CN106025182A - Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof - Google Patents
Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN106025182A CN106025182A CN201610632548.7A CN201610632548A CN106025182A CN 106025182 A CN106025182 A CN 106025182A CN 201610632548 A CN201610632548 A CN 201610632548A CN 106025182 A CN106025182 A CN 106025182A
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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Abstract
The invention provides a titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and a preparation method thereof. The material sis prepared through coating a doped iron fluoride precursor with a carbon-containing conductive material, the doped iron fluoride precursor is represented by formula I, and the positive electrode material is represented by formula II. Titanium ions and chromium ions are doped to adjust the crystal lattice parameters of crystals, so the lithium ion diffusion performance is substantially improved, the electricity conduction performance of the material is enhanced, and the specific capacity of the material is improved. The doped iron fluoride precursor is coated and compounded with the carbon-containing conductive material in order to further improve the electricity conduction performance of the material and reduce particle agglomeration. The rate characteristics and the cycle performances of the material are excellent. The invention also provides a lithium ion battery comprising the positive electrode material. The formula I is Fe1-x-yCrxTi0.75yF3(H2O)0.33, and the formula II is represented by Fe1-x-yCrxTi0.75yF3(H2O)0.33@C.
Description
Technical field
The present invention relates to lithium ion battery material technical field, particularly relate to a kind of titanium chromium doping ferric flouride-carbon
Nano composite anode material and its preparation method and application.
Background technology
As the lithium ion battery of New Energy Industry owing to its running voltage is high, energy density ring big, green
Guarantor, memory-less effect, self-discharge rate is low, have extended cycle life and the discharge performance definitely advantage such as stable,
It is widely used in the fields such as various portable type electronic product, new-energy automobile.Mineral resources are the most withered at present
Exhaust, environmental pollution increases the weight of day by day, and exploring alternative and free of contamination novel energy is problem demanding prompt solution.
Although the regenerative resources such as solar energy, wind energy, water energy, biomass energy have been achieved for being in progress greatly,
But high cost and region restricted problem constrain it becomes main energy sources；The urban air that vehicle exhaust causes
Polluting day by day serious, the development of the new-energy automobiles such as electric motor car (EV) and hybrid electric vehicle (HEV) is
Through very urgent, these market demands are that the development of lithium ion battery brings opportunity, simultaneously to cell performance
The requirement of energy is more and more higher.
Anode material for lithium-ion batteries is the important component part of battery, which determines the energy of lithium ion battery
The Specifeca tion speeifications such as metric density, service life, security performance.The most business-like lithium ion battery is
With LiCoO2For positive pole, it has been utilized for as main flow positive electrode since commercially producing always
Manufacture mobile phone and notebook computer and the positive electrode of other portable electric appts.LiCoO2Theory
Capacity is up to 274mAh/g, and actual capacity is about 150mAh/g, and cobalt is poisonous, its price also
Expensive.Since the lithium ion battery commercialization nineties in 20th century, the actual specific capacity one of positive electrode
Directly be between 100～180mAh/g, the low specific capacity of positive electrode be cause capacity bottleneck main because of
Element, research novel high-capacity anode material for lithium-ion batteries is extremely urgent.
The positive electrode studying more at present has: lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), phosphoric acid
Ferrum lithium (LiFePO4) and nickle cobalt lithium manganate (Li (Ni, Co, Mn) O2) ternary material etc..LiNiO2Actual reversible ratio
Capacity is at about 200mAh/g, but Ni3+And unstable, it is difficult to the LiNiO of synthesis stoichiometric proportion2。
Spinelle LiMn2O4Material has the advantages such as voltage high, cheap, low toxicity, reliable synthetic method,
And its structure comparison is stable, but actual specific capacity is low, only about 110mAh/g, and generation of discharging
Mn3+Jahn-Teller effect make the high-pressure decomposing of distortion of lattice and electrolyte, make LiMn2O4Capacity
Decay, these shortcomings limit its actual application.The LiFePO of olivine crystal formation4Low cost, environmental protection,
Heat stability is good, but its theoretical specific capacity only has about 170mAh/g, and actual capacity also only has 140
About mAh/g.Stratiform Li (Ni, Co, Mn) O2Theoretical specific capacity reaches 280mAh/g, and actual capacity exceedes
150mAh/g, but its conductivity is poor.
And metal fluoride is good owing to having high theoretical specific capacity, low price, avirulence and safety
Etc. absolute advantage, cause the great attention of researcher.FeF3Have environmental protection, theoretical specific capacity big,
The advantages such as energy density is high, with low cost, Heat stability is good, and it converts 3 Li completely+Theoretical appearance
Amount up to 712mAh/g, though only 1 Li of conversion+, its capacity also can reach about 237mAh/g.
