CN106025182B - A kind of titanium chromium doping ferric flouride-carbon nano composite anode material and its preparation method and application - Google Patents
A kind of titanium chromium doping ferric flouride-carbon nano composite anode material and its preparation method and application Download PDFInfo
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- CN106025182B CN106025182B CN201610632548.7A CN201610632548A CN106025182B CN 106025182 B CN106025182 B CN 106025182B CN 201610632548 A CN201610632548 A CN 201610632548A CN 106025182 B CN106025182 B CN 106025182B
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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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The present invention provides a kind of titanium chromium doping ferric flouride-carbon nano composite anode materials and preparation method thereof, which is coated through carbon containing conductive material by doping ferric flouride presoma and be made；It is shown in formula I to adulterate ferric flouride presoma；Positive electrode is as shown in Formula II.The present invention adulterates titanium ion and chromium ion, adjusts crystal lattice parameters, so that lithium ion diffusion significantly improves, the enhancing of materials conductive performance improves the specific capacity of material.Above-mentioned doping ferric flouride presoma and carbon containing conductive material are carried out covered composite yarn by the present invention, further increase the electric conductivity of material, and reduce particle aggregation.Therefore, the multiplying power property of material of the present invention and cycle performance are excellent.The present invention provides a kind of lithium ion batteries comprising positive electrode described above.Fe1‑x‑yCrxTi0.75yF3(H2O)0.33Formulas I Fe1‑x‑ yCrxTi0.75yF3(H2O)0.33@C Formula II.
Description
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of titanium chromium doping fluorination iron-carbon nano are multiple
Close positive electrode and its preparation method and application.
Background technique
Lithium ion battery as New Energy Industry is since its operating voltage is high, energy density is big, environmentally protective, memoryless
Effect, self-discharge rate are low, have extended cycle life and the absolute advantages such as discharge performance stabilization, are widely used to various portable electronics
The fields such as product, new-energy automobile.Mineral resources are petered out at present, environmental pollution increasingly aggravates, and exploration is alternative and without dirt
The new energy of dye is a problem to be solved.Although the renewable energy such as solar energy, wind energy, water energy, biomass energy have taken
Great progress was obtained, but high cost and territory restriction problem constrain it as main energy sources；City caused by vehicle exhaust
Air pollution is got worse, and the development of the new-energy automobiles such as electric vehicle (EV) and hybrid electric vehicle (HEV) has been very urgent, this
A little market demands are that the development of lithium ion battery brings opportunity, while the requirement to battery performance is also higher and higher.
Anode material for lithium-ion batteries is the important component of battery, it determine lithium ion battery energy density,
The Specifeca tion speeifications such as service life, security performance.Earliest commercialized lithium ion battery is with LiCoO2For anode, from quotient
Industry metaplasia has been utilized for manufacture mobile phone and laptop and other portable as mainstream positive electrode always since producing
The positive electrode of electronic equipment.LiCoO2Theoretical capacity be up to 274mAh/g, and actual capacity is 150mAh/g or so, and
Cobalt is toxic, its price is also expensive.Since the commercialization of lithium ion battery the 1990s, the actual specific capacity one of positive electrode
Directly between 100~180mAh/g, the low specific capacity of positive electrode is to cause the principal element of capacity bottleneck, studies novel height
Capacity lithium ion battery positive electrode is extremely urgent.
The positive electrode for studying more at present has: lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), LiFePO4
(LiFePO4) and nickle cobalt lithium manganate (Li (Ni, Co, Mn) O2) ternary material etc..LiNiO2Practical reversible specific capacity is in 200mAh/g
Left and right, but Ni3+And it is unstable, it is difficult to synthesize the LiNiO of stoichiometric ratio2.Spinelle LiMn2O4Material possesses voltage height, price
The advantages that cheap, less toxic, reliable synthetic method, and its structure is more stable, but actual specific capacity is low, only 110mAh/g is left
The right side, and the Mn generated that discharges3+Jahn-Teller effect make the high-pressure decomposing of distortion of lattice and electrolyte, make LiMn2O4Hold
Amount decaying, these disadvantages limit its practical application.The LiFePO of olivine crystal form4At low cost, environmentally protective, thermal stability
It is good, but its theoretical specific capacity only has 170mAh/g or so, and actual capacity also only has 140mAh/g or so.Stratiform Li (Ni, Co, Mn)
O2Theoretical specific capacity reaches 280mAh/g, and actual capacity is more than 150mAh/g, but its conductivity is poor.
