CN105977448A - Ferric fluoride/conducting polymer composite material, preparation method thereof and lithium secondary battery - Google Patents
Ferric fluoride/conducting polymer composite material, preparation method thereof and lithium secondary battery Download PDFInfo
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- CN105977448A CN105977448A CN201610561893.6A CN201610561893A CN105977448A CN 105977448 A CN105977448 A CN 105977448A CN 201610561893 A CN201610561893 A CN 201610561893A CN 105977448 A CN105977448 A CN 105977448A
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- conducting polymer
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- ferric flouride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a ferric fluoride/conducting polymer composite material. The ferric fluoride/conducting polymer composite material comprises ferric fluoride and a conducting polymer compounded to the surface of ferric fluoride. The invention further provides a preparation method of the ferric fluoride/conducting polymer composite material. The preparation method comprises the step of mixing ferric fluoride powder, a ferric trichloride solution, conducting polymer monomers, an anionic surfactant and an organic solvent to react, so as to obtain the ferric fluoride/conducting polymer composite material. Aiming at the problems that ferric trichloride has over-low electronic conductivity and expands along the polarization in charging and discharging processes, ferric trifluoride nanoparticles are coated with the conducting polymer by virtue of in situ polymerization and compounding, so that the polarization phenomenon of a ferric trifluoride material in the charging and discharging processes can be effectively overcome, the stability and capacity of the cathode material can be enhanced, meanwhile, the problem that the conductivity of a ferric trifluoride cathode material is too low can be well solved, and therefore, the electrochemical performance of the ferric trifluoride cathode material is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of ferric flouride/conducting polymer
Thing composite and preparation method thereof, lithium ion battery.
Background technology
Along with the continuous progress of human society, the demand of the various energy is increased by people
Adding, the development trend of the most various emerging energies is the most irresistible, and lithium secondary battery is exactly it
In dazzling a member.Small-sized electronic product, electronic transit equipment, redundant electrical power, Aero-Space
All closely related with the development of lithium secondary battery Deng developing rapidly of field, and present stage is badly in need of merit
Rate is higher, the life-span is longer, energy density is bigger, capacity is higher, the lithium secondary of environmental protection electricity
Breakthrough is made in pond.
Lithium ion battery industry competition is the fiercest, and what wherein shared market ratio was the heaviest is positive pole
Material, accounts for 30%～40%, directly determines the price of this battery, therefore carries out positive electrode
Improvement is the key improving market interest.Circulate extensively on the market at present be cobalt acid lithium,
The positive electrode such as ternary compound, LiFePO4, they are because of cyclical stability preferably, high power
Rate performance etc. and extensively paid attention to, but there is also that technique preparation is complicated, theoretical capacity is too low etc. lacks
Fall into, be also vulnerable to limit in the occasion needing massive energy power supply.And metal fluoride is a class
Promising anode material of lithium battery.Owing to the electronegativity of fluorine is big, metal fluoride positive electrode
Running voltage far above other positive electrodes such as metal-oxide, metal sulfide.And it is golden
Genus fluoride is not merely that lithium ion is embedding as the energy storage mechanism of the positive electrode of lithium secondary battery
Entering/deviate from mechanism, it can also pass through reversible chemical conversion reaction storing energy.This reversible change
Learn conversion reaction and can make full use of the various oxidation state of material in oxidation-reduction process, exchange material
All of electronics in material, the Lithium-ion embeding on its capacity released significantly larger than tradition outline/
Deintercalation is reacted.And in numerous metal fluorides, the three of high theoretical specific capacity (712mAh/g)
It is anti-that ferric fluoride anode material has progressed into the sight line of researcher, the especially polyelectron of its uniqueness
Machine-processed can should the most therefrom promote the energy density of battery, borontrifluoride ferrum is as positive electrode
Time, charge and discharge process exists two kinds of different storage lithium mechanism, in 2.5～4.5V voltage ranges,
One lithium ion is at FeF3Intercalation/deintercalation reversible in crystal structure, along with Fe3+/Fe2+'s
Changing, be lithium mechanism the most embedding, de-, lithium storage content is 237mAh g-1.1.5～2.5V
Voltage range, ferric flouride can continue and two lithium ion generation electrochemical reducting reactions, is formed
Fe nanoparticle and LiF, for reversible chemical switching mechanism, storage reason capacity is 475m Ah g-1。
And borontrifluoride ferrum positive electrode has, and raw material is cheap, safety good, reversible capacity advantages of higher.
Even so, borontrifluoride ferrum still suffers from as positive electrode that electronic conductivity is too low and charge and discharge
Polarization adjoint in electric process and problem that volumetric expansion occurs.Therefore, a kind of tool how is obtained
There are the borontrifluoride ferrum positive electrode of more highly electron conductive, and the simplest preparation technology,
Research and development type scholar's problem demanding prompt solution forward-looking in becoming field.
Summary of the invention
In view of this, the present invention provides a kind of ferric flouride/conducting polymer composite material and preparation thereof
Method, lithium ion battery, the ferric flouride composite that the present invention provides, there is higher electronics
Electrical conductivity, and the preparation method that the present invention provides, technique is simple, mild condition, it is adaptable to
Large-scale production and application.
The invention provides a kind of ferric flouride/conducting polymer composite material, by ferric flouride and multiple
It is combined in the conductive polymer coating composition on its surface.
Preferably, described conducting polymer is polyaniline, polyurethane, polypyrrole and polythiophene
One or more.
