CN108321374A - A kind of iron and fluorin-doped composite material and preparation method - Google Patents
A kind of iron and fluorin-doped composite material and preparation method Download PDFInfo
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- CN108321374A CN108321374A CN201810113032.0A CN201810113032A CN108321374A CN 108321374 A CN108321374 A CN 108321374A CN 201810113032 A CN201810113032 A CN 201810113032A CN 108321374 A CN108321374 A CN 108321374A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides the preparation methods of a kind of iron and fluorin-doped composite material, include the following steps：By lithium salts, manganese source, source of iron, Fluorine source, water and agate pearl mixed grinding, mixture is obtained；It is crushed after the mixture is dried, obtains powder；By the powder sintering postcooling, intermediate product is obtained；It is ground, dries and is crushed successively after the intermediate product, carbon source and water are mixed, obtain powder；By the powder sintered postcooling, iron and fluorin-doped composite material are obtained.By adulterating Fe and F simultaneously in lithium manganate material, Fe and F have synergistic effect, can effectively inhibit spinel structure LiMn the present invention2O4Jahn Teller effects and manganese dissolving, make the positive electrode that is prepared of the present invention that there is good high rate performance and cycle performance.Moreover, this is simple for process, at low cost, environmental-friendly for preparation method provided by the invention, it is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of iron and fluorin-doped composite material and its preparations
Method.
Background technology
Lithium ion battery due to high with operating voltage, energy density is big, have extended cycle life, self-discharge rate is low, low stain,
The excellent properties such as memory-less effect are widely used in the portable electrics such as mobile phone, laptop, tablet computer, camera
In sub- equipment.With the enhancing of people's environmental consciousness and growing to even greater heights for oil price, the new energy such as electric bicycle, electric vehicle
Source industry has good development prospect, and lithium ion battery is because with the above many merits and as the dynamic of electric vehicle first choice
Power battery.However lithium ion battery is as power battery, still face the problems such as due to security performance, energy density, power density
Face many challenges, therefore the lithium ion battery for meeting power battery requirement need be developed.
Anode material for lithium-ion batteries is an important component of lithium ion battery, great on battery performance influence,
Wherein LiMn2O4 due to have many advantages, such as it is resourceful, cheap, nontoxic receive significant attention, the application in power battery
Very advantageous, but spinelle LiMn2O4Material has the shortcomings that fatal, and capacity attenuation is very fast, under high temperature (55 DEG C) particularly such as
This.Lithium manganate material generates capacity attenuation in cyclic process to be caused by the following aspects：(1) occur in charge and discharge process brilliant
Lattice distort, i.e. Jahn-Teller effects, cause LiMn2O4The contraction of cathode material structure and expansion are to lead to the weight of capacity attenuation
Want reason.(2) one of the reason of dissolving of manganese is also capacity attenuation.Due to containing Mn in spinelle3+, can send out in acid condition
Raw disproportionated reaction：2Mn3+=Mn4++Mn2+, Mn2+It is then dissolvable in water in electrolyte, to cause the reduction of active material, and in height
Under the conditions of temperature, disproportionated reaction speed is faster.(3) from cubic system to the structure of tetragonal crystal system caused by Jahn-Teller effects
Transformation hinders the channel of lithium ion disengaging, to make capacity attenuation.(4) crystallinity, granular size of synthetic material and pattern,
Particle diameter distribution etc. can all influence LiMn2O4Chemical property.(5)LiMn2O4With higher charge and discharge platform, electrolyte exists
Oxygenolysis is easy under high voltage.(6) improper to use battery, as super-charge super-discharge can all influence battery performance.
Cycle performance and the high rate performance for how improving manganate cathode material for lithium are urgently to be resolved hurrily as those skilled in the art
The problem of.
Invention content
In view of this, the purpose of the present invention is to provide a kind of iron and fluorin-doped composite material and preparation method, this
The composite material that invention provides has preferable cyclical stability and high rate performance.
