 3%.
Thickness of coating adopts laser particle analyzer comparative observation coated front and back fluorocarbons particle size to draw.
By the fluorocarbons after coated and PVDF 8:1 in mass ratio, stirring solvent is made even with NMP, electrode is made after coating on aluminium foil, oven dry, cut-parts, 2032 type button lithium batteries are assembled into again in the glove box of argon gas condition, negative pole is lithium sheet, electrolyte solute is the LiPF6 of 1mol/L, and electrolyte solvent is the PC (propene carbonate) of 1:1 and EC (ethylene carbonate), adopts polyethylene diagrams.
The battery that the fluorographite of the not coated nickel of battery embodiment assembled and the same terms makes positive pole carries out discharge test contrast, and discharging current is 100mA/g.Show that the CFx after the present embodiment nickel coated increases on discharge platform than pure CFx, and specific discharge capacity improves more than 2 times.
Claims (10)
1. a nickel coated fluorocarbons positive electrode, is characterized in that, is made up of the coated one deck nickel coating of fluorocarbons particle surface.
2. nickel coated fluorocarbons positive electrode as claimed in claim 1, it is characterized in that, described nickel coating thickness is 0.1 ~ 1.0 μm.
3. nickel coated fluorocarbons positive electrode as claimed in claim 1, it is characterized in that, described nickel coating is the nickel-phosphorus alloy of phosphorus mass percentage < 8%.
4. nickel coated fluorocarbons positive electrode as claimed in claim 1, it is characterized in that, described fluorocarbons particle is fluoridize one or more in coke, fluorographite, fluorinated graphene, fluorinated carbon fiber, carbon fluoride nano-tube granular materials.
5. nickel coated fluorocarbons positive electrode as claimed in claim 1, it is characterized in that, described fluorocarbons particle size distribution is between 2 ~ 20 μm, and fluorine carbon atom number ratio is 0.8 ~ 1.2.
6. the preparation method of the nickel coated fluorocarbons positive electrode described in any one of Claims 1 to 5, it is characterized in that, after fluorocarbons particle adopts the washing of alcohol water mixed solvent, carry out sensitization, activation and reduction pretreatment successively, pretreated fluorocarbons particle is dispersed in the mixing plating solution of sulfur acid nickel, inferior sodium phosphate, natrium citricum and ammonium chloride and carries out chemical nickel plating coating under the effect of dispersant; Again the fluorocarbons particle having plated nickel coating is heat-treated, to obtain final product.
7. preparation method as claimed in claim 6, it is characterized in that, described mixing plating solution pH is 8 ~ 8.5, solute in often liter of mixing plating solution is composed of the following components: nickelous sulfate 20 ~ 60g, inferior sodium phosphate 15 ~ 30g, natrium citricum 30 ~ 60g, ammonium chloride 30 ~ 70g, dispersant 0.2 ~ 2mL.
8. preparation method as claimed in claim 7, it is characterized in that, described dispersant is one or more in OP-10, sucrose ester, polysorbate.
9. preparation method as claimed in claim 6, is characterized in that, described alcohol water mixed solvent is the mixed solvent of second alcohol and water 1:2 ~ 3:1 composition by volume.
10. preparation method as claimed in claim 6, is characterized in that, described heat treatment the fluorocarbons particle having plated nickel coating is 100 ~ 200 DEG C in temperature be incubated 1 ~ 4 hour.
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| CN107369834A (en) * | 2017-07-12 | 2017-11-21 | 天津巴莫科技股份有限公司 | Compound fluorocarbons positive electrode and its production and use |
| CN109888268A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of lithium primary battery oxide/fluorination carbon composite anode material and preparation method thereof |
| CN109962240A (en) * | 2017-12-25 | 2019-07-02 | 中国电子科技集团公司第十八研究所 | Method for preparing anode slurry for lithium carbon fluoride battery with carbon nanotube as conductive agent |
| CN111029575A (en) * | 2019-11-06 | 2020-04-17 | 上海空间电源研究所 | Modified carbon fluoride positive electrode material, positive electrode plate containing modified carbon fluoride positive electrode material, battery and preparation method of modified carbon fluoride positive electrode material |
| CN111969188A (en) * | 2020-08-20 | 2020-11-20 | 贵州梅岭电源有限公司 | Low-temperature graphene/graphite fluoride cathode material |
| CN114400305A (en) * | 2021-12-14 | 2022-04-26 | 中国电子科技集团公司第十八研究所 | Thermal battery high-voltage spherical carbon fluoride anode material and preparation method thereof |
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| CN111969188A (en) * | 2020-08-20 | 2020-11-20 | 贵州梅岭电源有限公司 | Low-temperature graphene/graphite fluoride cathode material |
| CN114400305A (en) * | 2021-12-14 | 2022-04-26 | 中国电子科技集团公司第十八研究所 | Thermal battery high-voltage spherical carbon fluoride anode material and preparation method thereof |
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