Preferably, the particle diameter of described ferric flouride is 50～120nm, described conductive polymer coating
Thickness is 5～60nm.
Preferably, described ferric flouride is (10～18) with the mass ratio of described conducting polymer: 1.
The invention provides the preparation method of a kind of ferric flouride/conducting polymer composite material, including
Following steps:
A) by ferric flouride powder, liquor ferri trichloridi, conducting polymer monomer, anion table
After face activating agent and organic solvent hybrid reaction, obtain ferric flouride/conducting polymer composite material.
Preferably, described ferric flouride is (8～18) with the mass ratio of conducting polymer monomer: 1；
Described ferric flouride is (2～7) with the mol ratio of ferric chloride: 1；
Described ferric flouride is (3～8) with the mass ratio of anion surfactant: 1.
Preferably, described ferric flouride includes without water ferric fluoride and/or hydration ferric flouride；
Described conducting polymer monomer is the one in aniline, thiophene, pyrroles and urethane monomer
Or it is multiple；
Described anion surfactant is 12 ring groups phenyl ring acid sodium (SDBS), fatty acid sulphur alkane
One in base ester, N-oleoyl many contractings amino acid sodium and alkyl alcohol ethoxylates sodium phosphate
Or it is multiple.
Preferably, described step A) particularly as follows:
A1) by ferric flouride powder, conducting polymer monomer, anion surfactant and organic
After solvent mixing, obtain mixed liquor；
A2) the mixed liquor addition liquor ferri trichloridi obtained to above-mentioned steps reacts, and is dried
After obtain ferric flouride/conducting polymer composite material；
The temperature of described reaction is 0～60 DEG C, and the time of described reaction is 2～5h.
Preferably, described ferric flouride powder is prepared by following methods:
By source of iron solution, fluorine source solution and surfactant hybrid reaction, washing obtains after drying
Ferric flouride powder.
The invention provides a kind of lithium ion battery, it is characterised in that described lithium ion battery
Positive pole includes the ferric flouride/conducting polymer composite material described in technique scheme any one
Or the ferric flouride/conducting polymer composite material prepared by technique scheme any one.
The invention provides a kind of ferric flouride/conducting polymer composite material, by ferric flouride and compound
Conductive polymer coating composition on its surface.Present invention also offers a kind of ferric flouride/conducting polymer
The preparation method of thing composite, comprises the following steps, by molten to ferric flouride powder, ferric chloride
After liquid, conducting polymer monomer, anion surfactant and organic solvent hybrid reaction,
To ferric flouride composite.Compared with prior art, the present invention is directed to borontrifluoride ferrum and there is electronics
Electrical conductivity is too low and in charge and discharge process adjoint polarization and there is the problem of volumetric expansion, use
Conducting polymer in-situ polymerization compound coating, on borontrifluoride iron nano-particle, can effectively overcome
The ferric trifluoride material polarization phenomena when discharge and recharge, strengthen stability and the capacity of positive electrode,
Can also preferably solve the problem that borontrifluoride ferrum positive electrode electrical conductivity is low simultaneously, thus improve three
The chemical property of ferric fluoride anode material.Test result indicate that, ferric flouride prepared by the present invention
Lithium ion battery prepared by composite, initial discharge capacity can reach 215～226mAh/g.
After 100 charge and discharge cycles, discharge capacity remains to reach 204～211mAh/g, discharge and recharge
Efficiency can be stable 90%～93%.
Accompanying drawing explanation
Fig. 1 is the three of the borontrifluoride ferrum pure phase (a) in-stiu coating with the embodiment of the present invention 1 preparation
The SEM figure of ferric flouride composite (b)；
Fig. 2 is discharge capacity, the charging that the product that the embodiment of the present invention 1 obtains circulates 100 times
Capacity, efficiency for charge-discharge figure；
Fig. 3 is first discharge and recharge under the product 0.2C charge-discharge magnification that the embodiment of the present invention 1 obtains
Curve chart；
Fig. 4 is the borontrifluoride ferrum/conductive polythiophene composite of the embodiment of the present invention 4 preparation
SEM schemes；
Fig. 5 is the efficiency for charge-discharge figure that the product that the embodiment of the present invention 4 obtains circulates 100 times；
Fig. 6 is the discharge and recharge that the product that the embodiment of the present invention 4 obtains circulates 100 times under 0.1C
Cycle performance figure；
Fig. 7 is the borontrifluoride ferrum/electric polypyrrole composite of the embodiment of the present invention 5 preparation
SEM schemes；
Fig. 8 is borontrifluoride ferrum/electric polypyrrole composite difference of the embodiment of the present invention 5 preparation
The discharge capacity performance map of 50 times is circulated under 0.1C, 0.5C, 1C.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with embodiment to the present invention side of being preferable to carry out
Case is described, but it is to be understood that these describe is simply the spy further illustrating the present invention
Advantage of seeking peace rather than the restriction to patent requirements of the present invention.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or press
Prepare according to conventional method well known to those skilled in the art.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analysis
The conventional purity that pure or field of lithium ion battery uses.
The invention provides a kind of ferric flouride/conducting polymer composite material, by ferric flouride and compound
Conductive polymer coating composition on its surface.