And metal fluoride is due to good etc. absolutely excellent with high theoretical specific capacity, low price, nontoxicity and safety
Point causes the great attention of researcher.FeF3Possess environmentally protective, theoretical specific capacity is big, energy density is high, it is low in cost,
The advantages that thermal stability is good, and its 3 Li of conversion completely+Theoretical capacity be up to 712mAh/g, even if only convert 1 Li+,
Capacity can also reach 237mAh/g or so.The working principle of the material and conventional lithium ion positive electrode are different, it is to pass through
Phase chemical conversion reaction occurs with lithium metal and carrys out storing energy, passes through Li+Insertion and abjection carry out storage lithium, to obtain remote height
In traditional Li+Obtainable discharge capacity is reacted in insertion/deintercalation.But be fluorinated iron material electric conductivity and kinetic property it is poor,
Cause material high rate performance low, to limit its practical application.
It therefore, is raising FeF3The chemical property of positive electrode, need to find it is a kind of can enhance cyclical stability, improve
Its electron conduction, and then enhance the method for its high rate performance and energy density, this is to positive electrode using particularly significant.
Summary of the invention
In view of this, the application provides a kind of titanium chromium doping ferric flouride-carbon nano composite anode material and preparation method thereof
And application, modified fluorinated iron positive electrode specific capacity provided by the invention is high, has excellent multiplying power property and cycle performance, benefit
In application.
The present invention provides a kind of titanium chromium doping ferric flouride-carbon nano composite anode material, by doping ferric flouride presoma
It is made through carbon containing conductive material cladding；
The doping ferric flouride presoma has Formulas I general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
The titanium chromium doping ferric flouride-carbon nano composite anode material has Formula II general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Preferably, the carbon containing conductive material is selected from one of conductive black and active carbon or a variety of.
Preferably, passed through by doping ferric flouride presoma and carbon containing conductive material dispersion liquid according to weight ratio 100:5~7
Cladding is made.
Preferably, the titanium chromium doping ferric flouride-carbon nano composite anode material is nano particle.
Preferably, the doping ferric flouride presoma has -3 general formula of Formulas I -1, Formulas I -2 or Formulas I:
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 a kind of preparation method of modified fluorinated iron positive electrode, comprising the following steps:
1) it is reacted after mixing hydration molysite, hydration chromic salts and titanium salt and fluoride, obtains adulterating fluorine shown in Formulas I
Change iron presoma:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated after mixing the doping ferric flouride presoma and carbon containing conductive material, obtains titanium shown in Formula II
Chromium adulterates ferric flouride-carbon nano composite anode material；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Preferably, the hydration molysite is Fe (NO3)3·9H2O and FeCl3·6H2At least one of O, the hydrated chromium
Salt is CrCl3·6H2O、Cr2(SO4)3·18H2O and Cr2(SO4)3·6H2One of O or a variety of, the titanium salt are Ti
(NO3)4With Ti (SO4)2·9H2At least one of O, the fluoride are NH4F and NH4HF2At least one of.
Preferably, the step 1) specifically:
After molysite, hydration chromic salts and titanium salt and fluoride mixing will be hydrated, ball milling is carried out in the presence of SiC, is then heated
Reaction obtains adulterating ferric flouride presoma shown in Formulas I.
Preferably, the step 2) specifically:
Ball milling after the doping ferric flouride presoma and carbon containing conductive material dispersion liquid are mixed, is sintered, obtains titanium chromium
Adulterate ferric flouride-carbon nano composite anode material.
The present invention also provides a kind of lithium ion batteries comprising positive electrode described above.
Compared with prior art, modified fluorinated iron positive electrode provided by the invention is titanium chromium doping fluorination iron-carbon nano
Composite positive pole is coated through carbon containing conductive material by doping ferric flouride presoma and is made, wherein the doping ferric flouride forerunner
Body has Formulas I general formula: Fe1-x-yCrxTi0.75yF3(H2O)0.33；The titanium chromium doping ferric flouride-carbon nano composite anode material tool
There is Formula II general formula: Fe1-x-yCrxTi0.75yF3(H2O)0.33@C.The present invention passes through doping Cr3+And Ti4+Both metal ions are adjusted
Crystal lattice parameters are saved, so that lithium ion diffusion significantly improves, the enhancing of materials conductive performance improves the specific capacity of material.