The present invention uses the iron that high temperature solid-state method is prepared and fluorin-doped composite material to be co-doped with for iron (Fe) and fluorine (F)
The LiMn of miscellaneous modified spinelle structure2-xFexO4-yFy/ C composite, x=0.01~0.1, y=0.01~0.1.In the present invention
In, doping of the iron (Fe) in the iron and fluorin-doped composite material is preferably 0.01~0.1, more preferably 0.03~
0.07, most preferably 0.05~0.08；Doping of the fluorine (F) in the iron and fluorin-doped composite material be preferably 0.01~
0.1, more preferably 0.03~0.07, most preferably 0.05~0.08；Matter of the carbon in the iron and fluorin-doped composite material
It is preferably 0.1~20% to measure content, more preferably 0.5~15%, more preferably 1~10%, more preferably 2~8%, most preferably
It is 3~6%；LiMn2-xFexO4-yFyMass content in the iron and fluorin-doped composite material is preferably 80~99.9%,
More preferably 85~99%, more preferably 90~95%.
In the present invention, the preparation method of the iron and fluorin-doped composite material includes the following steps：
(1) by lithium salts, manganese source, source of iron, Fluorine source, water and agate pearl mixed grinding, mixture is obtained；
(2) it is crushed after drying the mixture, obtains powder；
(3) by the powder sintering postcooling, intermediate product is obtained；
(4) it is ground, dries and is crushed successively after mixing the intermediate product, carbon source and water, obtain powder；
(5) by the powder sintered postcooling, iron and fluorin-doped composite material are obtained.
In the present invention, the preparation method of the mixture is preferably：
Lithium source, manganese source, water and agate pearl are mixed, the first mixture is obtained；
Source of iron and the first mixture are mixed, the second mixture is obtained；
Fluorine source and the second mixture are mixed, mixture is obtained.
In the present invention, the lithium source is preferably one or more of lithium hydroxide, lithium carbonate and lithium acetate；The manganese
Source is preferably one or more of manganese nitrate, manganese dioxide, mangano-manganic oxide, manganese sulfate and manganese acetate.In the present invention, institute
It is preferably deionized water to state water.In the present invention, the dosage of the lithium source and manganese source meets LiMn2O4Stoichiometric ratio,
The molar ratio of the lithium source and manganese source is preferably 1:1.In the present invention, the dosage of the water is preferably lithium source and manganese source gross mass
20~80%, more preferably 30~60%, most preferably 40~50%.In the present invention, the quality of the agate pearl with
The ratio of lithium source, manganese source and water gross mass is preferably 1:(1~10), more preferably 1:(2~8), most preferably 1:(3~6).
In the present invention, the source of iron is preferably in ferric sulfate, ferric nitrate, ferrous oxalate, ferrous sulfate and ferrous nitrate
One or more.In the present invention, the molar ratio of the manganese source and source of iron is preferably 2-x：X, x are 0.01~0.5, preferably
0.05~0.4, more preferably 0.1~0.3, most preferably 0.2.
In the present invention, the Fluorine source is preferably one in Kynoar (PVDF), lithium fluoride, sodium fluoride and ammonium fluoride
Kind is several.In the present invention, the molar ratio of the lithium source and Fluorine source is preferably 1:Y, y be 0.01~0.1, preferably 0.02~
0.08, more preferably 0.03~0.06, most preferably 0.04~0.05.
In the present invention, the method ground in the step (1) is preferably ball milling, and the rotating speed of the ball milling is preferably 100
~1000rpm, more preferably 200~800rpm, most preferably 300~600rpm；The time of the ball milling is preferably 1~12 small
When, more preferably 3~10 hours, most preferably 4~8 hours.
In the present invention, temperature dry in the step (2) is preferably 80~150 DEG C, more preferably 90~130 DEG C,
Most preferably 100~120 DEG C；The time of the drying is preferably 8~15 hours, more preferably 10~12 hours.
In the present invention, it is preferably air atmosphere by the atmosphere that the powder is sintered, the method for the sintering is preferred
For：
At the first time from room temperature to the first temperature by the powder, cooling, obtain intermediate product.
In the present invention, the speed of the heating is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/min, most preferably
3℃/min.In the present invention, the room temperature is preferably 20~30 DEG C, more preferably 25 DEG C.In the present invention, first temperature
Preferably 550~850 DEG C of degree, more preferably 600~800 DEG C, most preferably 750 DEG C.In the present invention, the first time is excellent
It is selected as 8~24 hours, more preferably 10~20 hours, most preferably 12~16 hours.In the present invention, the cooling is preferably
Cooled to room temperature.In the present invention, the intermediate product is preferably iron (Fe) and the codoping modified spinelle knot of fluorine (F)
Structure LiMn2-xFexO4-yFyMaterial.