The operation principle of this material is different with conventional lithium ion positive electrode, it be by with lithium metal generation phase
Chemical conversion reaction carrys out storing energy, passes through Li+Embedding and abjection carry out storing up lithium, thus be far above
Tradition Li+Obtainable discharge capacity is reacted in embedding/deintercalation.But, the electric conductivity of ferric flouride material and power
Character is poor, causes material high rate performance low, thus limits its actual application.
Therefore, for improving FeF3The chemical property of positive electrode, needs to find a kind of can enhancing to circulate surely
Qualitative, improve its electron conduction, and then the method strengthening its high rate performance and energy density, this aligns
The application of pole material is particularly significant.
Summary of the invention
In view of this, the application provides a kind of titanium chromium doping fluorination iron-carbon nano composite positive pole and system thereof
Preparation Method and application, the modified fluorinated ferrum positive electrode specific capacity that the present invention provides is high, has excellent times
Rate characteristic and cycle performance, be beneficial to application.
The present invention provides a kind of titanium chromium doping fluorination iron-carbon nano composite positive pole, and it is by the ferric flouride that adulterates
Presoma prepares through carbon containing conductive material cladding；
Described doping ferric flouride presoma has a Formulas I formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Described titanium chromium doping fluorination iron-carbon nano composite positive pole has a Formula II formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Preferably, one or more in conductive black and activated carbon of described carbon containing conductive material.
Preferably, by doping ferric flouride presoma and carbon containing conductive material dispersion liquid according to weight ratio
100:5～7, is prepared by cladding.
Preferably, described titanium chromium doping fluorination iron-carbon nano composite positive pole is nano-particle.
Preferably, described doping ferric flouride presoma has Formulas I-1, Formulas I-2 or Formulas I-3 formula:
Fe0.84Cr0.1Ti0.045F3(H2O)0.33Formulas I-1；
Fe0.77Cr0.15Ti0.06F3(H2O)0.33Formulas I-2；
Fe0.7Cr0.2Ti0.075F3(H2O)0.33Formulas I-3.
The present invention provides the preparation method of a kind of modified fluorinated ferrum positive electrode, comprises the following steps:
1) react after hydration iron salt, hydration chromic salts and titanium salt and fluoride mixing, obtain Formulas I institute
The doping ferric flouride presoma shown:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated with after described doping ferric flouride presoma and carbon containing conductive material being mixed, obtains Formula II
Shown titanium chromium doping fluorination iron-carbon nano composite positive pole；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Preferably, described hydration iron salt is Fe (NO3)3·9H2O and FeCl3·6H2At least one in O,
Described hydration chromic salts is CrCl3·6H2O、Cr2(SO4)3·18H2O and Cr2(SO4)3·6H2One in O or
Multiple, described titanium salt is Ti (NO3)4With Ti (SO4)2·9H2At least one in O, described fluoride is
NH4F and NH4HF2In at least one.
Preferably, described step 1) particularly as follows:
After being hydrated iron salt, hydration chromic salts and titanium salt and fluoride mixing, in the presence of SiC, carry out ball milling,
Then reacting by heating, obtains the doping ferric flouride presoma shown in Formulas I.
Preferably, described step 2) particularly as follows:
Ball milling after described doping ferric flouride presoma and carbon containing conductive material dispersion liquid are mixed, sintered,
Obtain titanium chromium doping fluorination iron-carbon nano composite positive pole.
The present invention also provides for a kind of lithium ion battery, and it includes positive electrode mentioned above.
