CN105098137B - Lithium ion battery, positive electrode material thereof and preparation method - Google Patents
Lithium ion battery, positive electrode material thereof and preparation method Download PDFInfo
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Abstract
The invention provides a lithium ion battery, a positive electrode material thereof and a preparation method thereof. The anode material of the lithium ion battery is CeF3And carbon, wherein the chemical formula of the anode material is CeF3C, the carbon is porous carbon, the CeF3Located within pores of the porous carbon. The lithium ion battery includes: a positive electrode sheet comprising a positive electrode material; a negative plate; the isolation film is positioned between the positive plate and the negative plate; and an electrolyte. The positive electrode material is the positive electrode material of the lithium ion battery. The positive electrode material of the lithium ion battery has high first charge capacity, first discharge capacity, first coulombic efficiency and good cycle performance. The lithium ion battery has high energy density, good safety performance and low cost.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of lithium ion battery and its positive electrode and preparation method.
Background technology
In the battery having been commercialized, lithium ion battery has high energy density, operating voltage height, had extended cycle life, certainly
Discharge rate is low, memory-less effect, small volume and it is lightweight the advantages of, be widely used to various portable type electronic products, and into
One of first choice for electrokinetic cell and energy-storage battery.But, lithium ion battery is in the side such as security, production cost and energy density
Face still suffers from deficiency, constrains lithium ion battery further applying in advanced electronic equipment, electric automobile and energy storage field.
Generally, lithium ion battery is overcharging, under the conditions of short circuit or high temperature etc., and heat can be led in inside lithium ion cell accumulation
Cause the internal temperature rise of lithium ion battery, when temperature is increased to a certain degree by cause the decomposition of SEI films, electrolyte point
Heat release and the analysis oxygen heat release of positive electrode etc. are solved, now heat is further accumulated in inside lithium ion cell and lost until occurring heat
Control, ultimately results in lithium ion battery burning or explodes.Wherein, the analysis oxygen heat release of positive electrode is to cause inside lithium ion cell heat
Key factor out of control.In addition, the energy density of lithium ion battery can not still fully meet portable electric pool equipment and electronic vapour
The demand of Vehicular dynamic battery.Wherein, the relatively low specific capacity of positive electrode is that limiting lithium ion cell energy density is further carried
One of key factor risen.Meanwhile, the current widest positive electrode LiCoO of commercial applications2Due to the valency containing Elements C o
Lattice are expensive, are unfavorable for lithium ion battery and develop to cost degradation direction, limit the application of lithium ion.Therefore, research and
Development structure is stable, low cost, the positive electrode of high-energy-density are to improve one of effective way of performance of lithium ion battery.
The content of the invention
In view of problem present in background technology, present invention aims at provide a kind of lithium ion battery and its positive electrode
And preparation method, the positive electrode of the lithium ion battery has high initial charge capacity, first discharge capacity, first coulomb
Efficiency and good cycle performance, the lithium ion battery have high energy density, good security performance and low cost.
To achieve these goals, in the first aspect of the present invention, the invention provides a kind of positive pole of lithium ion battery
Material, the positive electrode is by CeF3It is composited with carbon, the chemical formula of the positive electrode is CeF3/ C, the carbon is porous
Carbon, the CeF3In the hole of the porous carbon.
In the second aspect of the present invention, the invention provides a kind of preparation method of the positive electrode of lithium ion battery, use
In preparing positive electrode described according to a first aspect of the present invention, it includes step：(1) cerium source is added in organic solvent, risen
Temperature promotes the dissolving of cerium source, obtains certain density cerium source solution；(2) a certain amount of porous carbon source is added into cerium source solution, so
Ultrasonic disperse makes porous carbon source be dispersed in the solution of cerium source afterwards, obtains the first mixture；(3) after the first mixture is heated up
Vacuumize；(4) under continuous agitation, Fluorine source is added into the first mixture and obtains the second mixture；(5) second is mixed
Compound is stood, and then obtains CeF through separation, absolute ethyl alcohol washing3/C。
In the third aspect of the present invention, the invention provides a kind of lithium ion battery, it includes：Positive plate, includes positive pole
Material；Negative plate；Barrier film, between positive plate and negative plate；And electrolyte.Wherein, according to the positive electrode
The positive electrode of the lithium ion battery of first aspect present invention.
Beneficial effects of the present invention are as follows：
(1) in CeF3In, Ce-F keys are strong covalent bond, and dissociation energy may be up to 582KJ/mol, therefore CeF3With high heat
Stability, and then the security performance of lithium ion battery can be improved.