In the present invention, the carbon source is preferably one kind or several in citric acid, glucose, sucrose, starch and tartaric acid
Kind.In the present invention, the quality of the carbon source is preferably the 10~50% of intermediate product quality, more preferably 20~40%, most
Preferably 25~35%.
In the present invention, the intermediate product, carbon source and water are mixed and is carried out under conditions of preferably stirring, the stirring
Time be preferably 1~5 hour, more preferably 2~4 hours, most preferably 3 hours.In the present invention, the method for the grinding
The rotating speed of preferably ball milling, the ball milling is preferably 200~500rpm, more preferably 250~450rpm, most preferably 300~
400rpm；The time of the ball milling is preferably 5~12 hours, more preferably 8~10 hours.In the present invention, the ball milling mistake
Intermediate product, carbon source and the mass ratio of water gross mass and agate pearl are preferably 1 in journey：(1~5), more preferably 1：(2~4),
Most preferably 1:3.
In the present invention, temperature dry in the step (4) is preferably 80~120 DEG C, more preferably 90~110 DEG C,
Most preferably 100 DEG C；The time of the drying is preferably 10~15 hours, more preferably 11~14 hours, most preferably 12~
13 hours.
In the present invention, the powder is sintered and is preferably sintered under an inert atmosphere；The inert atmosphere
Preferably one or both of nitrogen and argon gas.In the present invention, it is preferably by the method that the powder is sintered：
The powder was kept the temperature into for the second time from room temperature to second temperature, it is cooling, it obtains iron (Fe) and fluorine (F) is co-doped with
Miscellaneous composite material.
In the present invention, the heating rate is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/min, most preferably 3
℃/min.In the present invention, the room temperature is preferably 20~30 DEG C, most preferably 25 DEG C.In the present invention, the second temperature
Preferably 550~750 DEG C, more preferably 600~700 DEG C, most preferably 650 DEG C.In the present invention, second time is preferred
It is 5~10 hours, more preferably 6~8 hours.In the present invention, the cooling is preferably cooled to room temperature.In the present invention
In, the iron (Fe) and fluorine (F) codope composite material are iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite.
By adulterating Fe and F simultaneously in lithium manganate material, Fe and F have synergistic effect, can effectively inhibit point the present invention
Spinel structure LiMn2O4Jahn-Teller effects and manganese dissolving, so that the positive electrode that is prepared of the present invention is had good
High rate performance and cycle performance.Moreover, this is simple for process, at low cost, environmental-friendly for preparation method provided by the invention, it is applicable in
In large-scale industrial production.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is to iron (Fe) made from the embodiment of the present invention 1 and fluorine (F) codope composite material and pure LiMn2O4XRD
Collection of illustrative plates；
Fig. 2 is the SEM of iron (Fe) and fluorine (F) codope composite material figures made from the embodiment of the present invention 1；
Fig. 3 is the pure LiMn used in embodiment 12O4The SEM of positive electrode schemes；
Fig. 4 is the charging and discharging curve figure of button cell made from the embodiment of the present invention 2；
Fig. 5 is charging and discharging curve figure in 100 circle cyclic processes of button cell made from the embodiment of the present invention 2.
Specific implementation mode
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 describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
According to spinel structure LiMn2O4Ball is added in lithium hydroxide and manganese sulfate by molar ratio shown in positive electrode chemical formula
Grinding jar, while the deionized water of lithium hydroxide and manganese sulfate gross mass 20% is added, mixed liquor is obtained, by the mixed liquor and agate
Nao pearls mix, and obtaining the first mixture, (mass ratio of pearl and mixed liquor is 1：1).
It is 1.99 according to manganese sulfate and ferric sulfate molar ratio：Ferric sulfate is added in the first mixture by 0.01 amount, is obtained
To the second mixture.
It is 1 according to lithium hydroxide and PVDF molar ratios：PVDF is added in the second mixture by 0.01 amount, obtains third
Mixture.
By the third mixture, the slurry is put into drying box by ball milling 1h, acquisition uniform sizing material at 1000rpm
80 DEG C of dry 15h take out dried object and carry out ball mill crushing, obtain powder.
The powder is raised to 550 DEG C of heat preservations for 24 hours with 1 DEG C/min in air atmosphere from 25 DEG C, cooled to room temperature,
Obtain intermediate product i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFyMaterial.