Compared with prior art, the present invention provide modified fluorinated ferrum positive electrode be titanium chromium doping ferric flouride-
Carbon nano composite anode material, is prepared through carbon containing conductive material cladding by doping ferric flouride presoma, wherein,
Described doping ferric flouride presoma has Formulas I formula: Fe1-x-yCrxTi0.75yF3(H2O)0.33；Described titanium chromium is mixed
Miscellaneous ferric flouride-carbon nano composite anode material has Formula II formula: Fe1-x-yCrxTi0.75yF3(H2O)0.33@C。
The present invention is by doping Cr3+And Ti4+Both metal ions, regulate crystal lattice parameters so that lithium ion
Diffusion significantly improves, and materials conductive performance strengthens, and improves the specific capacity of material.Further, the present invention
Above-mentioned doping ferric flouride presoma and carbon containing conductive material are carried out covered composite yarn, improves material further
Electric conductivity, reduces particle aggregation simultaneously.Experimental result shows, the positive electrode that the present invention prepares is in room temperature
Under, voltage is when being 1.5～4.5V, under 0.1C multiplying power, first charge-discharge specific volume is up to 208mAh/g, at 0.2C
After lower 30 circulations of multiplying power, specific discharge capacity is still up to 180mAh/g.Show that material of the present invention has
There are excellent multiplying power property and cycle performance, beneficially lithium ion battery applications.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of embodiment 1 gained titanium chromium doping fluorination iron-carbon nano composite positive pole；
Fig. 2 is the SEM photograph of embodiment 1 gained doping ferric flouride presoma；
Fig. 3 is embodiment gained positive electrode and comparative example gained undoped p material is 0.2C in electric current density
Under cyclic curve；
Fig. 4 is embodiment gained positive electrode with comparative example gained undoped p material at voltage range 1.5～4.5
The high rate performance figure of front 50 circulations under V, different electric current density；
Fig. 5 is embodiment gained positive electrode and comparative example gained undoped p material is 0.1C in electric current density
Under first charge-discharge curve；
Fig. 6 is embodiment gained positive electrode with comparative example gained undoped p material at voltage range 2.0～4.5
V, sweep speed are the cyclic voltammetry curve under 0.1mV/s.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that retouched
The embodiment stated is only a part of embodiment of the present invention rather than whole embodiments.Based on the present invention
In embodiment, the institute that those of ordinary skill in the art are obtained under not making creative work premise
There are other embodiments, broadly fall into the scope of protection of the invention.
The invention provides a kind of titanium chromium doping fluorination iron-carbon nano composite positive pole, it is by fluorination of adulterating
Ferrum presoma prepares through carbon containing conductive material cladding；
Described doping ferric flouride presoma has a Formulas I formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Described titanium chromium doping fluorination iron-carbon nano composite positive pole has a Formula II formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
The modified fluorinated ferrum positive electrode that the present invention provides is titanium chromium doping fluorination iron-carbon nano anode composite material
Material, its specific capacity is high, has excellent multiplying power property and cycle performance etc., just can effectively solve ferric flouride
The problems such as the stable circulation performance that pole material exists is poor, electronic conductivity is low, reversible capacity is less.
Before the titanium chromium doping fluorination iron-carbon nano composite positive pole that the present invention provides is by including doping ferric flouride
The material driving body is made；Described doping ferric flouride presoma has Formulas I formula, containing minor amount of water
FeF3·0.33H2Doped with a certain amount of Ti in the ferric flouride of O4+And Cr3+, wherein, 0.1≤x≤0.2,
Such as x=0.1,0.15,0.2；0.06≤y≤0.1, such as y=0.06,0.08,0.1.In material of the present invention,
Cr3+Radius and Fe3+Radius is close, along with Cr3+Incorporation, FeF3Band gap reduce, Li+Electrical conductivity increases
Adding, electric conductivity strengthens；Ti at high price4+Accelerating Li+Diffusion while, it is also possible to fine setting channel sized,
Thus improve the specific capacity of material.The present invention is by doping both metal ions, regulation crystal lattices ginseng
Number so that lithium ion diffusion significantly improves.
In the titanium chromium doping fluorination iron-carbon nano composite positive pole that the present invention provides, above-mentioned doping is fluorinated
Ferrum presoma is coated with carbon containing conductive material；Material formula is as shown in Formula II:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II.
The present invention will adulterate ferric flouride presoma (Fe1-x-yCrxTi0.75yF3(H2O)0.33) preferably contain with electric conductivity
Material with carbon element carries out covered composite yarn, can play and improves material conductivity and reduce the effect of particle aggregation.?
In the present invention, described carbon containing conductive material preferably is selected from one or more in conductive black and activated carbon.This
Invent the source to described carbon containing conductive material to be not particularly limited, use commercially available prod.According to weight
Amount than be 100:5～7, the embodiment of the present invention provide titanium chromium doping fluorination iron-carbon nano composite positive pole by
Doping ferric flouride presoma and carbon containing conductive material dispersion liquid are prepared by cladding.
Modified fluorinated ferrum positive electrode described in the embodiment of the present invention is doping Ti4+、Cr3+And cladding is containing carbonaceous conductive
The ferric flouride nano composite anode material of material, has bigger specific surface area, it is thus possible to increase activity material
Material and the contact area of electrolyte, increase electro-chemical activity；Also Li can be reduced+Diffusion admittance, improves charge and discharge
Electricity speed, thus improve high rate performance.Meanwhile, active material change in volume during removal lithium embedded produces
Internal stress can be improved by nanorize, make the cycle performance of active material improve.In the present invention
Embodiment in, described titanium chromium doping fluorination iron-carbon nano composite positive pole be nano-particle, its particle diameter
Scope can be 10nm～200nm, preferably 50nm.