(2) in CeF3In, F molecular weight is relatively low, and Ce3+Can occur polyelectron reaction；In addition, CeF3Also there is height
Voltage and high density, its energy density are higher；Although CeF3Electronic conductivity it is relatively low, but by CeF3Nano particle in situ life
It is longer than in the hole of porous carbon, the duct of porous carbon can limit CeF3The growth of nano particle, while can also limit CeF3Nanometer
Expansion/contraction of the grain in charge and discharge process, so as to improve CeF3The electronic conductivity of nano particle, finally improves CeF3/ C is just
The chemical property of pole material, makes it have high initial charge capacity, first discharge capacity, first coulombic efficiency and good
Cycle performance, and then can also improve the energy density of lithium ion battery.
(3) due to CeF3Cost it is relatively low, only LiCoO21/20~1/10, therefore the cost of lithium ion battery is relatively low.
(4) due to CeF3It is insoluble in organic solvent, therefore without the various technological parameters of accuracy controlling reaction system, enter
And the CeF of the present invention3The preparation method of/C positive electrode material is simple and feasible, easy to operate, the CeF of gained3The purity of/C positive electrode material
High, electrochemical performance, is adapted to industrialization production.
Brief description of the drawings
Fig. 1 is the CeF that embodiment 1 is obtained3/ C TEM figures.
Embodiment
The following detailed description of the lithium ion battery and its positive electrode and preparation method and embodiment, ratio according to the present invention
Compared with example and test result.
Illustrate the positive electrode of lithium ion battery according to a first aspect of the present invention first.
The positive electrode of lithium ion battery according to a first aspect of the present invention is by CeF3It is composited with carbon, the positive pole material
The chemical formula of material is CeF3/ C, the carbon is porous carbon, the CeF3In the hole of the porous carbon.
In CeF3In, Ce-F keys are strong covalent bond, and dissociation energy may be up to 582KJ/mol, far above LiCoO2Middle Co-O keys
Dissociation energy 384KJ/mol, therefore CeF3With high heat endurance, i.e., with high security.Meanwhile, F molecular weight is relatively low, and
And Ce3+Can occur polyelectron reaction, therefore CeF3Can have high initial charge capacity and first discharge capacity.CeF3Also have
There are high voltage and high density, the voltage of its theoretical de-/embedding lithium is 3.2V, and density is 6.2gcm-3, the CeF of calculating3Energy density
Up to 8.1KWh/L, far above LiCoO2、LiFePO4And LiMn2O4.Although CeF3Electronic conductivity it is relatively low, but by CeF3
Nano particle in situ be grown in the hole of porous carbon and (refer to Fig. 1), CeF can be improved3The electronic conductivity of nano particle, simultaneously
The duct of porous carbon can limit CeF3The growth of nano particle, and limit CeF3Expansion of the nano particle in charge and discharge process/
Shrink, finally improve CeF3The chemical property of/C positive electrode material.In addition, CeF3Cost it is relatively low, only LiCoO21/20~
1/10。
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, the CeF3Particle diameter can be
0.1nm~50nm, preferably can be 0.1nm~20nm.
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, the aperture of the porous carbon can be
0.1nm~50nm, preferably can be 0.1nm~20nm.
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, the specific surface area of the porous carbon
Can >=20m2/ g, preferably can be >=100m2/g。
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, the porous carbon may be selected from carbon and receive
One or more in mitron, Super-P, acetylene black, Ketjen black carbon blacks, XC-72 carbon blacks, ordered mesopore carbon CMK-3.
The preparation method of the positive electrode of next lithium ion battery of explanation according to a second aspect of the present invention.