10% starch of above-mentioned intermediate product quality is dissolved in deionized water, above-mentioned intermediate product is added, stirs 1h
Afterwards, obtained mixture is transferred in ball grinder to (mass ratio of mixture and agate pearl is 1：1), turn in 500rpm/min
The lower ball milling 5h of speed, obtains uniform sizing material, the slurry is put into 80 DEG C of dry 15h in drying box, take out dried object and carry out ball milling
It is broken, obtain powder.
The powder is raised to 1 DEG C/min from 25 DEG C to 550 DEG C of heat preservation 10h in nitrogen atmosphere, cooled to room temperature,
Obtain iron (Fe) and fluorine (F) codope composite material, i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite.
To the iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F) in the embodiment of the present invention 12-xFexO4-yFy/ C is multiple
Condensation material and pure LiMn2O4Microstructure and phase structure characterized, testing result is as shown in FIG. 1 to 3, and A is in Fig. 1
Iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFyThe XRD spectrum of/C composite, B are pure
LiMn2O4XRD spectrum.By Fig. 1 comparison iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFy/ C is multiple
Condensation material and pure LiMn2O4After the XRD spectrum of positive electrode, it can be seen that iron (Fe) and fluorine (F) codoping modified spinelle
Structure LiMn2-xFexO4-yFy/ C composite does not occur dephasign peak, this shows LiMn2O4It can't be because of iron (Fe) and fluorine
(F) cladding of codope and carbon and influence its phase structure, iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite equally has spinel structure.
The spinel structure LiMn obtained by Fig. 2 and Fig. 3 iron (Fe) and fluorine (F) codope and coated modified carbon2-xFexO4- yFy/ C composite and pure LiMn2O4SEM figure comparison it is found that LiMn2-xFexO4-yFyThe microstructure of/C composite is not
It changes.
Embodiment 2
According to 90:5:5 ratio, the iron that embodiment 1 is prepared (Fe) and fluorine (F) codope composite material, bonding
Agent (PVDF) and conductive black Super P mixing, are then added in N-Methyl pyrrolidone, and the mixed of three is obtained after stirring 12h
Close object slurry.
Said mixture slurry is uniformly coated on ready aluminium foil, carries out 12h's in 120 DEG C of vacuum drying chamber
Vacuum drying, obtains positive plate.
Using above-mentioned positive plate as positive electrode, using metal lithium sheet as negative material, diaphragm is polypropylene, electrolysis
Liquid uses LiPF6, battery assembling is carried out in the glove box full of argon gas, obtains button cell.
After battery is cleaned after standing 12h at 25 DEG C, electrochemical property test, testing result are carried out in 3.0~4.3V
As shown in Figure 4 and Figure 5.As shown in Figure 4, the iron (Fe) made from embodiment 1 and fluorine (F) codoping modified spinel structure
LiMn2-xFexO4-yFy/ C composite shows excellent high rate performance, and specific discharge capacity is respectively under 0.1C and 5C multiplying powers
138.3mAh/g and 127.5mAh/g.By Fig. 5 it can be seen that iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite shows preferable cyclical stability, and recycling 100 capacity retention ratios under 1C multiplying powers can reach
93.8%.
Embodiment 3
According to spinel structure LiMn2O4Ball is added in lithium carbonate and manganese dioxide by molar ratio shown in positive electrode chemical formula
Grinding jar, while adding the deionized water that lithium carbonate and manganese dioxide gross mass contain 30%, obtains mixed liquor, by the mixed liquor and
Agate pearl mixes, and obtaining the first mixture, (mass ratio of agate pearl and mixed liquor is 1：3).
It is 1.9 according to manganese dioxide and ferric nitrate molar ratio：Source of iron is added in the first mixture by 0.1 amount, is obtained
Second mixture.
It is 0.98 according to lithium carbonate and ammonium fluoride molar ratio：Fluorine source is added in the second mixture by 0.02 amount, is obtained
Third mixture.
By above-mentioned third mixture in 200rpm ball milling 3h, uniform sizing material is obtained, the slurry is put into 90 in drying box
After DEG C dry 9h, takes out dried object and carry out ball mill crushing, obtain powder.
The powder is raised to 2 DEG C/min from 25 DEG C to 650 DEG C of heat preservation 10h in air atmosphere, cooled to room temperature,
Obtain intermediate product i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFyMaterial.