In a preferred embodiment of the invention, described doping ferric flouride presoma have Formulas I-1, Formulas I-2 or
Formulas I-3 formula；Described modified fluorinated ferrum positive electrode has Formula II-1, Formula II-2 or Formula II-3 formula.
Fe0.84Cr0.1Ti0.045F3(H2O)0.33Formulas I-1；Fe0.84Cr0.1Ti0.045F3(H2O)0.33@C Formula II-1；
Fe0.77Cr0.15Ti0.06F3(H2O)0.33Formulas I-2；Fe0.77Cr0.15Ti0.06F3(H2O)0.33@C Formula II-2；
Fe0.7Cr0.2Ti0.075F3(H2O)0.33Formulas I-3；Fe0.7Cr0.2Ti0.075F3(H2O)0.33@C Formula II-3.
The invention provides the preparation method of a kind of titanium chromium doping fluorination iron-carbon nano composite positive pole, bag
Include following steps:
1) react after hydration iron salt, hydration chromic salts and titanium salt and fluoride mixing, obtain Formulas I institute
The doping ferric flouride presoma shown:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated with after described doping ferric flouride presoma and carbon containing conductive material being mixed, obtains Formula II
Shown titanium chromium doping fluorination iron-carbon nano composite positive pole；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
The present invention uses a kind of method of simple possible to go to realize FeF3The metal ion lattice of positive electrode is mixed
The modified synergic that miscellaneous and carbon containing conductive material is coated with, obtained modified fluorinated ferrum positive electrode is that titanium chromium is mixed
Miscellaneous ferric flouride-carbon nano composite anode material, has excellent multiplying power property and cycle performance, is beneficial to application.
The embodiment of the present invention, according to the ratio of the mole of Fe, Cr, Ti, F in Formulas I chemical formula, weighs respectively
Hydration iron salt, hydration chromic salts, titanium salt and fluoride, mixing carries out dispensing, reacted, obtains Ti4+、
Cr3+Doping ferric flouride presoma, its formula is shown in formula I.
The present invention, with hydration iron salt, hydration chromic salts, titanium salt and fluoride as raw material, prepares doping ferric flouride
Presoma.Wherein, described hydration iron salt is preferably Fe (NO3)3·9H2O and FeCl3·6H2In O at least
One, more preferably Fe (NO3)3·9H2O.Described hydration chromic salts is preferably CrCl3·6H2O、
Cr2(SO4)3·18H2O and Cr2(SO4)3·6H2One or more in O, more preferably CrCl3·6H2O。
Described titanium salt is preferably Ti (NO3)4With Ti (SO4)2·9H2At least one in O, more preferably Titanium Nitrate
(Ti(NO3)4).Described fluoride is preferably NH4F and NH4HF2In at least one, more preferably
Ammonium fluoride (NH4F), the embodiment of the present invention utilizes the fluoride of low toxicity to be fluorine source, is beneficial to operation, environmental protection.
In an embodiment of the present invention, Ti and fluorination in Cr, titanium salt in Fe, hydration chromic salts in described hydration iron salt
In thing, the mol ratio of F is as shown in chemical formula Formulas I.
The embodiment of the present invention prepares Ti4+、Cr3+The step of doping ferric flouride presoma is particularly as follows: by hydrated iron
After salt, hydration chromic salts and titanium salt and fluoride mix, carrying out ball milling in the presence of SiC, then heating is anti-
Should, obtain the doping ferric flouride presoma with Formulas I formula.
Wherein, batching mode well known to those skilled in the art it is mixed into described in.In preparation process, this
Invention preferably employs SiC as ball-milling additive, surfactant and conductive agent, and SiC hardness is high, helps ball milling
Performance is good, can grind for a long time, can reduce the grain diameter of raw material, contributes to reducing second stage and converts
The activation energy of reaction, improves material reversible capacity.The embodiment of the present invention adds appropriate when feed proportioning
Water and alcoholic solution are dispersant, and SiC is auxiliary agent, carry out ball milling, after obtaining ball milling in high energy ball mill
Material.Wherein, described alcoholic solution is preferably one or more in ethanol, ethylene glycol and propanol, more excellent
Elect ethanol as.Amount enough submergences mixtures of materials of described water and alcoholic solution；SiC and mixtures of materials
Mass ratio be preferably 0～0.05:1, more preferably 0.05:1.The temperature of described ball milling can be that room temperature is (general
Can be regarded as 15～30 DEG C)；Described ball milling is preferably carried out under nitrogen or inert gas shielding.The present invention is excellent
Choosing carries out ball milling with the rotating speed of 250～450r/min；The time of described ball milling is preferably 5 hours～24 hours,
More preferably 8 hours～20 hours, most preferably 10 hours～15 hours.