The preparation method of the positive electrode of lithium ion battery according to a second aspect of the present invention, for preparing according to the present invention
The positive electrode of lithium ion battery described in first aspect, including step：(1) cerium source is added in organic solvent, heating promotes
Cerium source is dissolved, and obtains certain density cerium source solution；(2) a certain amount of porous carbon source is added into cerium source solution, it is then ultrasonic
It is scattered porous carbon source is dispersed in the solution of cerium source, obtain the first mixture；(3) take out true after the first mixture is heated up
It is empty；(4) under continuous agitation, Fluorine source is added into the first mixture and obtains the second mixture；(5) by the second mixture
Stand, then obtain CeF through separation, absolute ethyl alcohol washing3/C。
The CeF of the present invention3/ C positive electrode material utilizes the duct of porous carbon, can limit CeF3The growth of nano particle, simultaneously
Also CeF can be limited3Expansion/contraction of the nano particle in charge and discharge process, and improve CeF3Electronic conductivity, it is final to improve
CeF3The chemical property of/C positive electrode material.Due to CeF3It is insoluble in organic solvent, therefore without accuracy controlling reaction system
Various technological parameters simple and quick can obtain purity height, the CeF of electrochemical performance3/ C positive electrode material.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (1)
In, the cerium source may be selected from Ce3+Chloride, bromide, nitrate, sulfate, acetate, one kind in oxalates or several
Kind.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (1)
In, the organic solvent may be selected from polyethylene glycol, glycerine, 2- phenoxetols, diethylene glycol (DEG), one kind in dimethyl sulfoxide or several
Kind.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, the poly- second two
The weight average molecular weight of alcohol can be 200~600.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (1)
In, the temperature of the heating can be 80 DEG C~120 DEG C.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (1)
In, the concentration of cerium source solution can be 0.01M~0.5M.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (2)
In, the porous carbon source may be selected from CNT, Super-P, acetylene black, Ketjen black carbon blacks, XC-72 carbon blacks, in order
One or more in mesoporous carbon CMK-3.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (2)
In, the porous carbon source and the mol ratio in the cerium source can be (30~1.5):1.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (2)
In, the time of the ultrasonic disperse can be 3min~60min.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (3)
In, the temperature of the heating can be 150 DEG C~210 DEG C.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (3)
In, the time vacuumized can be 0.5h~5h.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (4)
In, the Fluorine source may be selected from alkali metal fluoride, alkali earth metal fluoride, HF, NH4One or more in F.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (4)
In, the speed of the stirring can be 40r/min~1000r/min.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (4)
In, the Fluorine source and the mol ratio in the cerium source can be (0.9~3.1):1.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (5)
In, the time of the standing can be 12h~36h；
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, in step (5)
In, the separation can be centrifugation.
Illustrate lithium ion battery according to a third aspect of the present invention again.
Lithium ion battery according to a third aspect of the present invention, including：Positive plate, includes positive electrode；Negative plate；Isolation
Film, between positive plate and negative plate；And electrolyte.The positive electrode is the lithium ion according to first aspect present invention
The positive electrode of battery.
Next explanation is according to the lithium ion battery of the present invention and its embodiment of positive electrode and preparation method and right
Ratio.
Embodiment 1
1. prepare the positive electrode of lithium ion battery
(1) by cerium source Ce (NO3)3Weight average molecular weight is added in 600 solvent polyethylene glycol, to be warming up to 80 DEG C of promotion ceriums
Source is dissolved, and obtains the cerium source solution that molar concentration is 0.01M；
(2) added and cerium source Ce (NO into cerium source solution3)3Mol ratio be 1.5:1 porous carbon source CNT, so
Ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source afterwards, obtains the ratio of the first mixture, wherein CNT
Surface area is 1100m2/ g, aperture 10nm≤r≤50nm；
(3) 0.5h is vacuumized after the first mixture being warming up into 150 DEG C；
(4) under conditions of 100r/min is persistently stirred, added and cerium source Ce (NO into the first mixture3)3Mol ratio
For 0.9:1 Fluorine source NaF, obtains the second mixture；
(5) the second mixture is stood into 12h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
2. prepare the positive plate of lithium ion battery
CeF prepared by step 13/ C positive electrode material, binding agent PVDF, conductive agent acetylene black in mass ratio 75:15:10 is molten
In solvent NMP, stir and anode sizing agent is made, then anode sizing agent is uniformly coated on to the plus plate current-collecting body Al of 13 μ m-thicks
On positive and negative two surfaces of paper tinsel and dry, obtain the positive pole diaphragm of 130 μ m-thicks, afterwards by cold pressing, section, soldering polar ear, obtain
To the positive plate of lithium ion battery.
3. prepare the negative plate of lithium ion battery
By negative material Delanium, binding agent SBR/CMC, conductive agent carbon black in mass ratio 92.5:6:1.5 are dissolved in solvent
In deionized water, stir and cathode size is made, then cathode size is uniformly coated on to the negative current collector copper foil of 8 μ m-thicks
Positive and negative two surfaces on and dry, obtain the cathode membrane of 120 μ m-thicks, afterwards by cold pressing, section, soldering polar ear, obtain
The negative plate of lithium ion battery.