Described conducting polymer is not particularly limited by the present invention, knows with those skilled in the art
Conducting polymer, those skilled in the art can be according to practical condition, compound feelings
Condition and properties of product select, and conducting polymer of the present invention is preferably polyaniline, gathers
One or more of urethane, polypyrrole and polythiophene, more preferably polyaniline, polyurethane, poly-
Pyrroles or polythiophene, the most preferably polyaniline (PANI).Described conduction is gathered by the present invention
The thickness of compound layer is not particularly limited, those skilled in the art can according to practical condition,
Combining case and properties of product select, and the thickness of conductive polymer coating of the present invention is excellent
Elect 5～60nm as, more preferably 10～50nm, more preferably 10～40nm, most preferably
10～25nm.The ratio of described conducting polymer and ferric flouride is not particularly limited by the present invention,
Those skilled in the art can be carried out according to practical condition, combining case and properties of product
Selecting, ferric flouride of the present invention is preferably (10～18) with the mass ratio of described conducting polymer:
1, more preferably (11～16): 1, more preferably (12～15): 1, most preferably (13～14):
1.Described being combined is not particularly limited, with well known to those skilled in the art compound by the present invention
Concept, of the present invention compound can be to be coated with, be partly coated with, adulterate, embed, load
Or one or more of deposition.
Described ferric flouride is not particularly limited by the present invention, with well known to those skilled in the art three
Ferric flouride material or be usually used in the ferric trifluoride material of field of lithium ion battery, this area skill
Art personnel can select according to practical condition, combining case and properties of product, this
Invent described ferric flouride to preferably include without water ferric fluoride and/or (the ferric flouride hydration of hydration ferric flouride
Thing), it is particularly preferred as FeF3、FeF3·4.5H2O、FeF3·3H2O and FeF3·0.33H2In O
One or more, more preferably FeF3Or FeF3·0.33H2O, most preferably FeF3.This
The bright particle diameter to described ferric flouride is not particularly limited, and those skilled in the art can be according to reality
The condition of production, combining case and properties of product select, the grain of ferric flouride of the present invention
Footpath is preferably 50～120nm, more preferably 60～110nm, more preferably 70～100nm,
It is preferably 80～90nm.
The source of described ferric flouride is not particularly limited by the present invention, ripe with those skilled in the art
The source of the ferric trifluoride material known or the ferric trifluoride material being usually used in field of lithium ion battery is i.e.
Can, those skilled in the art can be according to practical condition, combining case and properties of product
Selecting, ferric flouride of the present invention is prepared the most in accordance with the following methods:
By source of iron solution, fluorine source solution and surfactant hybrid reaction, it is fluorinated after drying
Iron powder.
Described source of iron is not particularly limited by the present invention, and those skilled in the art can be according to reality
The condition of production, combining case and properties of product select, and source of iron of the present invention is preferably
FeCl3·6H2O；The concentration of described source of iron solution is not particularly limited by the present invention, this area skill
Art personnel can select according to practical condition, combining case and properties of product, this
The concentration inventing described source of iron solution is preferably 0.01～0.5mol/L, more preferably
0.05～0.45mol/L, more preferably 0.1～0.4mol/L, most preferably 0.3～0.4mol/L.This
Described fluorine source is not particularly limited by invention, and those skilled in the art can be according to actual production feelings
Condition, combining case and properties of product select, and fluorine source of the present invention is preferably NH4F；
The concentration of described fluorine source solution is not particularly limited by the present invention, and those skilled in the art can root
Select according to practical condition, combining case and properties of product, fluorine source of the present invention
The concentration of solution is preferably 0.03～1.5mol/L, more preferably 0.3～1.4mol/L, more preferably
0.6～1.3mol/L, most preferably 0.9～1.2mol/L.Described surfactant is not had by the present invention
Limiting especially, those skilled in the art can be according to practical condition, combining case and product
Moral character can select, and surfactant of the present invention is preferably NH4F lauryl trimethyl
Ammonium bromide (DTAB).
Amount ratio between described source of iron and fluorine source is not particularly limited by the present invention, with this area
The ratio of the similar reaction known to technical staff, those skilled in the art can be according to reality
The condition of production, combining case and properties of product select, source of iron of the present invention and fluorine source
The ratio of amount of material be preferably (1～5): 1, more preferably (1.5～4.5): 1, more preferably
(2～4): 1, most preferably (2.5～4): 1.The consumption of described surfactant is not had by the present invention
There is restriction especially, with the ratio of similar reaction well known to those skilled in the art, this area
Technical staff can select according to practical condition, combining case and properties of product.
Above-mentioned preparation process is not had other to limit especially by the present invention, and those skilled in the art are permissible
Selecting according to practical condition, combining case and properties of product, the present invention can be excellent
Elect as:
Source of iron solution is put into politef reactor (PTFE) adds surfactant powder
End, stirs 1～4h；In the PTFE the most again fluorine source solution being added dropwise to, room temperature
(20～30 DEG C) lower seal reaction 2～6h；
Reactor is put into agitator again, and stir speed (S.S.) is 100～500r/min, temperature is
In the oil bath pan of 50～110 DEG C, reaction 9～26h, obtains the FeF containing water of crystallization3Precipitation, i.e. contains
There is the FeF of water of crystallization3Nano material, then after being dried, obtain anhydrous FeF3。
The time sealing reaction of the present invention is preferably 2～6h, more preferably 3～5 hours,
It is preferably 4h；Described stir speed (S.S.) is preferably 100～500r/min, more preferably 200～400
r/min；The temperature of oil bath reaction is preferably 50～110 DEG C, more preferably 60～100 DEG C, optimum
Elect 65～85 DEG C as；The time of oil bath reaction is preferably 9～26h, more preferably 12～24h, more
It is preferably 17～23h.