Taking out the material after ball milling, the embodiment of the present invention can put it in electron tubes type atmosphere furnace and be warmed up to
300～500 DEG C, cool down after isothermal reaction, obtain Ti4+、Cr3+Doping ferric flouride presoma.Described reaction
Preferably carry out under the inert gas shieldings such as argon；The time of described reaction is preferably 5 hours～12 hours,
More preferably 8 hours～11 hours.Described it is cooled to technological means well known to those skilled in the art, cooling
To room temperature.
After obtaining the doping ferric flouride presoma shown in Formulas I, the embodiment of the present invention is coated with the material Han carbonaceous conductive
Material, obtains modified fluorinated ferrum positive electrode, i.e. titanium chromium doping fluorination iron-carbon nano composite positive pole.This
Inventive embodiments is preferably particularly as follows: mix described doping ferric flouride presoma and carbon containing conductive material dispersion liquid
Ball milling after conjunction, sintered, obtain titanium chromium doping fluorination iron-carbon nano composite positive pole.
The present invention is coated with using carbon containing conductive material as conductive material source, and described carbon containing conductive material is excellent
One or more in conductive black and activated carbon, have preferable electric conductivity, can improve material and lead
Electrically.The source of described carbon containing conductive material is not particularly limited by the present invention, can be by carbon containing conductive material
Mix with solvent, dispersion, form carbon containing conductive material dispersion liquid, standby.The solvent forming dispersion liquid can
For ethylene glycol or ethanol, carbon containing conductive material is preferably 1:1～3 with its mass ratio, according to conventional ultrasonic
Disperse.In an embodiment of the present invention, described doping ferric flouride presoma and carbon containing conductive material divide
The weight ratio dissipating liquid is preferably 100:5～7.The embodiment of the present invention is by Ti4+、Cr3+Doping ferric flouride presoma
Mix according to a certain percentage with carbon containing conductive material dispersion liquid, obtain compound；Then can be by described mixing
Material carries out ball milling in planetary ball mill, obtains the material after ball milling.The rotating speed of described ball milling is preferably
300～500r/min；The time of described ball milling is preferably 10h～15h.
Material after ball milling is dried by the embodiment of the present invention in a conventional manner, then enters in tube-type atmosphere furnace
Row sintering, obtains modified fluorinated ferrum positive electrode.Wherein, described sintering is a kind of heat treatment process, can
Include intensification, constant temperature and temperature-fall period successively.The present invention is preferably with the ramp of 5～10 DEG C/min, permanent
After temperature reaction certain time, lower the temperature with the speed of 10～15 DEG C/min, obtain sintering feed.The temperature of described reaction
Degree is preferably 500～700 DEG C；The time of described reaction is preferably 5h～10h.
After being down to room temperature, the sintering feed obtained is pulverized by the embodiment of the present invention, screening, obtains the Ti that adulterates4+、
Cr3+And the ferric flouride nano composite anode material of cladding carbon containing conductive material
(Fe1-x-yCrxTi0.75yF3(H2O)0.33@C, wherein, x=0.1～0.2, y=0.06～0.1), the most modified fluorinated
Ferrum positive electrode.
The method that the embodiment of the present invention provides is by chromic salts, titanium salt and synthesis material warp in high energy ball mill
Ball milling after a while, and carry out appropriate heat treatment, obtain the Ti that adulterates4+、Cr3+Borontrifluoride ferrum presoma,
Again it is coated with carbonaceous material, obtains modified fluorinated ferrum nano composite anode material.System of the present invention
The standby modified fluorinated ferrum positive electrode obtained has excellent multiplying power property and cycle performance, and, this
Bright can be simple to operation by the preparation utilizing solid-phase ball milling method to carry out positive electrode, reduce production
Cost, and do not produce waste liquid, be suitable to industrialization promotion.
Present invention also offers a kind of lithium ion battery, it includes positive electrode mentioned above.The present invention
The modified fluorinated ferrum positive electrode that the lithium ion battery of offer is described herein above is the active material of positive pole, times
Rate performance and good cycle, be beneficial to it in the fields such as electronic product, the vehicles and energy storage material
Actual application.