Also, above-mentioned doping ferric flouride presoma and carbon containing conductive material are carried out covered composite yarn by the present invention, further increase material
Electric conductivity, while reducing particle aggregation.Experimental result shows, positive electrode produced by the present invention at room temperature, voltage be 1.5~
When 4.5V, first charge-discharge specific volume is up to 208mAh/g under 0.1C multiplying power, the specific discharge capacity after 30 circulations under 0.2C multiplying power
Still up to 180mAh/g.Show that material of the present invention has excellent multiplying power property and cycle performance, is conducive to lithium-ion electric
Pond application.
Detailed description of the invention
Fig. 1 is that 1 gained titanium chromium of embodiment adulterates ferric flouride-carbon nano composite anode material SEM photograph；
Fig. 2 is the SEM photograph that ferric flouride presoma is adulterated obtained by embodiment 1；
Fig. 3 is obtained by positive electrode obtained by embodiment and comparative example undoped with circulation of the material in the case where current density is 0.2C
Curve；
Fig. 4 is undoped with material obtained by positive electrode obtained by embodiment and comparative example in 1.5~4.5V of voltage range, difference
The high rate performance figure of preceding 50 circulations under current density；
Fig. 5 be obtained by positive electrode and comparative example obtained by embodiment undoped with material in the case where current density is 0.1C for the first time
Charging and discharging curve；
Fig. 6 is undoped with material obtained by positive electrode obtained by embodiment and comparative example in 2.0~4.5V of voltage range, scanning
Rate is the cyclic voltammetry curve under 0.1mV/s.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of titanium chromium to adulterate ferric flouride-carbon nano composite anode material, by doping ferric flouride forerunner
Body is coated through carbon containing conductive material and is made；
The doping ferric flouride presoma has Formulas I general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
The titanium chromium doping ferric flouride-carbon nano composite anode material has Formula II general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
Modified fluorinated iron positive electrode provided by the invention is that titanium chromium adulterates ferric flouride-carbon nano composite anode material,
Specific capacity is high, has excellent multiplying power property and cycle performance etc., and it is steady to can effectively solve the existing circulation of ferric fluoride anode material
It is qualitative can it is poor, electronic conductivity is low, reversible capacity is smaller the problems such as.
Titanium chromium doping ferric flouride-carbon nano composite anode material provided by the invention is by including doping ferric flouride presoma
Material is made；The doping ferric flouride presoma has Formulas I general formula, is the FeF containing minor amount of water3·0.33H2It is mixed in the ferric flouride of O
It is miscellaneous to have a certain amount of Ti4+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, with Cr3+Incorporation, FeF3Band gap
It reduces, Li+Conductivity increases, electric conductivity enhancing；High price Ti4+Accelerating Li+Diffusion while, it is big can also to finely tune channel
It is small, to improve the specific capacity of material.The present invention adjusts crystal lattice parameters, so that lithium by adulterating both metal ions
Ionic diffusion can significantly improve.
In titanium chromium provided by the invention doping ferric flouride-carbon nano composite anode material, above-mentioned doping ferric flouride forerunner
Body is coated with carbon containing conductive material；Material general 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) with electric conductivity preferably contain carbon materials
Material carries out covered composite yarn, can play the role of improving material conductivity and reduce particle aggregation.In the present invention, described carbon containing
Conductive material preferably is selected from one of conductive black and active carbon or a variety of.The present invention does not have the source of the carbon containing conductive material
Have it is specifically limited, using commercial product.It is 100:5~7 according to weight ratio, titanium chromium provided in an embodiment of the present invention adulterates fluorine
Change iron-carbon nano composite positive pole and is made by doping ferric flouride presoma and carbon containing conductive material dispersion liquid by cladding.
Modified fluorinated iron positive electrode described in the embodiment of the present invention is doping Ti4+、Cr3+And the carbon containing conductive material of cladding
Ferric flouride nano composite anode material has biggish specific surface area, to can increase the contact surface of active material and electrolyte
Product increases electro-chemical activity；Also it can reduce Li+Diffusion admittance improves charge-discharge velocity, to improve high rate performance.Meanwhile it is living
Property material during removal lithium embedded volume change generate internal stress can be improved by nanosizing, make following for active material
Ring performance improves.In an embodiment of the present invention, the titanium chromium doping ferric flouride-carbon nano composite anode material is nanometer
Grain, particle size range can be 10nm~200nm, preferably 50nm.