The glucose of intermediate product quality 20% is dissolved in deionized water, above-mentioned intermediate product is added, it, will after stirring 2h
Obtained mixture is transferred in ball grinder that (mass ratio of mixture and agate pearl is 1：2), the ball milling under 300rpm rotating speeds
6h obtains uniform sizing material, and the uniform sizing material is put into 90 DEG C of dry 11h in drying box, takes out dried object and carries out ball mill crushing,
Obtain powder.
The powder is raised to 2 DEG C/min from 25 DEG C to 600 DEG C of heat preservation 6h in nitrogen inert atmosphere, naturally cools to room
Temperature obtains iron (Fe) and fluorine (F) codope composite material, i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite.
Button cell is prepared according to the method for embodiment 2, the difference from example 2 is that, it is prepared using embodiment 3
Iron (Fe) and fluorine (F) codope composite material alternative embodiment 1 prepare iron (Fe) and fluorine (F) codope composite material.
Button cell prepared by the embodiment of the present invention 3 carries out electrochemical property test at 25 DEG C, in 3.0~4.3V,
Testing result is close with embodiment 2, the results showed that the codoping modified point of iron (Fe) and fluorine (F) prepared by the embodiment of the present invention 3 is brilliant
Stone structure LiMn2-xFexO4-yFy/ C composite has high specific capacity, stable circulation, excellent high rate performance.
Embodiment 4
According to spinel structure LiMn2O4Ball milling is added in lithium acetate and manganese acetate by molar ratio shown in positive electrode chemical formula
Tank, while the deionized water of lithium acetate and manganese acetate gross mass 50% is added, obtain mixed liquor；By the mixed liquor and agate bead
Son mixing, obtaining the first mixture, (mass ratio of agate pearl and mixed liquor is 1：5.5).
It is 1.75 according to manganese acetate and ferrous oxalate molar ratio：Ferrous oxalate is added to above-mentioned first mixing by 0.25 amount
In object, the second mixture is obtained.
It is 0.95 according to lithium acetate and sodium fluoride molar ratio：Sodium fluoride is added to above-mentioned second mixture by 0.05 amount
In, obtain third mixture.
By above-mentioned third mixture in 550rpm ball milling 6.5h, uniform sizing material is obtained, the uniform sizing material is put into drying
In case after 115 DEG C of dry 11.5h, takes out dried object and carry out ball mill crushing, obtain powder.
The powder is raised to 3 DEG C/min from 25 DEG C to 700 DEG C of heat preservation 16h in air atmosphere, cooled to room temperature,
Obtain intermediate product i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFyMaterial.
The sucrose of above-mentioned intermediate product quality 30% is dissolved in deionized water, above-mentioned iron (Fe) is added and fluorine (F) is co-doped with
The spinel structure LiMn of miscellaneous modification2-xFexO4-yFyMaterial after stirring 3h, obtained mixture is transferred in ball grinder (mixed
The mass ratio for closing object and agate pearl is 1：3), the ball milling 8.5h under 350rpm rotating speeds, obtains uniform sizing material, by the uniform object
Material is put into 100 DEG C of dry 17.5h in drying box, takes out dried object and carries out ball mill crushing, obtains powder.
The powder is raised to 3 DEG C/min from 25 DEG C to 650 DEG C of heat preservation 7.5h in nitrogen atmosphere, naturally cools to room
Temperature obtains iron (Fe) and fluorine (F) codope composite material, i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite.
Button cell is prepared according to the method for embodiment 2, the difference from example 2 is that, it is prepared using embodiment 4
Iron (Fe) and fluorine (F) codope composite material alternative embodiment 1 prepare iron (Fe) and fluorine (F) codope composite material.
Button cell prepared by the embodiment of the present invention 4 carries out electrochemical property test at 25 DEG C, in 3.0~4.3V,
Testing result is close with embodiment 2, the results showed that the codoping modified point of iron (Fe) and fluorine (F) prepared by the embodiment of the present invention 4 is brilliant
Stone structure LiMn2-xFexO4-yFy/ C composite has high specific capacity, stable circulation, excellent high rate performance.
Embodiment 5
According to spinel structure LiMn2O4Ball milling is added in lithium carbonate and manganese acetate by molar ratio shown in positive electrode chemical formula
Tank, while the deionized water of lithium carbonate and manganese acetate gross mass 60% is added, mixed liquor is obtained, by the mixed liquor and agate bead
Son mixing, obtaining the first mixture, (mass ratio of agate pearl and mixed liquor is 1：6).