The post processing of above-mentioned preparation process is not particularly limited by the present invention, those skilled in the art
Can select according to practical condition, combining case and properties of product, the present invention is excellent
Elect as and obtaining the FeF containing water of crystallization3After precipitation, after precipitation being cleaned, then carry out first
Secondary dry, after being cooled to room temperature, then carry out second time and be dried, finally obtain without water of crystallization
FeF3Nano material；More preferably obtaining the FeF containing water of crystallization3After precipitation, will be heavy
Form sediment preferably with after washes of absolute alcohol 2～3 times, then proceed to be connected with 60～100 DEG C of protection gas Ar
It is dried 10～15h, after being cooled to room temperature in drying baker for the first time, is then placed in the pipe of Ar protection
Formula atmosphere furnace is dried 0.5～3h with 250～450 DEG C of second time, finally obtains without water of crystallization
FeF3Nano material.
The temperature that first time of the present invention is dried is preferably 60～100 DEG C, more preferably
60～90 DEG C, most preferably 70～80 DEG C；The time that described first time is dried is preferably 10～15h,
More preferably 11～14h, more preferably 12～13h.The temperature that described second time is dried is preferably
250～450 DEG C, more preferably 280～350 DEG C；The time that described second time is dried is preferably
0.5～3h, more preferably 1～2.5h, more preferably 1.5～2h.
Above-mentioned steps of the present invention provides a kind of ferric flouride composite, and the present invention is by conducting polymer
Thing in-stiu coating is on borontrifluoride iron nano-particle, it is possible to preferably overcome ferric trifluoride material to exist
Polarization phenomena during discharge and recharge, additionally it is possible to strengthen the stability of positive electrode, and preferably solve
The problem that certainly borontrifluoride ferrum positive electrode electrical conductivity is low, thus effectively improve borontrifluoride ferrum positive pole
The chemical property of material.
Present invention also offers the preparation method of a kind of ferric flouride/conducting polymer composite material, bag
Include following steps:
A) by ferric flouride powder, liquor ferri trichloridi, conducting polymer monomer, anion table
After face activating agent and organic solvent hybrid reaction, obtain ferric flouride/conducting polymer composite material.
The present invention is to optimum principles such as selection, source and the ratios of described raw material, as without note especially
Bright, the most consistent with aforementioned ferric flouride/conducting polymer composite material, go to live in the household of one's in-laws on getting married the most one by one at this
State.
The specifically chosen of described liquor ferri trichloridi is not particularly limited by the present invention, this area skill
Art personnel can select according to practical condition, combining case and properties of product, this
Invent described liquor ferri trichloridi and be preferably acid liquor ferri trichloridi.The present invention is to described trichlorine
The concentration changing ferrous solution is not particularly limited, with normal concentration well known to those skilled in the art i.e.
Can, those skilled in the art can be according to practical condition, combining case and properties of product
Selecting, the concentration of liquor ferri trichloridi of the present invention is preferably 0.1～0.7g/mL, more excellent
Elect 0.3～0.6g/mL as, more preferably 0.35～0.45g/mL.
Described the specifically chosen of conducting polymer monomer is not particularly limited, with ability by the present invention
Conducting polymer monomer known to field technique personnel, those skilled in the art can be according to reality
The border condition of production, combining case and properties of product select, conducting polymer of the present invention
Thing monomer is preferably one or more in aniline, thiophene, pyrroles and urethane monomer, more excellent
Elect aniline monomer, thiophene monomer, pyrrole monomer or urethane monomer, most preferably aniline list as
Body.
The specifically chosen of described anion surfactant is not particularly limited by the present invention, with this
Anion surfactant known to skilled person, those skilled in the art can root
Select according to practical condition, combining case and properties of product, the moon of the present invention from
Sub-surface activating agent is preferably 12 ring groups phenyl ring acid sodium (SDBS), fatty acid sulfoalkyl ester, N-
One or more in oleoyl many contractings amino acid sodium and alkyl alcohol ethoxylates sodium phosphate,
More preferably 12 ring groups phenyl ring acid sodium (SDBS), fatty acid sulfoalkyl ester, the many contractings of N-oleoyl
Amino acid sodium or alkyl alcohol ethoxylates sodium phosphate, most preferably 12 ring group phenyl ring acid sodium
(SDBS)。
The specifically chosen of described organic solvent is not particularly limited by the present invention, with art technology
The organic solvent of the similar reaction known to personnel, those skilled in the art can be according to reality
The condition of production, combining case and properties of product select, and organic solvent of the present invention is excellent
Elect one or more in dehydrated alcohol, absolute ether, anhydrous propanone and hexamethylene as, more excellent
Elect dehydrated alcohol or absolute ether, most preferably dehydrated alcohol as.
The ratio of described ferric flouride and conducting polymer monomer is not particularly limited by the present invention, this
Skilled person can select according to practical condition, combining case and properties of product
Selecting, ferric flouride of the present invention is preferably with the mass ratio of described conducting polymer monomer
(8～18): 1, more preferably (10～17): 1, more preferably (12～16): 1, most preferably
For (13～15): 1.The consumption of described anion surfactant is limited by the present invention the most especially
System, those skilled in the art can be according to practical condition, combining case and properties of product
Selecting, ferric flouride of the present invention is preferably with the mass ratio of anion surfactant
(3～8): 1, more preferably (4～8): 1, most preferably (5～7): 1.