In a preferred embodiment of the invention, the doping ferric flouride presoma has Formulas I -1, Formulas I -2 or Formulas I -3 logical
Formula；The modified fluorinated iron positive electrode has -3 general formula of Formula II -1, Formula II -2 or Formula II.
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 present invention provides a kind of titanium chromium to adulterate ferric flouride-carbon nano composite anode material preparation method, including following
Step:
1) it is reacted after mixing hydration molysite, hydration chromic salts and titanium salt and fluoride, obtains adulterating fluorine shown in Formulas I
Change iron presoma:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated after mixing the doping ferric flouride presoma and carbon containing conductive material, obtains titanium shown in Formula II
Chromium adulterates ferric flouride-carbon nano composite anode material；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
The present invention goes to realize FeF using a kind of method of simple possible3The metal ion impurity of positive electrode and contain
The modified synergic of carbonaceous conductive material cladding, obtained modified fluorinated iron positive electrode are that titanium chromium doping fluorination iron-carbon nano is multiple
Positive electrode is closed, there is excellent multiplying power property and cycle performance, is conducive to application.
The embodiment of the present invention weighs hydration molysite, water according to the ratio between the mole of Fe, Cr, Ti, F in Formulas I chemical formula respectively
Chromic salts, titanium salt and fluoride are closed, mixing carries out ingredient, and it is reacted, obtain Ti4+、Cr3+Ferric flouride presoma is adulterated, general formula is such as
Shown in Formulas I.
For the present invention to be hydrated molysite, hydration chromic salts, titanium salt and fluoride as raw material, ferric flouride presoma is adulterated in preparation.Its
In, the hydration molysite is preferably Fe (NO3)3·9H2O and FeCl3·6H2At least one of O, more preferably Fe (NO3)3·
9H2O.The hydration chromic salts is preferably CrCl3·6H2O、Cr2(SO4)3·18H2O and Cr2(SO4)3·6H2One of O or more
Kind, more preferably CrCl3·6H2O.The titanium salt is preferably Ti (NO3)4With Ti (SO4)2·9H2At least one of O, it is more excellent
It is selected as Titanium Nitrate (Ti (NO3)4).The fluoride is preferably NH4F and NH4HF2At least one of, more preferably ammonium fluoride
(NH4F), the embodiment of the present invention is Fluorine source using the fluoride of low toxicity, is conducive to operation, environmental protection.In an embodiment of the present invention, institute
State Fe in hydration molysite, Cr in hydration chromic salts, in titanium salt in Ti and fluoride the molar ratio of F by shown in chemical formula Formulas I.
The embodiment of the present invention prepares Ti4+、Cr3+The step of adulterating ferric flouride presoma specifically: by hydration molysite, hydration
After chromic salts and the mixing of titanium salt and fluoride, ball milling is carried out in the presence of SiC, then heating reaction, obtains having mixing for Formulas I general formula
Miscellaneous ferric flouride presoma.
Wherein, described to be mixed into batching mode well known to those skilled in the art.During the preparation process, the present invention preferably adopts
Use SiC as ball-milling additive, surfactant and conductive agent, SiC hardness is high, helps ball milling performance good, can grind for a long time, can drop
The grain diameter of low raw material facilitates the activation energy for reducing second stage conversion reaction, improves material reversible capacity.The present invention is real
Applying example and suitable water and alcoholic solution are added in feed proportioning is dispersing agent, and SiC is auxiliary agent, and ball is carried out in high energy ball mill
Mill, the material after obtaining ball milling.Wherein, the alcoholic solution is preferably one of ethyl alcohol, ethylene glycol and propyl alcohol or a variety of, more excellent
It is selected as ethyl alcohol.The amount of the water and alcoholic solution submerges mixtures of materials enough；The mass ratio of SiC and mixtures of materials is preferred
For 0~0.05:1, more preferably 0.05:1.The temperature of the ball milling can be room temperature (generally can be regarded as 15~30 DEG C)；It is described
Ball milling preferably carries out under nitrogen or inert gas shielding.The present invention preferably carries out ball milling with the revolving speed of 250~450r/min；Institute
The time for stating ball milling is preferably 5 hours~24 hours, more preferably 8 hours~20 hours, most preferably 10 hours~15 hours.
