CN109148864A - Ferrous disulfide composite negative pole material, preparation method and battery - Google Patents
Ferrous disulfide composite negative pole material, preparation method and battery Download PDFInfo
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- CN109148864A CN109148864A CN201811037944.0A CN201811037944A CN109148864A CN 109148864 A CN109148864 A CN 109148864A CN 201811037944 A CN201811037944 A CN 201811037944A CN 109148864 A CN109148864 A CN 109148864A
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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
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of ferrous disulfide composite negative pole material, preparation method and battery, the ferrous disulfide composite negative pole material includes nucleocapsid structure, the core includes ferrous disulfide, and the shell includes conducting polymer, and the conducting polymer is coated on the ferrous disulfide surface.Ferrous disulfide composite negative pole material of the invention, in ferrous disulfide surface coated with conductive polymeric layer, on the one hand the electric conductivity of ferrous disulfide can be improved in conductive polymer coating, another aspect conductive polymer coating has certain toughness, volume expansion of the ferrous disulfide in charge and discharge process can be buffered, to significantly improve the cyclical stability of battery.
Description
Technical field
The present invention relates to field of new energy technologies, and in particular to ferrous disulfide composite negative pole material, preparation method and electricity
Pond.
Background technique
The method for solving ferrous disulfide cyclical stability difference at present mainly includes optimization blanking voltage, reduces ferrous disulfide
Particle size improves battery although can alleviate volume expansion of the ferrous disulfide in charge and discharge process using these methods
Cyclical stability.But the electric conductivity of cathode can not be improved simultaneously using these methods；In addition, reducing the size of ferrous disulfide
To Nano grade, the pulping process that is unfavorable in industrialized production.Have in the prior art by ferrous disulfide and the compound system of carbon material
Standby ferrous disulfide/carbon composite, can improve the electric conductivity of ferrous disulfide material and alleviate its bulk effect.But due to
Ferrous disulfide is easily decomposed in air heating (600~700 DEG C), therefore cannot use the common glucose of industrialized production, sucrose, drip
Blueness etc. thermally decomposes the method packet carbon of (700 DEG C or more).It mostly uses porous carbon to be coated in iron particle at present, then sulphur is made by high temperature
Porous carbon is vaporized through to be reacted with iron to prepare carbon-coated ferrous disulfide composite material.This method and process is complicated, reacts
Condition requires height, and higher cost is unfavorable for commercially producing.
Summary of the invention
The main object of the present invention is to provide a kind of ferrous disulfide composite negative pole material, preparation method and battery, it is intended to
It solves the problems, such as to improve ferrous disulfide electric conductivity in the prior art and alleviates the complex process and higher cost of its bulk effect.
The present invention proposes a kind of ferrous disulfide composite negative pole material, and the ferrous disulfide composite negative pole material includes core-shell structure copolymer
Structure, the core include ferrous disulfide, and the shell includes conducting polymer, and the conducting polymer is coated on the ferrous disulfide
Surface.
Further, the particle size range of the ferrous disulfide includes 1 μm~5 μm, the thickness of the conductive polymer coating
Spending range includes 5nm~50nm.
Further, the conducting polymer includes one of polyaniline, polypyrrole, polythiophene.
The invention also provides a kind of preparation methods of ferrous disulfide composite negative pole material, are used to prepare any of the above-described institute
Ferrous disulfide composite negative pole material is stated, comprising steps of
Ferrous disulfide is added in designated solvent according to the first mass ratio, a certain amount of weak acid solution is added and adjusts pH
Value obtains the first mixed liquor less than 7 after ultrasonic disperse；
Under assigned temperature, conducting polymer monomer is added in first mixed liquor according to the second mass ratio, with
First specified revolving speed is stirred, and obtains the second mixed liquor, is then added to initiator in stirring according to third mass ratio
In second mixed liquor of state, a certain amount of weak acid solution is added and adjusts pH value less than 7, it is specified persistently to stir first
Time obtains reaction product；Wherein, second mass ratio refers to the quality of the conducting polymer monomer and the ferrous disulfide
Than the third mass ratio refers to the mass ratio of the initiator and the conducting polymer monomer；
After the reaction product is filtered, washed, it is dried with the first specified stoving process, obtains the ferrous disulfide
Composite negative pole material.
Further, described to be added to ferrous disulfide in designated solvent according to the first mass ratio, it adds a certain amount of
Before the step of weak acid solution adjusts pH value less than 7, and the first mixed liquor is obtained after ultrasonic disperse, further includes:
Ethylene glycol and n,N-Dimethylformamide are mixed according to the first volume ratio, third mixed liquor is obtained, by iron
Source is added in the third mixed liquor according to specified source of iron concentration, and persistently stirs for the second specified time with the second specified revolving speed,
Obtain source of iron solution；Wherein, the specified source of iron concentration refers to the ratio of the source of iron quality Yu the third mixeding liquid volume；
Sulphur source and urea are added according to the first molar ratio and the second molar ratio to the source of iron for being in stirring respectively
In solution, third specified time is persistently stirred, source of iron and sulphur source mixed solution are obtained；Wherein, first molar ratio refers to described
The molar ratio of source of iron and the sulphur source, second molar ratio refer to the molar ratio of the source of iron and the urea；
The source of iron and sulphur source mixed solution are reacted with specified hydrothermal condition, obtain hydrothermal product；
After the hydrothermal product is filtered, washed, it is dried with the second specified stoving process, obtains ferrous disulfide.