The compositions such as the negative pole of lithium ion battery, electrolyte are not particularly limited by the present invention, use this area
Conventional.The present invention can obtain lithium ion battery according to the assembling mode of this area routine.Wherein,
The present invention uses and includes above-mentioned modified Nano ferric flouride material, conductive agent and the slurry of binding agent, by being coated with
Cover the preparation carrying out electrode plates.Described nanometer ferric flouride material is as active material, and described conductive agent can
For acetylene black (AB), described binding agent can be Kynoar (PVDF).
Concrete, the embodiment of the present invention can weigh active material, AB (conduction respectively by the mass ratio of 8:1:1
Agent) and PVDF (binding agent), grind after mixing, add appropriate N-Methyl pyrrolidone (NMP) and wear into slurry
Shape, is evenly coated in gained slurry on collector body aluminium foil with coating machine, is placed in 80 DEG C of air dry ovens to slurry
After material surface solidification, transfer in 100 DEG C of vacuum drying ovens, be dried 24h；Finally can use tablet machine
It is sliced into the sequin of 15mm diameter, and weighs up quality, standby.
The embodiment of the present invention carries out battery assembling: using the above-mentioned roundlet pole piece cut out as active electrode, gold
Belonging to lithium sheet is reference electrode, and (electrolyte becomes with electrolyte to put Celgard 2400 barrier film between which
Part is 1mol/L LiPF6, solvent is ethylene carbonate (EC) and dimethyl carbonate (DMC), ratio
1:1), at full Ar and moisture in the glove box less than 10ppm, material is assembled into CR2025
Type button cell.
The present invention carries out performance test to positive electrode mentioned above, and experimental result shows, system of the present invention
Positive electrode at room temperature, voltage is when being 1.5～4.5V, under 0.1C multiplying power, first charge-discharge specific volume can
Reaching 208mAh/g, under 0.2C multiplying power after 30 circulations, specific discharge capacity is still up to 180mAh/g.
Show that material of the present invention has excellent multiplying power property and cycle performance, be beneficial in lithium ion battery
Application.
In order to be further appreciated by the application, titanium chromium doping fluorination the application provided below in conjunction with embodiment
Iron-carbon nano composite positive pole and its preparation method and application is specifically described.
Embodiment 1
According to Fe0.84Cr0.1Ti0.045F3(H2O)0.33The mole of Fe, Cr, Ti, F in chemical formula, point
Another name takes ferric nitrate (Fe (NO3)3·9H2O), Chlorizate chromium (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride,
Carrying out dispensing, add appropriate water and ethanol submergence mixture, SiC is auxiliary agent, itself and the quality of mixture
Ratio is 0.05:1, with rotating speed as 250r/min in high energy ball mill under the protection of room temperature, nitrogen, and ball milling 10
Hour.Take out the material after ball milling, then put it in the electron tubes type atmosphere furnace of argon shield,
Being warmed up to 300 DEG C, constant temperature cooled down after 8 hours, obtained Ti4+、Cr3+Doping ferric flouride presoma.
Being mixed by the mass ratio of 1:1 with ethylene glycol by conductive black, and ultrasonic disperse is in ethanol, formation is led
Electrical carbon dispersion liquid；By described Ti4+、Cr3+Doping ferric flouride presoma and conductive carbon dispersion liquid are according to weight ratio
100:5 ratio mixing, obtain compound, by this compound in planetary ball mill with rotating speed 300r/min,
Ball milling 10h；Material after ball milling is dried, then in the tube-type atmosphere furnace of full Ar atmosphere, carries out heat
Process sintering: with 5 DEG C/min ramp, at 500 DEG C of isothermal reaction 5h of temperature, with 10 DEG C/min speed
Rate is lowered the temperature, and after being down to room temperature, then the sintering feed obtained is pulverized, is sieved, obtains the Ti that adulterates4+、Cr3+Bag
Cover the ferric flouride nano composite anode material (Fe of conductive material0.84Cr0.1Ti0.045F3(H2O)0.33@C)。
Material is scanned electronic microscope photos (SEM), and Fig. 1 is the doping fluorination of embodiment 1 gained titanium chromium
The SEM photograph of iron-carbon nano composite positive pole, the particle diameter of this positive electrode is 50nm；Fig. 2 is real
Execute the SEM photograph of example 1 gained doping ferric flouride presoma.
Embodiment 2
According to Fe0.77Cr0.15Ti0.06F3(H2O)0.33The mole of Fe, Cr, Ti, F in chemical formula, point
Another name takes ferric nitrate (Fe (NO3)3·9H2O), Chlorizate chromium (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride,
Carrying out dispensing, add appropriate water and ethanol submergence mixture, SiC is auxiliary agent, itself and the quality of mixture
Ratio is 0.05:1, with rotating speed as 350r/min in high energy ball mill under the protection of room temperature, nitrogen, and ball milling 15
Hour.Take out the material after ball milling, then put it in the electron tubes type atmosphere furnace of argon shield,
Being warmed up to 400 DEG C, constant temperature cooled down after 10 hours, obtained Ti4+、Cr3+Doping ferric flouride presoma.