Material after taking out ball milling, the embodiment of the present invention can put it into electron tubes type atmosphere furnace and be warming up to 300~500
DEG C, it is cooling after isothermal reaction, obtain Ti4+、Cr3+Adulterate ferric flouride presoma.The reaction is preferably protected in inert gases such as argon gas
Shield is lower to be carried out；The time of the reaction is preferably 5 hours~12 hours, more preferably 8 hours~11 hours.It is described to be cooled to this
Technological means known to the technical staff of field, is cooled to room temperature.
After obtaining doping ferric flouride presoma shown in Formulas I, the embodiment of the present invention is coated carbon containing conductive material, is obtained
Modified fluorinated iron positive electrode, i.e. titanium chromium adulterate ferric flouride-carbon nano composite anode material.The embodiment of the present invention is preferably specific
Are as follows: ball milling after mixing the doping ferric flouride presoma and carbon containing conductive material dispersion liquid is sintered, and titanium chromium doping fluorine is obtained
Change iron-carbon nano composite positive pole.
The present invention is coated using carbon containing conductive material as conductive material source, the carbon containing preferred self-conductive of conductive material
One of carbon black and active carbon are a variety of, have preferable electric conductivity, can improve material conductivity.The present invention is to described carbon containing
The source of conductive material is not particularly limited, and can mix carbon containing conductive material with solvent, and dispersion forms carbon containing conductive material point
Dispersion liquid, it is spare.The solvent for forming dispersion liquid can be ethylene glycol or ethyl alcohol, and carbon containing conductive material and its mass ratio are preferably 1:1
~3, according to conventional ultrasonic disperse.In an embodiment of the present invention, the doping ferric flouride presoma and contain carbonaceous conductive
The weight ratio of material dispersion liquid is preferably 100:5~7.The embodiment of the present invention is by Ti4+、Cr3+Adulterate ferric flouride presoma with it is carbon containing
Conductive material dispersion liquid mixes according to a certain percentage, obtains mixture；Then can by the mixture in planetary ball mill into
Row ball milling, the substance after obtaining ball milling.The revolving speed of the ball milling is preferably 300~500r/min；The time of the ball milling is preferred
For 10h~15h.
The embodiment of the present invention dries the substance after ball milling in a conventional manner, then is sintered in tube-type atmosphere furnace,
Obtain modified fluorinated iron positive electrode.Wherein, the sintering is a kind of heat treatment process, can successively include heating, constant temperature and drop
Thermophase.The present invention is preferably heated up with the rate of 5~10 DEG C/min, isothermal reaction after a certain period of time, with 10~15 DEG C/min's
Rate cooling, obtains sintering feed.The temperature of the reaction is preferably 500~700 DEG C；The time of the reaction be preferably 5h~
10h。
It is cooled to room temperature, obtained sintering feed is crushed, sieved by the embodiment of the present invention, obtains doping Ti4+、Cr3+And it coats
Ferric flouride nano composite anode material (the Fe of carbon containing conductive material1-x-yCrxTi0.75yF3(H2O)0.33@C, wherein x=0.1~
0.2, y=0.06~0.1), i.e., modified fluorinated iron positive electrode.
Method provided in an embodiment of the present invention is when chromic salts, titanium salt and synthesis material to be passed through to one section in high energy ball mill
Between ball milling, and carry out appropriate heat treatment, obtain doping Ti4+、Cr3+Borontrifluoride iron presoma, then itself and carbonaceous material are carried out
Cladding, obtains modified fluorinated iron nano composite anode material.The modified fluorinated iron positive electrode that the present invention is prepared has excellent
Good multiplying power property and cycle performance, also, the present invention can pass through the preparation using solid-phase ball milling method progress positive electrode, operation
It is simple and convenient, production cost is reduced, and do not generate waste liquid, is suitable for industrialization promotion.
The present invention also provides a kind of lithium ion batteries comprising positive electrode described above.Lithium provided by the invention
Ion battery modified fluorinated iron positive electrode described herein above is the active material of anode, high rate performance and good cycle,
Conducive to its practical application in the fields such as electronic product, the vehicles and energy storage material.