Further, the source of iron includes one of frerrous chloride, ferrous nitrate, ferrous sulfate or a variety of；The sulphur
Source includes one of elemental sulfur, thiocarbamide or a variety of；First molar ratio includes 1:6~1:10；The second molar ratio packet
Include 1:5~1:9；The specified hydrothermal condition includes hydro-thermal reaction 8h~14h at 150 DEG C~180 DEG C.
Further, the designated solvent includes one of deionized water, monochloro methane or a variety of；The weak acid includes
One of oxalic acid, acetic acid, citric acid are a variety of；The conducting polymer monomer includes one of aniline, pyrroles, thiophene；
The initiator includes one of ammonium persulfate, frerrous chloride or a variety of.
Further, second mass ratio includes 0.5:1~1:1；The third mass ratio includes 3.2:1~4:1.
Further, the assigned temperature includes 0 DEG C~5 DEG C, and first specified time includes 6h~8h.
The invention also provides a kind of battery, including anode, cathode, isolation film and electrolyte, the cathode is using above-mentioned
Described in any item ferrous disulfide composite negative pole materials.
Beneficial effects of the present invention:
Ferrous disulfide composite negative pole material of the invention, in ferrous disulfide surface coated with conductive polymeric layer, conducting polymer
On the one hand the electric conductivity of ferrous disulfide can be improved in nitride layer, another aspect conductive polymer coating has certain toughness, Ke Yihuan
Volume expansion of the ferrous disulfide in charge and discharge process is rushed, to significantly improve the cyclical stability of battery.
Further, the particle size of ferrous disulfide is micron level in ferrous disulfide composite negative pole material of the present invention, is had
Conducive to the dispersion of production pulping process, and preparation process is simple, and reaction condition is of less demanding, and cost is relatively low, is conducive to industrialize
Production.
Detailed description of the invention
Fig. 1 is the preparation method flow diagram of ferrous disulfide composite negative pole material in one embodiment of the invention；
Fig. 2 is the preparation method flow diagram of ferrous disulfide in one embodiment of the invention；
Fig. 3 is the XRD diagram of ferrous disulfide composite negative pole material in one embodiment of the invention；
Fig. 4 is the SEM figure of ferrous disulfide composite negative pole material in one embodiment of the invention；
Fig. 5 is the TEM figure of ferrous disulfide composite negative pole material in one embodiment of the invention；
Fig. 6 is that (wherein hollow star refers to for the cycle performance test result of fastening lithium ionic cell in one embodiment of the invention
Show coulombic efficiency, is answered with right side coordinate pair in figure；Left side coordinate pair is answered in solid circles instruction gram volume, with figure)；
Fig. 7 is that (wherein hollow star refers to for the cycle performance test result of button sodium-ion battery in one embodiment of the invention
Show coulombic efficiency, is answered with right side coordinate pair in figure；Left side coordinate pair is answered in solid circles instruction gram volume, with figure)；
Fig. 8 is cycle performance test result (the wherein hollow star instruction of fastening lithium ionic cell in comparative example 1 of the present invention
Right side coordinate pair is answered in coulombic efficiency, with figure；Left side coordinate pair is answered in solid circles instruction gram volume, with figure)；
Fig. 9 is cycle performance test result (the wherein hollow star instruction of button sodium-ion battery in comparative example 1 of the present invention
Right side coordinate pair is answered in coulombic efficiency, with figure；Left side coordinate pair is answered in solid circles instruction gram volume, with figure).
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its
Its embodiment, shall fall within the protection scope of the present invention.
In addition, the description for being such as related to " first ", " second " in the present invention is used for description purposes only, and should not be understood as
Its relative importance of indication or suggestion or the quantity for implicitly indicating indicated technical characteristic.Define as a result, " first ",
The feature of " second " can explicitly or implicitly include at least one of the features.In addition, the technical side between each embodiment
Case can be combined with each other, but must be based on can be realized by those of ordinary skill in the art, when the combination of technical solution
Conflicting or cannot achieve when occur will be understood that the combination of this technical solution is not present, also not the present invention claims guarantor
Within the scope of shield.
The embodiment of the present invention proposes that a kind of ferrous disulfide composite negative pole material, the ferrous disulfide composite negative pole material include
Nucleocapsid structure, the core include ferrous disulfide, and the shell includes conducting polymer, and the conducting polymer is coated on described two
Vulcanize iron surface.