The consumption of described ferric chloride is not particularly limited by the present invention, and those skilled in the art can
To select according to practical condition, combining case and properties of product, of the present invention
Ferric flouride is preferably (2～7) with the mol ratio of ferric chloride: 1, more preferably (3～6): 1,
More preferably (3.5～5.5): 1, most preferably (4.5～5.5): 1.The present invention is to described organic
The consumption of solvent is not particularly limited, with the routine of similar reaction well known to those skilled in the art
Solvent load, those skilled in the art can according to practical condition, combining case with
And properties of product select.
Described reaction condition is not particularly limited by the present invention, with well known to those skilled in the art
Similar monomer carries out the condition of polyreaction, and the temperature of reaction of the present invention is preferably
0～60 DEG C, more preferably 10～50 DEG C, more preferably 20～40 DEG C, most preferably 30～40 DEG C；
The time of described reaction is preferably 2～5h, more preferably 2.5～4h, most preferably 2.5～3.5h.
The present invention is to improve the effect of home position polymerization reaction, described step A) it is particularly preferred as:
A1) by ferric flouride powder, conducting polymer monomer, anion surfactant and organic
After solvent mixing, obtain mixed liquor；
A2) the mixed liquor addition liquor ferri trichloridi obtained to above-mentioned steps reacts, washing
Obtain ferric flouride/conducting polymer composite material after drying.
Step A1 of the present invention) more specifically it is preferably: ferric flouride powder is joined containing leading
In the organic solvent of electric polymer monomer and anion surfactant；Wherein conducting polymer list
The mass concentration of body is preferably 10%～40%, more preferably 20%～35%, most preferably
25%～35%；Mixing is preferably stirred in mixing of the present invention.Step A2 of the present invention)
In addition be preferably dropping, the speed of described dropping is not particularly limited by the present invention, ability
Field technique personnel can select according to practical condition, combining case and properties of product,
The present invention is preferably slowly added dropwise.
Described washing and dry concrete steps and condition are not particularly limited by the present invention, ability
Field technique personnel can select according to practical condition, combining case and properties of product,
Washing of the present invention preferably absolute alcohol washes 2～5 times, or 3～4 times；Described dry preferred
For being dried under the protection of noble gas or nitrogen, more preferably it is dried under the protection of argon；
Described dry temperature is preferably 50～95 DEG C, more preferably 55～85 DEG C, most preferably
60～75 DEG C；It is preferably 20～27h described drying time, more preferably 23～26h, most preferably
23～25h.
The invention provides a kind of lithium ion battery, the positive pole of described lithium ion battery includes above-mentioned
Ferric flouride/conducting polymer composite material described in technical scheme any one or above-mentioned technical side
Ferric flouride/conducting polymer composite material prepared by case any one.The present invention to described lithium from
The definition of sub-battery is not particularly limited, with lithium ion battery well known to those skilled in the art or
The definition of lithium secondary battery.The present invention does not has spy to the concrete structure of described lithium ion battery
Do not limit, with the structure of lithium ion battery well known to those skilled in the art, this area skill
Art personnel can select according to practical condition, combining case and properties of product, this
The positive electrode inventing described lithium ion battery is ferric flouride/conducting polymer of the present invention
Composite or containing ferric flouride/conducting polymer composite material of the present invention.This
The bright preparation process to described lithium ion battery is not particularly limited, ripe with those skilled in the art
The preparation process of the lithium ion battery known, those skilled in the art can be according to actual production
Situation, combining case and properties of product select.
The present invention through above-mentioned steps prepared ferric flouride/conducting polymer composite material and
Lithium ion battery, the present invention uses conducting polymer in-situ polymerization compound coating to receive at borontrifluoride ferrum
In rice grain, when in-stiu coating, aniline monomer molecule enters in borontrifluoride iron molecule gap,
The fixing borontrifluoride iron construction that after polymerization, energy is fabulous, strengthens stability and the capacity of positive electrode,
Can also preferably solve the problem that borontrifluoride ferrum positive electrode electrical conductivity is low simultaneously, thus improve three
The chemical property of ferric fluoride anode material；And the raw material that the present invention uses is easy to get, price is fitted
In, technique is simple, mild condition, it is adaptable to industrialization large-scale production.Test result indicate that,
Lithium ion battery prepared by ferric flouride composite prepared by the present invention, initial discharge capacity can reach
To 215～226mAh/g.After 100 charge and discharge cycles, discharge capacity remains to reach
204～211mAh/g, efficiency for charge-discharge can be stable 90%～93%.
In order to further illustrate the present invention, a kind of fluorine present invention provided below in conjunction with embodiment
Change ferrum/conducting polymer composite material and preparation method thereof, lithium ion battery is described in detail,
It is understood that these embodiments are to implement under premised on technical solution of the present invention,
Give detailed embodiment and concrete operating process, simply for further illustrating the present invention
Feature and advantage rather than limiting to the claimed invention, protection scope of the present invention
It is also not necessarily limited to following embodiment.
Embodiment 1
First it is respectively configured source of iron FeCl that concentration is 0.35M3Solution and concentration are the fluorine of 1.2M
Source NH4F solution, then add a small amount of in the politef reactor (PTFE) equipped with source of iron
Lauryl trimethyl ammonium bromide (DTAB) powder, it is 200r/min that PTFE is placed on rotating speed simultaneously
DF-101S type constant-temperature heating magnetic stirring apparatus on stir 2h；Press and source of iron mol ratio the most again
Being added dropwise to be in the PTFE of whipping process by fluorine source for 4:1, room temperature lower seal reacts
4h；Reactor is put into agitator, the oil that stir speed (S.S.) is 300r/min, temperature is 70 DEG C
In bath, reaction 22h, obtains the precipitation containing water of crystallization；By precipitation washes of absolute alcohol 3
After secondary, in then proceeding to be connected with 75 DEG C of drying baker of Ar, it is dried 12h, after being cooled to room temperature,
It is then placed in the tube-type atmosphere furnace of Ar protection with 300 DEG C of dry 2h, finally obtains structure special
The different FeF without water of crystallization3Nano material.