The present invention is not particularly limited the compositions such as cathode, the electrolyte of lithium ion battery, is using commonly used in the art
It can.The present invention can obtain lithium ion battery according to the assembling mode of this field routine.Wherein, it includes above-mentioned change that the present invention, which uses,
Property nanometer fluorination iron material, conductive agent and binder slurry, pass through coating carry out electrode plates preparation.The nanometer fluorination
Iron material can be acetylene black (AB) as active material, the conductive agent, and the binder can be Kynoar (PVDF).
Specifically, the embodiment of the present invention can be weighed respectively active material, AB (conductive agent) and PVDF by the mass ratio of 8:1:1
(binder) is ground after mixing, and appropriate N-Methyl pyrrolidone (NMP) is added and wears into pulpous state, with coating machine that gained slurry is equal
It is even to be coated on collector aluminium foil, after being placed in 80 DEG C of air dry ovens to pulp surface solidification, transfer to 100 DEG C of vacuum ovens
In, drying is for 24 hours；The sequin that tablet press machine is sliced into 15mm diameter finally can be used, and weigh up quality, it is spare.
The embodiment of the present invention carries out battery assembly: using the above-mentioned roundlet pole piece cut out as active electrode, metal lithium sheet is
Reference electrode, putting 2400 diaphragm of Celgard and electrolyte between them, (composition of electrolyte is 1mol/L LiPF6, solvent
For ethylene carbonate (EC) and dimethyl carbonate (DMC), ratio 1:1), it is being full of Ar and gloves of the moisture content lower than 10ppm
In case, material is assembled into CR2025 type button cell.
The present invention is tested for the property positive electrode described above, and experimental result is shown, anode produced by the present invention
Material is at room temperature, voltage is when being 1.5~4.5V, and first charge-discharge specific volume is up to 208mAh/g under 0.1C multiplying power, at 0.2C times
After lower 30 circulations of rate, specific discharge capacity is still up to 180mAh/g.Show that material of the present invention has excellent multiplying power special
Property and cycle performance, conducive to the application in lithium ion battery.
For a further understanding of the application, titanium chromium provided by the present application doping ferric flouride-carbon is received below with reference to embodiment
Rice 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, weigh nitric acid respectively
Iron (Fe (NO3)3·9H2O), chromium chloride (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride carry out ingredient, suitable water and second are added
Alcohol submerges mixture, and SiC is auxiliary agent, is 0.05:1 with the mass ratio of mixture, in high energy ball mill under room temperature, nitrogen protection
In with revolving speed be 250r/min, ball milling 10 hours.Then material after taking out ball milling puts it into the vacuum tube of argon gas protection
It is cooling after being warming up to 300 DEG C, constant temperature 8 hours in formula atmosphere furnace, obtain Ti4+、Cr3+Adulterate ferric flouride presoma.
Conductive black is mixed with ethylene glycol by the mass ratio of 1:1, and ultrasonic disperse forms conductive carbon dispersion into ethyl alcohol
Liquid；By the Ti4+、Cr3+It adulterates ferric flouride presoma and conductive carbon dispersion liquid to mix according to the ratio of weight ratio 100:5, obtain
Mixture, by the mixture with revolving speed 300r/min, ball milling 10h in planetary ball mill；Substance after ball milling is dry, then
Heat treatment sintering is carried out in the tube-type atmosphere furnace full of Ar atmosphere: anti-in 500 DEG C of constant temperature of temperature with the heating of 5 DEG C/min rate
5h is answered, with the cooling of 10 DEG C/min rate, is cooled to room temperature, then obtained sintering feed is crushed, screening, doping Ti is obtained4+、Cr3+
Ferric flouride nano composite anode material (the Fe of coated with conductive material0.84Cr0.1Ti0.045F3(H2O)0.33@C)。
Material is scanned electron microscope analysis (SEM), Fig. 1 is that 1 gained titanium chromium of embodiment doping ferric flouride-carbon is nano combined
The SEM photograph of positive electrode, the partial size of the positive electrode are 50nm；Fig. 2 is doping ferric flouride presoma obtained by embodiment 1
SEM photograph.
Embodiment 2
According to Fe0.77Cr0.15Ti0.06F3(H2O)0.33The mole of Fe, Cr, Ti, F in chemical formula, weigh nitric acid respectively
Iron (Fe (NO3)3·9H2O), chromium chloride (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride carry out ingredient, suitable water and second are added
Alcohol submerges mixture, and SiC is auxiliary agent, is 0.05:1 with the mass ratio of mixture, in high energy ball mill under room temperature, nitrogen protection
In with revolving speed be 350r/min, ball milling 15 hours.Then material after taking out ball milling puts it into the vacuum tube of argon gas protection
It is cooling after being warming up to 400 DEG C, constant temperature 10 hours in formula atmosphere furnace, obtain Ti4+、Cr3+Adulterate ferric flouride presoma.