The ferrous disulfide composite negative pole material of the present embodiment, in ferrous disulfide surface coated with conductive polymeric layer, conduction is poly-
On the one hand closing nitride layer can be improved the electric conductivity of ferrous disulfide, another aspect conductive polymer coating has certain toughness, can be with
Volume expansion of the ferrous disulfide in charge and discharge process is buffered, to significantly improve the cyclical stability of battery.
Further, the particle size range of the ferrous disulfide includes 1 μm~5 μm, the thickness of the conductive polymer coating
Spending range includes 5nm~50nm.
In the present embodiment, the particle size of ferrous disulfide is micron level in ferrous disulfide composite negative pole material, after cladding
The partial size of composite negative pole material be also micron level, be conducive in production pulping process composite negative pole material in the slurry
Dispersion, it is not easy to reunite, be conducive to industrialized production.
Further, the conducting polymer includes one of polyaniline, polypyrrole, polythiophene.
In the present embodiment, the conducting polymers such as polyaniline, polypyrrole, polythiophene have electric conductivity, and curing can be improved
The electric conductivity of iron additionally has certain toughness, can buffer volume expansion of the ferrous disulfide in charge and discharge process, thus aobvious
Write the cyclical stability for improving battery.
Referring to Fig.1, the embodiment of the present invention also proposed a kind of preparation method of ferrous disulfide composite negative pole material, for making
Ferrous disulfide composite negative pole material described in standby any of the above-described, comprising the following steps:
S1, ferrous disulfide is added in designated solvent according to the first mass ratio, adds a certain amount of weak acid solution tune
PH value is saved less than 7, the first mixed liquor is obtained after ultrasonic disperse；
S2, under assigned temperature, conducting polymer monomer is added in first mixed liquor according to the second mass ratio,
It is stirred with the first specified revolving speed, obtains the second mixed liquor, then be added to be according to third mass ratio by initiator and stir
It mixes in second mixed liquor of state, a certain amount of weak acid solution is added and adjusts pH value less than 7, persistently stirs first and refers to
It fixes time, obtains reaction product；Wherein, second mass ratio refers to the matter of the conducting polymer monomer and the ferrous disulfide
Ratio is measured, the third mass ratio refers to the mass ratio of the initiator and the conducting polymer monomer；
S3, it after being filtered, washed the reaction product, is dried with the first specified stoving process, obtains two sulphur
Change iron composite negative pole material.
In the present embodiment, in step S1, the first mixed liquor is the acid mixed solution for having dispersed ferrous disulfide.In step S2,
Polymer monomer is added in the first mixed liquor, conducting polymer monomer is caused by initiator, polymerization reaction occurs, generation
Conducting polymer is coated on iron disulfide particles surface.
The preparation process of the ferrous disulfide composite negative pole material of the present embodiment is simple, and reaction condition is of less demanding, cost compared with
It is low, be conducive to industrialized production.
Further, described to be added to ferrous disulfide in designated solvent according to the first mass ratio referring to Fig. 2, it adds
A certain amount of weak acid solution adjusts pH value less than 7, before the step S1 that the first mixed liquor is obtained after ultrasonic disperse, further includes:
S01, ethylene glycol and n,N-Dimethylformamide are mixed according to the first volume ratio, obtain third mixed liquor,
Source of iron is added in the third mixed liquor according to specified source of iron concentration, and with the second specified revolving speed persistently stir second it is specified when
Between, obtain source of iron solution；Wherein, the specified source of iron concentration refers to the ratio of the source of iron quality and the third mixeding liquid volume
Value；
S02, sulphur source and urea are added according to the first molar ratio and the second molar ratio in described in stirring respectively
In source of iron solution, third specified time is persistently stirred, source of iron and sulphur source mixed solution are obtained；Wherein, first molar ratio refers to
The molar ratio of the source of iron and the sulphur source, second molar ratio refer to the molar ratio of the source of iron and the urea；
S03, the source of iron and sulphur source mixed solution are reacted with specified hydrothermal condition, obtains hydrothermal product；
S04, it after being filtered, washed the hydrothermal product, is dried with the second specified stoving process, obtains two sulphur
Change iron.
In the present embodiment, by hydro-thermal method synthesizing ferrous disulfide, the condition of control hydrothermal synthesis, such as hydro-thermal can be passed through
Temperature, reaction time, to control and the grain diameter of hydrothermal product ferrous disulfide.The preferred scope of first volume ratio includes 1:1
~1.5:1, specifying source of iron concentration range includes 0.005~0.012g/ml.In the present embodiment, ferrous disulfide preparation method is simple,
To the of less demanding of reaction condition, energy consumption is small, at low cost, is conducive to industrialized production.
Further, in step S01~S04, the source of iron includes frerrous chloride, ferrous nitrate, one in ferrous sulfate
Kind is a variety of；The sulphur source includes one of elemental sulfur, thiocarbamide or a variety of；First molar ratio includes 1:6~1:10；Institute
Stating the second molar ratio includes 1:5~1:9；The specified hydrothermal condition includes, at 150 DEG C~180 DEG C hydro-thermal reaction 8h~
14h。
In the present embodiment, using the first molar ratio and the second molar ratio of above-mentioned optimization, be conducive to product ferrous disulfide
Synthesis.It is synthesized under the hydrothermal condition of above-mentioned optimization, is conducive to generate the ferrous disulfide that particle size is rank, micron order
Other ferrous disulfide is easily dispersed in pulping process, is conducive to industrialized production.