By gained FeF3Nano-particle joins containing 0.3g 12 ring group phenyl ring acid sodium (SDBS)
With in the dehydrated alcohol of 30%wt aniline monomer, at 35 DEG C, stir with the magnetic force of 300r/min
Mix device stirring, be simultaneously introduced the acid FeCl of 6 0.4g/mL3It is raw that solution carries out polyreaction
Becoming conducting polymer, the response time is 3h, and the solid dehydrated alcohol obtained after reacting is repeatedly
Wash 4 times, finally the drying baker that the solid after washing is put under Ar atmosphere is done with 65 DEG C
Dry 24h, has obtained the borontrifluoride ferrum composite positive pole of electrically conductive polyaniline in-stiu coating.
Detecting the embodiment of the present invention 1 preparation, seeing Fig. 1, Fig. 1 is borontrifluoride ferrum
The borontrifluoride iron composite material (b) of the in-stiu coating that pure phase (a) is prepared with the embodiment of the present invention 1
SEM figure.As shown in Figure 1, borontrifluoride ferrum/conducting polymer that the present invention provides is compound just
Pole material achieves conducting polymer and is evenly coated on borontrifluoride iron nano-particle.
It is coated on borontrifluoride ferrum/conducting polyaniline composite material prepared by above-mentioned steps of the present invention
On aluminium foil, a section fritter area, as positive pole, takes an equal amount of lithium sheet as negative pole, assembling
Become lithium-ion button battery, its chemical property is tested.
Seeing Fig. 2, Fig. 2 is the electric discharge that the product that the embodiment of the present invention 1 obtains circulates 100 times
Capacity, charging capacity, efficiency for charge-discharge figure.As shown in Figure 2, the above-mentioned button cell of the present invention
At voltage range 2V～4V, charging and discharging currents is to circulate the discharge capacity after 100 times under 0.2C
For 208.6mAh/g, efficiency for charge-discharge is 92.1%.
Seeing Fig. 3, Fig. 3 is under the product 0.2C charge-discharge magnification that the embodiment of the present invention 1 obtains
First charging and discharging curve figure.From the figure 3, it may be seen that the borontrifluoride ferrum of the embodiment of the present invention 1 preparation/
Polyaniline composite material initial discharge capacity has reached 225.2mAh/g, closely its theoretical value
237mAh/g。
Embodiment 2
First it is respectively configured source of iron FeCl that concentration is 0.5M3Solution and concentration are the fluorine of 1.5M
Source NH4F solution, then add a small amount of in the politef reactor (PTFE) equipped with source of iron
Lauryl trimethyl ammonium bromide (DTAB) powder, it is 200r/min that PTFE is placed on rotating speed simultaneously
DF-101S type constant-temperature heating magnetic stirring apparatus on stir 2h；Press and source of iron mol ratio the most again
Being added dropwise to be in the PTFE of whipping process by fluorine source for 3.5:1, room temperature lower seal reacts
3h；Reactor is put into agitator, the oil that stir speed (S.S.) is 300r/min, temperature is 75 DEG C
In bath, reaction 24h, obtains the precipitation containing water of crystallization；By precipitation washes of absolute alcohol 3
After secondary, in then proceeding to be connected with 65 DEG C of drying baker of Ar, it is dried 13h, after being cooled to room temperature,
It is then placed in the tube-type atmosphere furnace of Ar protection with 400 DEG C of dry 2.5h, finally obtains structure special
The different FeF without water of crystallization3Nano material.
By gained FeF3Nano-particle joins containing 0.4g 12 ring group phenyl ring acid sodium (SDBS)
With in the dehydrated alcohol of 35%wt aniline monomer, at 30 DEG C, stir with the magnetic force of 300r/min
Mix device stirring, be simultaneously introduced the acid FeCl of 5 0.5g/mL3It is raw that solution carries out polyreaction
Becoming conducting polymer, the response time is that 2.5h will the solid dehydrated alcohol that obtain be repeatedly after reaction
Wash 3 times, finally the drying baker that the solid after washing is put under Ar atmosphere is done with 75 DEG C
Dry 23h, has just obtained the borontrifluoride ferrum composite positive pole of electrically conductive polyaniline in-stiu coating.
It is coated on borontrifluoride ferrum/conducting polyaniline composite material prepared by above-mentioned steps of the present invention
On aluminium foil, a section fritter area, as positive pole, takes an equal amount of lithium sheet as negative pole, assembling
Become lithium-ion button battery, its chemical property is tested.
Test result shows, under the charge-discharge magnification of 0.2C, the embodiment of the present invention 2 preparation
Borontrifluoride ferrum/polyaniline composite material initial discharge capacity has reached 222.4mAh/g, fills at this
Under discharge-rate, after 100 times circulate, discharge capacity is 207.3mAh/g.