Conductive black is mixed with ethylene glycol by the mass ratio of 1:2, and ultrasonic disperse forms conductive carbon dispersion into ethyl alcohol
Liquid；By the Ti4+、Cr3+It adulterates ferric flouride presoma and conductive carbon dispersion liquid to mix according to the ratio of weight ratio 100:6, obtain
Mixture, by the mixture with revolving speed 400r/min, ball milling 12h in planetary ball mill；Substance after ball milling is dry, then
Heat treatment sintering is carried out in the tube-type atmosphere furnace full of Ar atmosphere: with the heating of 10 DEG C/min rate, under 600 DEG C of constant temperature of temperature
8h is reacted, with the cooling of 10 DEG C/min rate, is cooled to room temperature, then obtained sintering feed is crushed, screening, doping Ti is obtained4+、
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, weigh ferric nitrate respectively
(Fe(NO3)3·9H2O), chromium chloride (CrCl3·6H2O), Titanium Nitrate and ammonium fluoride carry out ingredient, suitable water and ethyl alcohol are added
Mixture is submerged, it is 0.05:1 with the mass ratio of mixture that SiC, which is auxiliary agent, under room temperature, nitrogen protection in high energy ball mill
It is 450r/min with revolving speed, ball milling 15 hours.Then material after taking out ball milling puts it into the electron tubes type of argon gas protection
It is cooling after being warming up to 500 DEG C, constant temperature 12 hours in atmosphere furnace, obtain Ti4+、Cr3+Adulterate ferric flouride presoma.
Active carbon is mixed with ethylene glycol by the mass ratio of 1:3, and ultrasonic disperse forms conductive carbon dispersion into ethyl alcohol
Liquid；By the Ti4+、Cr3+It adulterates ferric flouride presoma and conductive carbon dispersion liquid to mix according to the ratio of weight ratio 100:7, obtain
Mixture, by the mixture with revolving speed 500r/min, ball milling 15h in planetary ball mill；Substance after ball milling is dry, then
Heat treatment sintering is carried out in the tube-type atmosphere furnace full of Ar atmosphere: with the heating of 10 DEG C/min rate, under 700 DEG C of constant temperature of temperature
10h is reacted, with the cooling of 10 DEG C/min rate, is cooled to room temperature, then obtained sintering feed is crushed, screening, doping Ti is obtained4+、
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 the chemistry of Fe, Ti, F
It measures the ratio than 0.94:0.045:3 to weigh, is dissolved in a certain amount of ethanol solution and obtains slurry, by slurry and graphite quality
It is 0.05:1 with the mass ratio of mixture using SiC as auxiliary agent, in high energy ball mill under room temperature, nitrogen protection than 15:1 mixing
In with revolving speed be 350r/min, after ball milling 15 hours, take out material, stir drying at 80 DEG C.Gained powder will be ground after drying
Body material is then placed in the electron tubes type atmosphere furnace of argon gas protection, is warming up to 600 DEG C with 10 DEG C/min rate, 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
Positive electrode obtained by Examples 1 to 3 and comparative example is subjected to electrochemical property test, using multichannel indigo plant electrical testing
At room temperature, voltage range is 1.5~4.5V to system, and electric current is progress charge and discharge under conditions of 0.1~3C (1C=237mA/g)
Electric performance test.Using CHI1000B electrochemical workstation between 2.0~4.5V, sweeps under conditions of speed is 0.1mV/s and followed
Ring volt-ampere (CV) test.It as a result is obtained by positive electrode obtained by embodiment and comparative example undoped with material referring to Fig. 3~Fig. 6, Fig. 3
Cyclic curve in the case where current density is 0.2C, Fig. 4 are to exist obtained by positive electrode obtained by embodiment and comparative example undoped with material
The high rate performance figure of preceding 50 circulations under 1.5~4.5V of voltage range, different current densities, Fig. 5 are anode obtained by embodiment
First charge-discharge curve obtained by material and comparative example undoped with material in the case where current density is 0.1C, Fig. 6 are obtained by embodiment
It is lied prostrate obtained by positive electrode and comparative example undoped with the circulation under material is 0.1mV/s in 2.0~4.5V of voltage range, sweep speed
Pacify curve.