Further, in step S1~S3, the designated solvent includes one of deionized water, monochloro methane or more
Kind；The weak acid includes one of oxalic acid, acetic acid, citric acid or a variety of；The conducting polymer monomer includes aniline, pyrrole
It coughs up, one of thiophene；The initiator includes one of ammonium persulfate, frerrous chloride or a variety of.
In the present embodiment, polyaniline is aggregated at conducting polymer, such as aniline monomer by conducting polymer monomer polymerization,
Pyrrole monomer aggregates into polypyrrole, and thiophene monomer aggregates into polythiophene etc., these conducting polymers have electric conductivity, can be improved
The electric conductivity of ferrous disulfide additionally has certain toughness, can buffer volume expansion of the ferrous disulfide in charge and discharge process,
To significantly improve the cyclical stability of battery.Designated solvent, weak acid, the initiator type of above-mentioned optimization are conducive to conductive poly-
Object is closed preferably to occur to polymerize and be coated on ferrous disulfide surface.
Further, in step S2, second mass ratio includes 0.5:1~1:1；The third mass ratio includes 3.2:
1~4:1.
In the present embodiment, the second mass ratio is related with the thickness of the surface coated conducting polymer of ferrous disulfide.Above-mentioned
Second mass of optimization is than under range, being conducive to control the thickness of the ironing surface conductive polymer coating of product curing preferably
In range, it is preferable that the thickness range of the surface coated conducting polymer of ferrous disulfide includes 5nm~50nm, in this optimization
Thickness range in, the electric conductivity of ferrous disulfide composite negative pole material is more excellent, and volume expansion is smaller.
In the present embodiment, third mass ratio is related with the polymerization initiation of polymer monomer.In the third quality of above-mentioned optimization
Than under range, polymer monomer polymerization speed is suitable for that it is poly- to advantageously form the conduction with preferable electric conductivity and preferable toughness
Close nitride layer.
Further, the assigned temperature in step S2 include 0 DEG C~5 DEG C, first specified time include 6h~
8h。
In the present embodiment, produced in the specified for temperature ranges of above-mentioned optimization and the reaction obtained under the first specified time of optimization
Object, the thickness range of conductive polymer coating include 5nm~50nm.Additionally due to ferrous disulfide high temperature easily decomposes, the present embodiment is adopted
Be conducive to keep the structural stability of ferrous disulfide with low temperature synthetic method.
The embodiment of the present invention also proposed a kind of battery, including anode, cathode, isolation film and electrolyte, which is characterized in that
The cathode uses ferrous disulfide composite negative pole material described in any of the above embodiments.
In the present embodiment, battery includes lithium ion battery and sodium-ion battery.It is compound using the ferrous disulfide of the present embodiment
The battery of negative electrode material, negative conductive is good and bulk effect greatly reduces, and cycle performance of battery is good.
Embodiment
Step 1: ethylene glycol and n,N-Dimethylformamide are mixed according to first volume ratio 1.5:1~1:1, obtained
To third mixed liquor, source of iron is added in the third mixed liquor according to specified source of iron concentration, and is continued with the second specified revolving speed
It stirred for the second specified time, obtains source of iron solution；Wherein, the source of iron includes frerrous chloride, ferrous nitrate, in ferrous sulfate
It is one or more；The specified source of iron concentration refers to the ratio of the source of iron quality Yu the third mixeding liquid volume, the iron
Source concentration range includes 0.008~0.012g/mL；
Step 2: sulphur source and urea are added to the institute for being in stirring according to the first molar ratio and the second molar ratio respectively
It states in source of iron solution, persistently stirs third specified time, obtain source of iron and sulphur source mixed solution；Wherein, the sulphur source includes single
One of matter sulphur, thiocarbamide are a variety of；First molar ratio refers to the molar ratio of the source of iron and the sulphur source, and described first rubs
You are than including 1:6~1:10；Second molar ratio refers to the molar ratio of the source of iron and the urea, the second molar ratio packet
Include 1:5~1:9；
Step 3: the source of iron and sulphur source mixed solution are reacted with specified hydrothermal condition, obtain hydrothermal product, institute
Stating specified hydrothermal condition includes, hydro-thermal reaction 8h~14h at 150 DEG C~180 DEG C；
Step 4: after the hydrothermal product is filtered, washed, with the second dry 10- of 60-80 DEG C of specified stoving process vacuum
12h obtains the ferrous disulfide.