4. prepare the electrolyte of lithium ion battery
By LiPF6With non-aqueous organic solvent (EC:DMC=1:1, mass ratio) with 8:The solution that 92 mass ratio is formulated
It is used as the electrolyte of lithium ion battery.
5. prepare lithium ion battery
By positive plate, barrier film (thickness be 25 μm of Celgard2325 polypropylene screens) and negative plate is after the coiling, obtains
To naked battery core, then lithium-ion electric is obtained by terminal welding, packaging foil encapsulation, injection electrolyte, chemical conversion, pumping shaping
Pond.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1),
(1) by cerium source Ce (NO3)3Weight average molecular weight is added in 600 solvent polyethylene glycol, to be warming up to 80 DEG C of promotion ceriums
Source is dissolved, and obtains the cerium source solution that molar concentration is 0.01M；
(2) added and cerium source Ce (NO into cerium source solution3)3Mol ratio be 1.5:1 porous carbon source CNT, so
Ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source afterwards, obtains the ratio of the first mixture, wherein CNT
Surface area is 1100m2/ g, aperture 5nm≤r≤10nm；
(3) 0.5h is vacuumized after the first mixture being warming up into 150 DEG C；
(4) under conditions of 100r/min is persistently stirred, added and cerium source Ce (NO into the first mixture3)3Mol ratio
For 0.9:1 Fluorine source NaF, obtains the second mixture；
(5) the second mixture is stood into 12h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1),
(1) by cerium source Ce2(SO4)3Add molecular weight and promote cerium source in 200 solvent polyethylene glycol, to be warming up to 100 DEG C
Dissolving, obtains the cerium source solution that molar concentration is 0.5M；
(2) added and cerium source Ce into cerium source solution2(SO4)3Mol ratio be 30:1 porous carbon source Ketjen black
Carbon black, then ultrasonic disperse 60min porous carbon source is dispersed in the solution of cerium source, obtain the first mixture, wherein
The specific surface area of Ketjen black carbon blacks is 750m2/ g, aperture 0.1nm≤r≤5nm；
(3) 5h is vacuumized after the first mixture being warming up into 210 DEG C；
(4) under conditions of 100r/min is persistently stirred, added and cerium source Ce into the first mixture2(SO4)3Mole
Than for 3.1:1 Fluorine source NH4F, obtains the second mixture；
(5) the second mixture is stood into 36h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1),
(1) by cerium source CeCl3Add in solvent glycerin, be warming up to 120 DEG C and promote the dissolving of cerium source, obtaining molar concentration is
0.5M cerium source solution；
(2) added and cerium source CeCl into cerium source solution3Mol ratio be 3:1 porous carbon source ordered mesopore carbon CMK-3,
Then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, wherein ordered mesopore carbon
CMK-3 specific surface area is 1500m2/ g, aperture 2nm≤r≤6nm；
(3) 2h is vacuumized after the first mixture being warming up into 180 DEG C；
(4) under conditions of 40r/min is persistently stirred, added and cerium source CeCl into the first mixture3Mol ratio be
0.9:1 Fluorine source KF, obtains the second mixture；
(5) the second mixture is stood into 24h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1),
(1) by cerium source Ce (CH3COO)3Add in solvent 2- phenoxetols, be warming up to 120 DEG C and promote the dissolving of cerium source, obtain
To the cerium source solution that molar concentration is 0.01M；
(2) added and cerium source Ce (CH into cerium source solution3COO)3Mol ratio be 15:1 porous carbon source acetylene black, so
Ultrasonic disperse 3min makes porous carbon source be dispersed in the solution of cerium source afterwards, obtains the ratio table of the first mixture, wherein acetylene black
Area is 20m2/ g, aperture 0.1nm≤r≤2nm；
(3) 3h is vacuumized after the first mixture being warming up into 180 DEG C；
(4) under conditions of 60r/min is persistently stirred, added and cerium source Ce (CH into the first mixture3COO)3Mole
Than for 1.1:1 Fluorine source HF, obtains the second mixture；
(5) the second mixture is stood into 24h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1),
(1) cerium source cerium oxalate is added in solvent diethylene glycol (DEG), is warming up to 120 DEG C and promotes the dissolving of cerium source, obtain molar concentration
For 0.5M cerium source solution；
(2) mol ratio added into cerium source solution with cerium source cerium oxalate is 20:1 porous carbon source Super-P, Ran Houchao
Sound, which disperses 60min, makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, wherein Super-P ratio surface
Product is 1500m2/ g, 0.1≤r of aperture≤8nm；
(3) 5h is vacuumized after the first mixture being warming up into 180 DEG C；
(4) under conditions of 80r/min is persistently stirred, the mol ratio added into the first mixture with cerium source cerium oxalate is
1.1:1 Fluorine source NaF, obtains the second mixture；
(5) the second mixture is stood into 24h, be then centrifuged, absolute ethyl alcohol washing obtains CeF3/ C positive electrode material.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1), by commercialized LiCoO2It is used as positive electrode.