Being mixed by the mass ratio of 1:2 with ethylene glycol by conductive black, and ultrasonic disperse is in ethanol, formation is led
Electrical carbon dispersion liquid；By described Ti4+、Cr3+Doping ferric flouride presoma and conductive carbon dispersion liquid are according to weight ratio
100:6 ratio mixing, obtain compound, by this compound in planetary ball mill with rotating speed 400r/min,
Ball milling 12h；Material after ball milling is dried, then in the tube-type atmosphere furnace of full Ar atmosphere, carries out heat
Process sintering: with 10 DEG C/min ramp, under 600 DEG C of constant temperature of temperature, react 8h, with 10 DEG C/min
Speed is lowered the temperature, and after being down to room temperature, then the sintering feed obtained is pulverized, is sieved, obtains the Ti that adulterates4+、Cr3+
Ferric flouride nano composite anode material (the Fe of coated with conductive material0.77Cr0.15Ti0.06F3(H2O)0.33@C)。
Embodiment 3
According to Fe0.7Cr0.2Ti0.075F3(H2O)0.33The mole of Fe, Cr, Ti, F in chemical formula, respectively
Weigh ferric nitrate (Fe (NO3)3·9H2O), Chlorizate chromium (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride,
Carrying out dispensing, add appropriate water and ethanol submergence mixture, SiC is auxiliary agent, itself and the quality of mixture
Ratio is 0.05:1, with rotating speed as 450r/min in high energy ball mill under the protection of room temperature, nitrogen, and ball milling 15
Hour.Take out the material after ball milling, then put it in the electron tubes type atmosphere furnace of argon shield,
Being warmed up to 500 DEG C, constant temperature cooled down after 12 hours, obtained Ti4+、Cr3+Doping ferric flouride presoma.
Activated carbon is mixed by the mass ratio of 1:3 with ethylene glycol, and ultrasonic disperse is in ethanol, forms conduction
Carbon dispersion liquid；By described Ti4+、Cr3+Doping ferric flouride presoma and conductive carbon dispersion liquid are according to weight ratio
100:7 ratio mixing, obtain compound, by this compound in planetary ball mill with rotating speed 500r/min,
Ball milling 15h；Material after ball milling is dried, then in the tube-type atmosphere furnace of full Ar atmosphere, carries out heat
Process sintering: with 10 DEG C/min ramp, under 700 DEG C of constant temperature of temperature, react 10h, with 10 DEG C/min
Speed is lowered the temperature, and after being down to room temperature, then the sintering feed obtained is pulverized, is sieved, obtains the Ti that adulterates4+、Cr3+
Ferric flouride nano composite anode material (the Fe of coated with conductive material0.7Cr0.2Ti0.075F3(H2O)0.33@C)。
Comparative example
Respectively with FeCl3·6H2O、Ti(SO4)2·9H2O and NH4F is source of iron, titanium source and fluorine source.By Fe,
The ratio of stoichiometric proportion 0.94:0.045:3 of Ti, F weighs, and is dissolved in a certain amount of ethanol solution and obtaining
Slurry, by slurry with graphite quality than 15:1 batch mixing, with SiC as auxiliary agent, itself and the mass ratio of mixture
For 0.05:1, with rotating speed as 350r/min in high energy ball mill under the protection of room temperature, nitrogen, ball milling 15 is little
Shi Hou, takes out material, and at 80 DEG C, stirring is dried.Gained powder body material will be ground after drying, then put
Enter to have in the electron tubes type atmosphere furnace of argon shield, with 10 DEG C/min ramp to 600 DEG C, constant temperature 17
After hour, it is cooled to room temperature, obtains Fe0.94Ti0.045F3(H2O)0.33@C nano composite positive pole.
Embodiment 4
By embodiment 1～3 and comparative example gained positive electrode carry out electrochemical property test, use multichannel
At room temperature, voltage range is 1.5～4.5V to blue electrical testing system, and electric current is 0.1～3C (1C=237mA/g)
Under conditions of, carry out charge-discharge performance test.CHI1000B electrochemical operation is used to stand in 2.0～4.5V
Between, sweep speed for being circulated volt-ampere (CV) test under conditions of 0.1mV/s.Result sees Fig. 3～Fig. 6,
Fig. 3 is embodiment gained positive electrode with comparative example gained undoped p material under electric current density is 0.2C
Cyclic curve, Fig. 4 is embodiment gained positive electrode with comparative example gained undoped p material at voltage range
1.5～4.5V, the high rate performance figure of front 50 circulations under different electric current densities, Fig. 5 is embodiment gained
Positive electrode and comparative example gained undoped p material first charge-discharge curve under electric current density is 0.1C,
Fig. 6 be embodiment gained positive electrode with comparative example gained undoped p material voltage range 2.0～4.5V,
Sweep speed is the cyclic voltammetry curve under 0.1mV/s.