Embodiment 3
First it is respectively configured source of iron FeCl that concentration is 0.3M3Solution and concentration are the fluorine source of 1M
NH4F solution, then add a small amount of moon in the politef reactor (PTFE) equipped with source of iron
Osmanthus base trimethylammonium bromide (DTAB) powder, it is 200r/min that PTFE is placed on rotating speed simultaneously
DF-101S type constant-temperature heating magnetic stirring apparatus on stir 3h；Press and source of iron mol ratio the most again
Being added dropwise to be in the PTFE of whipping process by fluorine source for 5:1, room temperature lower seal reacts
5h；Reactor is put into agitator, the oil that stir speed (S.S.) is 350r/min, temperature is 75 DEG C
In bath, reaction 20h, obtains the precipitation containing water of crystallization；By precipitation washes of absolute alcohol 3
After secondary, in then proceeding to be connected with 80 DEG C of drying baker of Ar, it is dried 11h, after being cooled to room temperature,
It is then placed in the tube-type atmosphere furnace of Ar protection with 350 DEG C of dry 1.5h, finally obtains structure special
The different FeF without water of crystallization3Nano material.
By gained FeF3Nano-particle joins containing 0.45g 12 ring group phenyl ring acid sodium (SDBS)
With in the dehydrated alcohol of 25%wt aniline monomer, at 35 DEG C, stir with the magnetic force of 350r/min
Mix device stirring, be simultaneously introduced the acid FeCl of 4 0.6g/mL3It is raw that solution carries out polyreaction
Becoming conducting polymer, the response time is 3.5h, by anti-for the solid dehydrated alcohol obtained after reaction
After backwashing is washed 5 times, finally the solid after washing is put into the drying baker under Ar atmosphere with 80 DEG C
It is dried 22h, just obtains the borontrifluoride ferrum composite positive pole of electrically conductive polyaniline in-stiu coating.
It is coated on borontrifluoride ferrum/conducting polyaniline composite material prepared by above-mentioned steps of the present invention
On aluminium foil, a section fritter area, as positive pole, takes an equal amount of lithium sheet as negative pole, assembling
Become lithium-ion button battery, its chemical property is tested.
Test result shows, under 0.2C charge-discharge magnification, and the three of the embodiment of the present invention 3 preparation
Ferric flouride/polyaniline composite material initial charge/discharge capacity is 220.1mAh/g, fills through 100 times
After discharge cycles, discharge capacity is 206.5mAh/g.
Embodiment 4
First obtain without water ferric fluoride nano-particle by case study on implementation 1.Take 0.1g thiophene monomer and
1.2g ferric flouride in reactor, adds 4ml chloroform, and it is ultrasonic to carry out 25min,
Monomer is made to adsorb on ferric flouride surface.Then, fill this blend into and mortar stands volatilization trichlorine
Methane 1.5h, adds 0.56g to methylbenzene naphthenic acid ferrum (monomer: Fe (OTs)3=1:5), grind
Mill 20min, puts into reaction 4.5h in 100 DEG C of vacuum drying ovens and obtains mixed-powder after mix homogeneously,
Washing and filtering is replaced for several times, directly with dehydrated alcohol and chloroform successively after being cooled down by gained powder
To filtrate close to colourless.Finally the powder after washing is dried 24h in 65 DEG C of vacuum drying ovens
Just the ferric flouride composite positive pole of required conducting polymer in-stiu coating is obtained.
Borontrifluoride ferrum/conductive polythiophene the composite of the embodiment of the present invention 4 preparation is examined
Survey, see borontrifluoride ferrum/conductive polythiophene that Fig. 4, Fig. 4 are the embodiment of the present invention 4 preparation multiple
The SEM figure of condensation material.As shown in Figure 4, the borontrifluoride ferrum anode composite material that the present invention provides
Material achieves conductive polythiophene and is preferably coated on borontrifluoride iron nano-particle.
Exist with borontrifluoride ferrum/conductive polythiophene composite coated prepared by above-mentioned steps of the present invention
On aluminium foil, a section fritter area, as positive pole, takes an equal amount of lithium sheet as negative pole, assembling
Become lithium-ion button battery, its chemical property is tested.
Seeing Fig. 5, Fig. 5 is the charge and discharge that the product that the embodiment of the present invention 4 obtains circulates 100 times
Electrical efficiency figure.As shown in Figure 5, after 100 charge and discharge cycles, efficiency for charge-discharge is still maintained at 90%
Above.Seeing Fig. 6, Fig. 6 is that the product that the embodiment of the present invention 4 obtains circulates 100 under 0.1C
Secondary charge-discharge performance figure.It will be appreciated from fig. 6 that the above-mentioned button cell of the present invention is in voltage zone
Between 2V～4V, under 0.1C charge-discharge magnification, initial discharge capacity is 218.4mAh/g, follows
Detecting its discharge capacity after ring 100 times is 207.8mAh/g, and charging capacity is 210.3mAh/g.
Embodiment 5
First obtain without water ferric fluoride nano-particle by the method in case 1.First take 10ml anhydrous
Ether makees solvent in the reactor, then by single for the 0.25ml pyrroles after 0.4g ferric flouride and purification
Body mixes ultrasonic 30min, is then added in reactor, and stirs 40min, temperature in ice bath
Degree maintains 0～3 DEG C, to be mixed uniformly after, stir wherein while be slowly added to 0.35g oxidation
Agent FeCl3, continue ice bath stirring 30min, now solution turned cloudy after adding completely, reacted
Become, then turbid solution organic membrane is carried out vacuum filtration, and with absolute ethanol washing 3 times,
After in the vacuum drying oven of 50 DEG C, be dried 6h, just obtain the compound of conducting polymer in-stiu coating
Positive electrode.