Step 5: ferrous disulfide is added in designated solvent according to first mass ratio 0.005:1~0.01:1, is added
A certain amount of weak acid solution adjusts pH value less than 7, and the first mixed liquor is obtained after ultrasonic disperse；The designated solvent include go from
One of sub- water, monochloro methane are a variety of；The weak acid includes one of oxalic acid, acetic acid, citric acid or a variety of；
Step 6: at 0 DEG C~5 DEG C of assigned temperature, by conducting polymer monomer aniline, pyrroles or thiophene according to the second matter
Amount is added in first mixed liquor than 0.5:1~1:1, is stirred with the first specified revolving speed, is obtained the second mixed liquor, so
Initiator is added in second mixed liquor in stirring according to third mass ratio 3.2:1~4:1 afterwards, is added one
The quantitative weak acid solution adjusts pH value less than 7, persistently stirs first specified time 6h~8h, obtains reaction product；Wherein,
Second mass ratio refers to that the mass ratio of the conducting polymer monomer and the ferrous disulfide, the third mass ratio refer to described
The mass ratio of initiator and the conducting polymer monomer；The initiator include one of ammonium persulfate, frerrous chloride or
It is a variety of；
Step 7: after the reaction product is filtered, washed, with the first dry 6- of 40-60 DEG C of specified stoving process vacuum
8h obtains the ferrous disulfide composite negative pole material.
The following are specific embodiments.
Embodiment 1
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 0.75g frerrous chloride is added to the mixed solution of 45mL ethylene glycol and 30mL N,N-dimethylformamide
In, 60min is stirred with 200r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 0.89g elemental sulfur and 1.39g urea are added in stirring
In, continue to stir 60min with 200r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 150 DEG C,
14h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 5 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 60
Pure ferrous disulfide is obtained after DEG C dry 12h；
Step 5: 0.15g ferrous disulfide made from step 4 being added in 30mL deionized water, 0.12g oxalic acid is added,
Ultrasonic 3h obtains the first mixed liquor；
Step 6: control reaction temperature is 5 DEG C, and 0.075g aniline is added in the first mixed liquor made from step 5,
With 200r/min rate stirring, in whipping process, add 20mL oxalic acid solution (oxalic acid solution concentration 0.004g/mL) and
0.26g ammonium persulfate continues to stir 6h, obtains reaction product；
Step 7: reaction product made from step 6 is cleaned into 8 removal impurity with deionized water, after 40 DEG C of dry 10h
Ferrous disulfide composite negative pole material is obtained, specifically, the present embodiment is polyaniline/ferrous disulfide composite material.
Test the preparation of pole piece:
By polyaniline made from step 7/ferrous disulfide composite material and PVDF (Kynoar) and NMP (N- methyl
Pyrrolidones) according to the mass ratio of 8:1:1 it is thoroughly mixed to form uniform paste；The paste is coated on copper foil matrix
On, obtain test pole piece.
The preparation of button cell:
(1) preparation of fastening lithium ionic cell: using lithium metal as to electrode, electrolyte uses 1M LiSO3CF3/DIG
Test pole piece, diaphragm, lithium metal and electrolyte are assembled into fastening lithium ionic cell by (diethylene glycol dimethyl ether).Test charge and discharge
The current density of electricity is 1A g-1.
(2) preparation of button sodium-ion battery: using metallic sodium as to electrode, electrolyte uses 1M NaSO3CF3/DIG
Test pole piece, diaphragm, metallic sodium and electrolyte are assembled into button sodium-ion battery by (diethylene glycol dimethyl ether).Test charge and discharge
The current density of electricity is 1A g-1.
Embodiment 2
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 0.56g frerrous chloride is added to the mixed solution of 40mL ethylene glycol and 30mL N,N-dimethylformamide
In, 40min is stirred with 300r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 0.88g elemental sulfur and 1.45g urea are added in stirring
In, continue to stir 40min with 300r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 170 DEG C,
10h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 7 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 70
Pure ferrous disulfide is obtained after DEG C dry 10h；
Step 5: 0.24g ferrous disulfide made from step 4 being added in 30mL deionized water, 0.15g oxalic acid is added,
Ultrasonic 5h obtains the first mixed liquor；
Step 6: control reaction temperature is 3 DEG C, and 0.192g aniline is added in the first mixed liquor made from step 5,
With 300r/min rate stirring, in whipping process, add 20mL oxalic acid solution (oxalic acid solution concentration 0.006g/mL) and
0.627g ammonium persulfate continues to stir 8h, obtains reaction product；
Step 7: cleaning 9 removal impurity with deionized water for reaction product made from step 6, after 50 DEG C of dry 8h
To ferrous disulfide composite negative pole material, specifically, the present embodiment is polyaniline/ferrous disulfide composite material.
The test pole piece of the present embodiment 2 and the preparation method of button cell are same as Example 1, and details are not described herein again.