Result shows, the Fe prepared1-x-yCrxTi0.75yF3(H2O)0.33@C positive electrode material at room temperature,
When voltage is 1.5～4.5V, under 0.1C multiplying power first charge-discharge specific volume respectively up to 195mAh/g (x=0.1,
Y=0.06), 208mAh/g (x=0.15, y=0.08), 190mAh/g (x=0.2, y=0.1)；At 0.2C times
Rate lower 30 times circulation after, specific discharge capacity the most respectively up to 165mAh/g (x=0.1, y=0.06), 180
MAh/g (x=0.15, y=0.08), 152mAh/g (x=0.2, y=0.1)；Show the positive pole that the present invention obtains
Material has stable capacity and excellent multiplying power property, is beneficial to the application in lithium ion battery.At this
In bright, use the excellent performance of the lithium ion battery that above-mentioned positive electrode assembles.
The above is only the preferred embodiment of the present invention, it is noted that for making the art
Professional and technical personnel, on the premise of without departing from the technology of the present invention principle, is that by implementing these
The multiple amendment of example, and these amendments also should be regarded as the scope that the present invention should protect.
Claims (10)
1. a titanium chromium doping fluorination iron-carbon nano composite positive pole, it is characterised in that be fluorinated by doping
Ferrum presoma prepares through carbon containing conductive material cladding；
Described doping ferric flouride presoma has a Formulas I formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Described titanium chromium doping fluorination iron-carbon nano composite positive pole has a Formula II formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Positive electrode the most according to claim 1, it is characterised in that described carbon containing conductive material selects
One or more in conductive black and activated carbon.
Positive electrode the most according to claim 2, it is characterised in that by doping ferric flouride presoma
With carbon containing conductive material dispersion liquid according to weight ratio 100:5～7, prepared by cladding.
Positive electrode the most according to claim 1, it is characterised in that described titanium chromium doping ferric flouride
-carbon nano composite anode material is nano-particle.
5. according to the positive electrode according to any one of Claims 1 to 4, it is characterised in that described doping
Ferric flouride presoma has Formulas I-1, Formulas I-2 or Formulas I-3 formula:
Fe0.84Cr0.1Ti0.045F3(H2O)0.33Formulas I-1；
Fe0.77Cr0.15Ti0.06F3(H2O)0.33Formulas I-2；
Fe0.7Cr0.2Ti0.075F3(H2O)0.33Formulas I-3.
6. a preparation method for titanium chromium doping fluorination iron-carbon nano composite positive pole, comprises the following steps:
1) react after hydration iron salt, hydration chromic salts and titanium salt and fluoride mixing, obtain Formulas I institute
The doping ferric flouride presoma shown:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated with after described doping ferric flouride presoma and carbon containing conductive material being mixed, obtains Formula II
Shown titanium chromium doping fluorination iron-carbon nano composite positive pole；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Preparation method the most according to claim 6, it is characterised in that described hydration iron salt is
Fe(NO3)3·9H2O and FeCl3·6H2At least one in O, described hydration chromic salts is CrCl3·6H2O、
Cr2(SO4)3·18H2O and Cr2(SO4)3·6H2One or more in O, described titanium salt is Ti (NO3)4With
Ti(SO4)2·9H2At least one in O, described fluoride is NH4F and NH4HF2In at least one.
Preparation method the most according to claim 6, it is characterised in that described step 1) particularly as follows:
After being hydrated iron salt, hydration chromic salts and titanium salt and fluoride mixing, in the presence of SiC, carry out ball milling,
Then reacting by heating, obtains the doping ferric flouride presoma shown in Formulas I.
9. according to the preparation method according to any one of claim 6～8, it is characterised in that described step
2) particularly as follows:
Ball milling after described doping ferric flouride presoma and carbon containing conductive material dispersion liquid are mixed, sintered,
Obtain the titanium chromium doping fluorination iron-carbon nano composite positive pole shown in Formula II.
10. a lithium ion battery, it is characterised in that include according to any one of Claims 1 to 5
The positive electrode that preparation method according to any one of positive electrode or claim 6～9 obtains.
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