It is 1.6 according to manganese acetate and ferrous nitrate molar ratio：Ferrous nitrate is added in the first mixture by 0.4 amount,
Obtain the second mixture.
It is 0.92 according to lithium carbonate and lithium fluoride molar ratio：Lithium fluoride is added in the second mixture by 0.08 amount, is obtained
To third mixture.
By the third mixture in 800rpm ball milling 10h, uniform sizing material is obtained, the uniform sizing material is put into drying box
In 140 DEG C of dry 12h, take out dried object carry out ball mill crushing, obtain powder.
The powder is raised to 4 DEG C/min from 25 DEG C to 750 DEG C of heat preservation 20h in air atmosphere, cooled to room temperature,
Obtain intermediate product, the i.e. codoping modified spinel structure LiMn of iron (Fe) and fluorine (F)2-xFexO4-yFyMaterial.
The starch of intermediate product quality 40% is dissolved in deionized water, above-mentioned iron (Fe) is added and fluorine (F) codope changes
The spinel structure LiMn of property2-xFexO4-yFyObtained mixture is transferred in ball grinder (mixture by material after stirring 4h
It is 1 with agate bead protonatomic mass ratio：4), the ball milling 10h under 300rpm rotating speeds, obtains uniform sizing material, and the uniform sizing material is put into
In drying box after 110 DEG C of dry 14h, takes out dried object and carry out ball mill crushing, obtain powder.
The powder is raised to 4 DEG C/min from 25 DEG C to 650 DEG C of heat preservation 8h in argon inert atmosphere, naturally cools to room
Temperature obtains iron (Fe) and fluorine (F) codope composite material, i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2- xFexO4-yFy/ C composite.
Button cell is prepared according to the method for embodiment 2, the difference from example 2 is that, it is prepared using embodiment 5
Iron (Fe) and fluorine (F) codope composite material alternative embodiment 1 prepare iron (Fe) and fluorine (F) codope composite material.
Button cell prepared by the embodiment of the present invention 5 carries out electrochemical property test at 25 DEG C, in 3.0~4.3V,
Testing result is close with embodiment 2, the results showed that the codoping modified point of iron (Fe) and fluorine (F) prepared by the embodiment of the present invention 5 is brilliant
Stone structure LiMn2-xFexO4-yFy/ C composite has high specific capacity, stable circulation, excellent high rate performance.
Embodiment 6
According to spinel structure LiMn2O4Ball milling is added in lithium carbonate and manganese sulfate by molar ratio shown in positive electrode chemical formula
Tank, while the deionized water of lithium carbonate and manganese sulfate gross mass 80% is added, obtain mixed liquor；By the mixed liquor and agate bead
Son mixing, obtaining the first mixture, (mass ratio of agate pearl and mixed liquor is 1:10).
It is 1.5 according to manganese sulfate and ferrous oxalate molar ratio：Ferrous oxalate is added in the first mixture by 0.5 amount,
Obtain the second mixture.
It is 0.9 according to lithium carbonate and ammonium fluoride molar ratio：Ammonium fluoride is added in the second mixture by 0.1 amount, is obtained
Third mixture.
By the third mixture in 1000rpm ball milling 1h, uniform sizing material is obtained, the uniform sizing material is put into drying box
In after 150 DEG C of dry 8h, take out dried object and carry out ball mill crushing, obtain powder.
The powder is raised to 5 DEG C/min from 25 DEG C to 850 DEG C of heat preservation 8h in air atmosphere, cooled to room temperature,
Obtain intermediate product i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4-yFyMaterial.
50% starch of intermediate product quality is dissolved in deionized water, iron obtained above (Fe) and fluorine (F) is added
Codoping modified spinel structure LiMn2-xFexO4-yFyObtained mixture is transferred in ball grinder by material after stirring 5h
(mass ratio of mixture and agate pearl is 1：5), the ball milling 5h under 500rpm rotating speeds, obtains uniform sizing material, will be described uniform
Slurry is put into drying box after 120 DEG C of dry 10h, is taken out dried object and is carried out ball mill crushing, obtains powder.
The powder is raised to 5 DEG C/min from 25 DEG C to 750 DEG C of heat preservation 5h in argon gas atmosphere, cooled to room temperature,
Obtain (Fe) and fluorine (F) codope composite material, i.e. iron (Fe) and the codoping modified spinel structure LiMn of fluorine (F)2-xFexO4- yFy/ C composite.