Embodiment 3
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 0.72g frerrous chloride is added to the mixed solution of 30mL ethylene glycol and 30mL N,N-dimethylformamide
In, 60min is stirred with 400r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 1.42g elemental sulfur and 2.40g urea are added in stirring
In, continue to stir 60min with 400r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 180 DEG C,
8h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 8 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 80
Pure ferrous disulfide is obtained after DEG C dry 8h；
Step 5: 0.5g ferrous disulfide made from step 4 being added in 50mL deionized water, 0.3g oxalic acid is added, and is surpassed
Sound 6h obtains the first mixed liquor；
Step 6: control reaction temperature is 0 DEG C, and 0.5g aniline is added in the first mixed liquor made from step 5, with
The stirring of 300r/min rate, in whipping process, adds 30mL oxalic acid solution (oxalic acid solution concentration 0.01g/mL) and 2g mistake
Ammonium sulfate continues to stir 10h, obtains reaction product；
Step 7: reaction product made from step 6 is cleaned into 10 removal impurity with deionized water, after 60 DEG C of dry 6h
Ferrous disulfide composite negative pole material is obtained, specifically, the present embodiment is polyaniline/ferrous disulfide composite material.
The test pole piece of the present embodiment 3 and the preparation method of button cell are same as Example 1, and details are not described herein again.
Embodiment 4
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 0.72g frerrous chloride is added to the mixed solution of 30mL ethylene glycol and 30mL N,N-dimethylformamide
In, 60min is stirred with 400r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 2.03g thiocarbamide and 2.40g urea are added in stirring
In, continue to stir 60min with 400r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 180 DEG C,
8h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 8 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 80
Pure ferrous disulfide is obtained after DEG C dry 8h；
Step 5: 0.5g ferrous disulfide made from step 4 being added in 50mL deionized water, 0.3g oxalic acid is added, and is surpassed
Sound 6h obtains the first mixed liquor；
Step 6: control reaction temperature is 0 DEG C, and 0.5g aniline is added in the first mixed liquor made from step 5, with
The stirring of 300r/min rate, in whipping process, adds 30mL oxalic acid solution (oxalic acid solution concentration 0.01g/mL) and 2g mistake
Ammonium sulfate continues to stir 10h, obtains reaction product；
Step 7: reaction product made from step 6 is cleaned into 10 removal impurity with deionized water, after 60 DEG C of dry 6h
Ferrous disulfide composite negative pole material is obtained, specifically, the present embodiment is polyaniline/ferrous disulfide composite material.
The test pole piece of the present embodiment 4 and the preparation method of button cell are same as Example 1, and details are not described herein again.
Embodiment 5
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 1.02g ferrous nitrate is added to the mixed solution of 30mL ethylene glycol and 30mL N,N-dimethylformamide
In, 60min is stirred with 400r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 2.03g thiocarbamide and 2.40g urea are added in stirring
In, continue to stir 60min with 400r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 180 DEG C,
8h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 8 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 80
Pure ferrous disulfide is obtained after DEG C dry 8h；
Step 5: 50mL monochloro methane (CH is added in 0.5g ferrous disulfide made from step 43Cl in), 0.3g is added
Acetic acid, ultrasonic 6h obtain the first mixed liquor；
Step 6: control reaction temperature is 0 DEG C, and 0.5g thiophene is added in the first mixed liquor made from step 5, with
The stirring of 300r/min rate, in whipping process, adds 30mL acetum (acetum concentration 0.01g/mL) and 2g chlorine
Change ferrous iron (FeCl2), continue to stir 10h, obtains reaction product；
Step 7: reaction product made from step 6 is cleaned into 10 removal impurity with deionized water, after 60 DEG C of dry 6h
Ferrous disulfide composite negative pole material is obtained, specifically, the present embodiment is polythiophene/ferrous disulfide composite material.
The test pole piece of the present embodiment 5 and the preparation method of button cell are same as Example 1, and details are not described herein again.
Embodiment 6
Ferrous disulfide composite negative pole material is prepared by following steps:
Step 1: 30mL ethylene glycol and 30mLN, the mixed solution of dinethylformamide is added in 0.86g ferrous sulfate
In, 60min is stirred with 400r/min, obtains source of iron solution；
Step 2: one resulting source of iron solution of the step of 2.03g thiocarbamide and 2.40g urea are added in stirring
In, continue to stir 60min with 400r/min, obtains source of iron and sulphur source mixed solution；
Step 3: the source of iron and sulphur source mixed solution that step 2 is obtained carry out hydro-thermal reaction, and hydrothermal condition is 180 DEG C,
8h is kept the temperature, hydrothermal product is obtained；
Step 4: washing 8 times removal impurity using deionized water and ethyl alcohol for hydrothermal product that step 3 obtains repeatedly, and 80
Pure ferrous disulfide is obtained after DEG C dry 8h；
Step 5: 0.5g ferrous disulfide made from step 4 being added in 50mL deionized water, 0.3g citric acid is added,
Ultrasonic 6h obtains the first mixed liquor；
Step 6: control reaction temperature is 0 DEG C, and 0.5g pyrroles is added in the first mixed liquor made from step 5, with
300r/min rate stirring, in whipping process, add 30mL citric acid solution (citric acid solution concentration 0.01g/mL) and
2g ammonium persulfate continues to stir 10h, obtains reaction product；
Step 7: reaction product made from step 6 is cleaned into 10 removal impurity with deionized water, after 60 DEG C of dry 6h
Ferrous disulfide composite negative pole material is obtained, specifically, the present embodiment is polypyrrole/ferrous disulfide composite material.