The results show that the Fe being prepared1-x-yCrxTi0.75yF3(H2O)0.33@C positive electrode material at room temperature, voltage 1.5
When~4.5V, first charge-discharge specific volume is respectively up to 195mAh/g (x=0.1, y=0.06), 208mAh/g (x under 0.1C multiplying power
=0.15, y=0.08), 190mAh/g (x=0.2, y=0.1)；Under 0.2C multiplying power after 30 circulations, specific discharge capacity is still
Respectively up to 165mAh/g (x=0.1, y=0.06), 180mAh/g (x=0.15, y=0.08), 152mAh/g (x=0.2, y
=0.1)；Show that obtained positive electrode of the invention has and stablize capacity and excellent multiplying power property, is conducive in lithium ion battery
In application.In the present invention, haveing excellent performance using the lithium ion battery of above-mentioned positive electrode assembling.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (9)
1. a kind of titanium chromium adulterates ferric flouride-carbon nano composite anode material, which is characterized in that by doping ferric flouride presoma through containing
Carbonaceous conductive material cladding is made；The titanium chromium doping ferric flouride-carbon nano composite anode material is nano particle；
The doping ferric flouride presoma has Formulas I general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
The titanium chromium doping ferric flouride-carbon nano composite anode material has Formula II general formula:
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
2. positive electrode according to claim 1, which is characterized in that the carbon containing conductive material is selected from conductive black and work
One of property charcoal is a variety of.
3. positive electrode according to claim 2, which is characterized in that by doping ferric flouride presoma and carbon containing conductive material
Dispersion liquid is made according to weight ratio 100:5~7 by coating.
4. positive electrode described in any one of claim 1 to 3, which is characterized in that the doping ferric flouride presoma
With -3 general formula of Formulas I -1, Formulas I -2 or Formulas I:
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.
5. a kind of titanium chromium adulterates ferric flouride-carbon nano composite anode material preparation method, comprising the following steps:
1) it is reacted after mixing hydration molysite, hydration chromic salts and titanium salt and fluoride, obtains adulterating ferric flouride shown in Formulas I
Presoma:
Fe1-x-yCrxTi0.75yF3(H2O)0.33Formulas I；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1；
2) it is coated after mixing the doping ferric flouride presoma and carbon containing conductive material, obtains titanium chromium shown in Formula II and mix
Miscellaneous ferric flouride-carbon nano composite anode material；
Fe1-x-yCrxTi0.75yF3(H2O)0.33@C Formula II；
Wherein, 0.1≤x≤0.2,0.06≤y≤0.1.
6. preparation method according to claim 5, which is characterized in that the hydration molysite is Fe (NO3)3·9H2O and
FeCl3·6H2At least one of O, the hydration chromic salts are CrCl3·6H2O、Cr2(SO4)3·18H2O and Cr2(SO4)3·
6H2One of O or a variety of, the titanium salt are Ti (NO3)4With Ti (SO4)2·9H2At least one of O, the fluoride are
NH4F and NH4HF2At least one of.
7. preparation method according to claim 5, which is characterized in that the step 1) specifically:
After molysite, hydration chromic salts and titanium salt and fluoride mixing will be hydrated, ball milling is carried out in the presence of SiC, then heating reaction,
It obtains adulterating ferric flouride presoma shown in Formulas I.
8. the preparation method according to any one of claim 5~7, which is characterized in that the step 2) specifically:
Ball milling after the doping ferric flouride presoma and carbon containing conductive material dispersion liquid are mixed, is sintered, is obtained shown in Formula II
Titanium chromium adulterate ferric flouride-carbon nano composite anode material.
9. a kind of lithium ion battery, which is characterized in that including positive electrode according to any one of claims 1 to 4 or right
It is required that the positive electrode that preparation method described in any one of 5~8 obtains.
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| CN109449408B (en) * | 2018-10-30 | 2021-08-17 | 中科廊坊过程工程研究院 | Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof |
| CN110713242B (en) * | 2019-08-09 | 2020-12-01 | 中国科学院地理科学与资源研究所 | Zero-valent iron material Fe @ iron fluoride and preparation method thereof |
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