Button cell is prepared according to the method for embodiment 2, the difference from example 2 is that, it is prepared using embodiment 6
Iron (Fe) and fluorine (F) codope composite material alternative embodiment 1 prepare iron (Fe) and fluorine (F) codope composite material.
Button cell prepared by the embodiment of the present invention 6 carries out electrochemical property test at 25 DEG C, in 3.0~4.3V,
Testing result is close with embodiment 2, the results showed that the codoping modified point of iron (Fe) and fluorine (F) prepared by the embodiment of the present invention 6 is brilliant
Stone structure LiMn2-xFexO4-yFy/ C composite has high specific capacity, stable circulation, excellent high rate performance.
The present invention uses Fe and F co-doped modified lithium manganate cathode materials, in Fe and F modifying process there is collaboration to make
With, while being modified using Fe and F and can make positive electrode compared to being modified using individually a kind of ingredient therein
Better cycle performance and high rate performance are obtained simultaneously, the present invention is identical in altered contents content, using Fe and F two
Kind of ingredient be modified the positive electrode of acquisition high rate performance and cycle performance better than Fe (content is identical as Fe and F total amounts) and
F (content is identical as Fe and F total amounts) is individually modified obtained positive electrode.
As seen from the above embodiment, the present invention provides the preparation methods of a kind of iron and fluorin-doped composite material, including
Following steps：By lithium salts, manganese source, source of iron, Fluorine source, water and agate pearl mixed grinding, mixture is obtained；The mixture is done
It is broken after dry, obtain powder；By the powder sintering postcooling, intermediate product is obtained；The intermediate product, carbon source and water are mixed
It is ground, dries and is crushed successively after conjunction, obtain powder；By the powder sintered postcooling, iron and fluorin-doped multiple is obtained
Condensation material.For the present invention by adulterating Fe and F simultaneously in lithium manganate material, Fe and F have synergistic effect, can effectively inhibit sharp brilliant
Stone structure LiMn2O4Jahn-Teller effects and manganese dissolving, so that the positive electrode that is prepared of the present invention is had good
High rate performance and cycle performance.Moreover, this is simple for process, at low cost, environmental-friendly for preparation method provided by the invention, it is suitable for
Large-scale industrial production.
Claims (10)
1. the preparation method of a kind of iron and fluorin-doped composite material, includes the following steps：
(1) by lithium salts, manganese source, source of iron, Fluorine source, water and agate pearl mixed grinding, mixture is obtained；
(2) it is crushed after drying the mixture, obtains powder；
(3) by the powder sintering postcooling, intermediate product is obtained；
(4) it is ground, dries and is crushed successively after mixing the intermediate product, carbon source and water, obtain powder；
(5) by the powder sintered postcooling, iron and fluorin-doped composite material are obtained.
2. according to the method described in claim 1, it is characterized in that, the lithium source is in lithium hydroxide, lithium carbonate and lithium acetate
One or more.
3. according to the method described in claim 1, it is characterized in that, the manganese source is manganese nitrate, manganese dioxide, four oxidations three
One or more of manganese, manganese sulfate and manganese acetate.
4. according to the method described in claim 1, it is characterized in that, the source of iron is ferric sulfate, ferric nitrate, ferrous oxalate, sulphur
One or more of sour ferrous and ferrous nitrate.
5. according to the method described in claim 1, it is characterized in that, the Fluorine source be Kynoar, lithium fluoride, sodium fluoride and
One or more of ammonium fluoride.
6. according to the method described in claim 1, it is characterized in that, the carbon source be citric acid, glucose, sucrose, starch and
One or more of tartaric acid.
7. according to the method described in claim 1, it is characterized in that, the method for grinding is ball milling, the ball in the step (1)
The rotating speed of mill is 100~1000rpm；The time of the ball milling is 1~12 hour.
8. according to the method described in claim 1, it is characterized in that, temperature dry in the step (2) is 80~150 DEG C；
The time of the drying is 8~15 hours.
9. according to the method described in claim 1, it is characterized in that, the temperature being sintered in the step (3) is 550~850 DEG C；
The temperature being sintered in the step (4) is 550~750 DEG C.
10. iron and fluorin-doped composite material that the method described in any one of claim 1~9 is prepared.
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| CN114452987A (en) * | 2021-12-28 | 2022-05-10 | 浙江理工大学桐乡研究院有限公司 | PVDF (polyvinylidene fluoride) modified metal oxide catalyst as well as preparation method and application thereof |
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