The test pole piece of the present embodiment 6 and the preparation method of button cell are same as Example 1, and details are not described herein again.
Comparative example 1
Ferrous disulfide is prepared using step one same as Example 3~step 4.
And using ferrous disulfide obtained preparation test pole piece and button cell, specific preparation method is same as Example 1,
This will not be repeated here.
It is the ferrous disulfide composite negative pole material (polyaniline/ferrous disulfide composite wood of the embodiment of the present invention 1 referring to Fig. 3
Material) XRD diagram.Can be seen that ferrous disulfide outer cladding from the characteristic peak of Fig. 3 is polyaniline.The tool of the characteristic peak of polyaniline
Body numerical value is referring to table 1.
1 polyaniline characteristic peak of table
| Wave number (cm-1) | Represent peak |
| 1700 | Benzene-quinone heterocycle polymerization |
| 1515 | N-Q-N |
| 1398/1349 | C-N |
| 1189 | C-H |
| 1050 | O-H |
| 796 | N-H |
| 535 | NH2 - |
It is the ferrous disulfide composite negative pole material (polyaniline/ferrous disulfide composite wood of the embodiment of the present invention 2 referring to Fig. 4
Material) SEM figure.
It is the ferrous disulfide composite negative pole material (polyaniline/ferrous disulfide composite wood of the embodiment of the present invention 2 referring to Fig. 5
Material) TEM figure, wherein A be ferrous disulfide, B is polyaniline.
In conjunction with Fig. 4 and Fig. 5, it can be seen that the thickness range of conductive polymer coating is less than 50nm, more specifically, range
Including 5nm~50nm.The particle size range of ferrous disulfide composite negative pole material includes 1 μm~5 μm.Due to the thickness of conductive polymer coating
Degree is Nano grade, influences the particle size of ferrous disulfide composite negative pole material less, so ferrous disulfide Compound Negative can be obtained
The core of pole material, the i.e. particle size range of ferrous disulfide include 1 μm~5 μm.
It is the cycle performance test result of the fastening lithium ionic cell of the embodiment of the present invention 3, the battery is in 1A referring to Fig. 6
g-1Electric current under, charging/discharging voltage range be 0.05~3V, recycle 30 weeks, capacity still has 480mAh g within the 30th week-1, cyclicity
It can be good.
It is the cycle performance test result of the button sodium-ion battery of the embodiment of the present invention 4, the battery is in 1A referring to Fig. 7
g-1Electric current under, charging/discharging voltage range be 0.8~3V, recycle 20 weeks, capacity still has 306mAh g within the 20th week-1, cycle performance
It is good.
It is the cycle performance test result of the fastening lithium ionic cell of comparative example 1 of the present invention, the battery is in 1A referring to Fig. 8
g-1Electric current under, charging/discharging voltage range be 0.05~3V, recycle 30 weeks, capacity only has 217mAh g within the 30th week-1.Pass through reality
The comparison of example 3 and comparative example 1 is applied it is found that after the coated with conductive polymeric layer of surface, the lithium ion of ferrous disulfide composite negative pole material
Cycle performance of battery greatly promotes.
It is the cycle performance test result of the button sodium-ion battery of comparative example 1 of the present invention, the battery is in 1A referring to Fig. 9
g-1Electric current under, charging/discharging voltage range be 0.8~3V, recycle 20 weeks, capacity only has 223mAh g within the 20th week-1.Pass through implementation
It is found that after the coated with conductive polymeric layer of surface, the sodium ion of ferrous disulfide composite negative pole material is electric for the comparison of example 4 and comparative example 1
Pond cycle performance greatly promotes.
It can be seen that the battery of the ferrous disulfide composite negative pole material using the embodiment of the present invention by the above test result
(including lithium ion battery and sodium-ion battery), negative conductive is good and bulk effect greatly reduces, and cycle performance of battery is good.
Ferrous disulfide composite negative pole material of the invention, in ferrous disulfide surface coated with conductive polymeric layer, conducting polymer
On the one hand the electric conductivity of ferrous disulfide can be improved in nitride layer, another aspect conductive polymer coating has certain toughness, Ke Yihuan
Volume expansion of the ferrous disulfide in charge and discharge process is rushed, to significantly improve the cyclical stability of battery.Further, this hair
The particle size of ferrous disulfide is micron level in bright ferrous disulfide composite negative pole material, is conducive to the slurrying in production process
Journey, and preparation process is simple, reaction condition is of less demanding, and cost is relatively low, is conducive to industrialized production.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content is applied directly or indirectly in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of ferrous disulfide composite negative pole material, which is characterized in that the ferrous disulfide composite negative pole material includes core-shell structure copolymer knot
Structure, the core include ferrous disulfide, and the shell includes conducting polymer, and the conducting polymer is coated on the ferrous disulfide table
Face.