Borontrifluoride ferrum/electric polypyrrole the composite of the embodiment of the present invention 5 preparation is examined
Survey, see borontrifluoride ferrum/electric polypyrrole that Fig. 7, Fig. 7 are the embodiment of the present invention 5 preparation multiple
The SEM figure of condensation material.As shown in Figure 7, the borontrifluoride ferrum anode composite material that the present invention provides
Material achieves electric polypyrrole and is preferably coated on borontrifluoride iron nano-particle.
Exist with borontrifluoride ferrum/electric polypyrrole composite coated prepared by above-mentioned steps of the present invention
On aluminium foil, a section fritter area, as positive pole, takes an equal amount of lithium sheet as negative pole, assembling
Become lithium-ion button battery, its chemical property is tested.
See borontrifluoride ferrum/electric polypyrrole that Fig. 8, Fig. 8 are the embodiment of the present invention 5 preparation multiple
Condensation material circulates the discharge capacity performance map of 50 times respectively under 0.1C, 0.5C, 1C.By scheming
8 understand, the product that the embodiment of the present invention 5 obtains under 0.1C, 0.5C, 1C, initial discharge
Capacity is respectively 216.8mAh/g, 213.5mAh/g, 207.6mAh/g, through 50 circulations
After, the discharge capacity of this composite remain to respectively 203.2mAh/g, 209mAh/g,
201.3mAh/g, it is the most stable that this shows that the discharge capacity of composite of the present invention has
Property.
A kind of ferric flouride/the conducting polymer composite material above present invention provided and preparation thereof
Method, lithium ion battery are described in detail, and specific case used herein is to this
Bright principle and embodiment are set forth, and the explanation of above example is only intended to help reason
Solve method and the core concept thereof of the present invention, including best mode, and also make this area
Any technical staff can put into practice the present invention, including manufacturing and using any device or system,
With the method implementing any combination.It should be pointed out that, for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement
And modification, these improve and modify in the protection domain also falling into the claims in the present invention.This
The scope of bright patent protection is defined by the claims, and can include those skilled in the art's energy
Other embodiments enough expected.If these other embodiments have is not different from claim
The structural element of character express, if or they include that the character express with claim is without reality
The equivalent structural elements of matter difference, then these other embodiments also should be included in claim
In the range of.
Claims (10)
1. ferric flouride/conducting polymer composite material, it is characterised in that by ferric flouride and
It is compounded in the conductive polymer coating composition on its surface.
Composite the most according to claim 1, it is characterised in that described conduction is gathered
Compound is one or more of polyaniline, polyurethane, polypyrrole and polythiophene.
Composite the most according to claim 1, it is characterised in that described ferric flouride
Particle diameter be 50～120nm, the thickness of described conductive polymer coating is 5～60nm.
Composite the most according to claim 1, it is characterised in that described ferric flouride
It is (10～18) with the mass ratio of described conducting polymer: 1.
5. the preparation method of ferric flouride/conducting polymer composite material, it is characterised in that
Comprise the following steps:
A) by ferric flouride powder, liquor ferri trichloridi, conducting polymer monomer, anion table
After face activating agent and organic solvent hybrid reaction, obtain ferric flouride/conducting polymer composite material.
Preparation method the most according to claim 5, it is characterised in that described ferric flouride
It is (8～18) with the mass ratio of conducting polymer monomer: 1；
Described ferric flouride is (2～7) with the mol ratio of ferric chloride: 1；
Described ferric flouride is (3～8) with the mass ratio of anion surfactant: 1.
Preparation method the most according to claim 5, it is characterised in that described ferric flouride
Including without water ferric fluoride and/or hydration ferric flouride；
Described conducting polymer monomer is the one in aniline, thiophene, pyrroles and urethane monomer
Or it is multiple；
Described anion surfactant is 12 ring groups phenyl ring acid sodium (SDBS), fatty acid sulphur alkane
One in base ester, N-oleoyl many contractings amino acid sodium and alkyl alcohol ethoxylates sodium phosphate
Or it is multiple.
Preparation method the most according to claim 5, it is characterised in that described step A)
Particularly as follows:
A1) by ferric flouride powder, conducting polymer monomer, anion surfactant and organic
After solvent mixing, obtain mixed liquor；
A2) the mixed liquor addition liquor ferri trichloridi obtained to above-mentioned steps reacts, washing
Obtain ferric flouride/conducting polymer composite material after drying；
The temperature of described reaction is 0～60 DEG C, and the time of described reaction is 2～5h.
Preparation method the most according to claim 5, it is characterised in that described ferric flouride
Powder is prepared by following methods:
By source of iron solution, fluorine source solution and surfactant hybrid reaction, it is fluorinated after drying
Iron powder.
10. a lithium ion battery, it is characterised in that the positive pole of described lithium ion battery includes
Ferric flouride/conducting polymer composite material or right described in Claims 1 to 4 any one are wanted
Seek the ferric flouride/conducting polymer composite material prepared by 5～9 any one.
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| CN108794996A (en) * | 2018-06-07 | 2018-11-13 | 查公祥 | A kind of Aluminum sol improves polythiophene conductive material and preparation method thereof |
| CN111129466A (en) * | 2019-12-30 | 2020-05-08 | 中科廊坊过程工程研究院 | High-performance positive electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN112103479A (en) * | 2020-07-13 | 2020-12-18 | 天津大学 | Preparation and application of polymer-coated carbon nanotube/ferrous fluoride composite material |
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| CN112103479B (en) * | 2020-07-13 | 2022-05-13 | 天津大学 | Preparation and application of polymer-coated carbon nanotube/ferrous fluoride composite material |
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