2. ferrous disulfide composite negative pole material as described in claim 1, which is characterized in that the particle size of the ferrous disulfide
Range includes 1 μm~5 μm, and the thickness range of the conductive polymer coating includes 5nm~50nm.
3. ferrous disulfide composite negative pole material as described in claim 1, which is characterized in that the conducting polymer includes polyphenyl
One of amine, polypyrrole, polythiophene.
4. a kind of preparation method of ferrous disulfide composite negative pole material, is used to prepare the curing of any one of claims 1 to 3
Iron composite negative pole material, which is characterized in that comprising steps of
Ferrous disulfide is added in designated solvent according to the first mass ratio, it is small to add a certain amount of weak acid solution adjusting pH value
In 7, the first mixed liquor is obtained after ultrasonic disperse；
Under assigned temperature, conducting polymer monomer is added in first mixed liquor according to the second mass ratio, with first
Specified revolving speed is stirred, and obtains the second mixed liquor, is then added to initiator in stirring according to third mass ratio
Second mixed liquor in, a certain amount of weak acid solution is added and adjusts pH value less than 7, persistently stir first it is specified when
Between, obtain reaction product；Wherein, second mass ratio refers to the quality of the conducting polymer monomer and the ferrous disulfide
Than the third mass ratio refers to the mass ratio of the initiator and the conducting polymer monomer；
After the reaction product is filtered, washed, it is dried with the first specified stoving process, it is compound obtains the ferrous disulfide
Negative electrode material.
5. the preparation method of ferrous disulfide composite negative pole material as claimed in claim 4, which is characterized in that described by curing
Iron is added in designated solvent according to the first mass ratio, is added a certain amount of weak acid solution and is adjusted pH value less than 7, through ultrasound point
Before the step of obtaining the first mixed liquor after dissipating, further includes:
Ethylene glycol and n,N-Dimethylformamide are mixed according to the first volume ratio, third mixed liquor is obtained, source of iron is pressed
It is added in the third mixed liquor according to specified source of iron concentration, and the second specified time was stirred persistently with the second specified revolving speed, obtained
Source of iron solution；Wherein, the specified source of iron concentration refers to the ratio of the source of iron quality Yu the third mixeding liquid volume；
Sulphur source and urea are added according to the first molar ratio and the second molar ratio to the source of iron solution for being in stirring respectively
In, third specified time is persistently stirred, source of iron and sulphur source mixed solution are obtained；Wherein, first molar ratio refers to the source of iron
With the molar ratio of the sulphur source, second molar ratio refers to the molar ratio of the source of iron and the urea；
The source of iron and sulphur source mixed solution are reacted with specified hydrothermal condition, obtain hydrothermal product；
After the hydrothermal product is filtered, washed, it is dried with the second specified stoving process, obtains the ferrous disulfide.
6. the preparation method of ferrous disulfide composite negative pole material as claimed in claim 5, which is characterized in that
The source of iron includes one of frerrous chloride, ferrous nitrate, ferrous sulfate or a variety of；
The sulphur source includes one of elemental sulfur, thiocarbamide or a variety of；
First molar ratio includes 1:6~1:10；
Second molar ratio includes 1:5~1:9；
The specified hydrothermal condition includes hydro-thermal reaction 8h~14h at 150 DEG C~180 DEG C.
7. the preparation method of ferrous disulfide composite negative pole material as claimed in claim 4, which is characterized in that
The designated solvent includes one of deionized water, monochloro methane or a variety of；
The weak acid includes one of oxalic acid, acetic acid, citric acid or a variety of；
The conducting polymer monomer includes one of aniline, pyrroles, thiophene；
The initiator includes one of ammonium persulfate, frerrous chloride or a variety of.
8. the preparation method of ferrous disulfide composite negative pole material as claimed in claim 4, which is characterized in that
Second mass ratio includes 0.5:1~1:1；
The third mass ratio includes 3.2:1~4:1.
9. the preparation method of ferrous disulfide composite negative pole material as claimed in claim 4, which is characterized in that the assigned temperature
Including 0 DEG C~5 DEG C, first specified time includes 6h~8h.
10. a kind of battery, including anode, cathode, isolation film and electrolyte, which is characterized in that the cathode is used as right is wanted
Seek the described in any item ferrous disulfide composite negative pole materials of 1-3.
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| CN109935779A (en) * | 2019-04-18 | 2019-06-25 | 电子科技大学 | A kind of ferrous disulfide positive electrode and preparation method thereof and alkali metal-ion battery |
| CN110518228A (en) * | 2019-09-17 | 2019-11-29 | 安徽大学 | It is a kind of embed inorganic nano-particle three-dimensional grapheme carbon nano-composite material and its application |
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| CN109755553A (en) * | 2019-03-20 | 2019-05-14 | 北京航空航天大学 | A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system |
| CN109935779A (en) * | 2019-04-18 | 2019-06-25 | 电子科技大学 | A kind of ferrous disulfide positive electrode and preparation method thereof and alkali metal-ion battery |
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