Comparative example 2
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1), by commercialized LiFePO4It is used as positive electrode.
Comparative example 3
Method according to embodiment 1 prepares lithium ion battery, simply the step of the positive electrode of lithium ion battery is prepared
In (i.e. step 1), by commercialized LiMn2O4It is used as positive electrode.
Finally illustrate the lithium ion battery according to the present invention and its test process and survey of positive electrode and preparation method
Test result.
(1) test of the performance of positive electrode：
The initial charge capacity of A positive electrodes, first discharge capacity, initial coulomb efficiency and cycle performance test
By each positive electrode in embodiment 1-6 and comparative example 1-3 and conductive agent acetylene black, binding agent PVDF in mass ratio
75:15:10 are mixed to get slurry, and slurry is coated uniformly on aluminium foil and obtains working electrode, using lithium piece as to electrode, with
Celgard2325 polypropylene screens are barrier film, with 1M LiPF6/EC+DMC(EC:DMC=1:1) it is electrolyte, full of argon gas
Glove box in be assembled into button cell.
Above-mentioned button cell is subjected to charge-discharge test (embodiment 1-6 charging/discharging voltage model on Land discharge and recharge instrument
Enclose for 1.5V~4.5V, the charging/discharging voltage scope of comparative example 1 is 3.0V~4.2V, and the charging/discharging voltage scope of comparative example 2 is
2.0V~4.2V, the charging/discharging voltage scope of comparative example 3 is 3.0V~4.3V), charge-discharge magnification is 0.2C, and thus test is obtained
The initial charge capacity of each positive electrode in embodiment 1-6 and comparative example 1-3, first discharge capacity, initial coulomb efficiency and
Capability retention after 50 circulations.
B particle diameters are tested
Each positive electrode in embodiment 1-6 and comparative example 1-3 is scattered in ethanol, suspension is obtained, a drop is then taken
Suspension is added dropwise on copper mesh, after after ethanol volatilization, using transmission electron microscope observation and measures comparative example 1-3 positive pole material
CeF in the particle diameter and embodiment 1-6 of material3Particle diameter.
(2) performance test of lithium ion battery
A energy densities are tested
At 25 DEG C, with 0.5C constant-current charges to certain voltage, (embodiment 1-6 charges to 4.5V, and comparative example 1-2 is charged to
4.2V, comparative example 3 charges to 4.3V), afterwards under this voltage constant pressure to current reduction be 0.05C, stand 5min, finally with
To certain voltage, (embodiment 1-6 is discharged to 1.5V to 0.5C constant-current discharges, and comparative example 1 and comparative example 3 are discharged to 3.0V, comparative example 2
It is discharged to 2.0V).
B over-chargings are tested
At 25 DEG C, with 0.5C constant-current charges to 10V, the constant-voltage charge 2h under this voltage, observes lithium ion battery afterwards
State.
C resistances to elevated temperatures are tested
At 25 DEG C, with 0.5C constant-current charges to certain voltage, (embodiment 1-6 charges to 4.5V, and comparative example 1-2 is charged to
4.2V, comparative example 3 charges to 4.3V), the constant-voltage charge 1h under this voltage, is then placed in baking oven by the lithium ion battery afterwards
In, 150 DEG C are warming up to from 25 DEG C, heating rate is 5 DEG C/min, observes the state of lithium ion battery.
Table 1 provides embodiment 1-6 and comparative example 1-3 parameter and the performance test results.
Next the performance test results to embodiment 1-6 and comparative example 1-3 are analyzed.
As can be seen that the CeF of the present invention from embodiment 1-6 and comparative example 1-3 contrast3/ C positive electrode material has high
Initial charge capacity, first discharge capacity, first coulombic efficiency and capability retention.During this is due to comparative example 1-3
LiCoO2、LiFePO4、LiMn2O4The redox reaction of 1 electronics can only at most occur for positive electrode, and contain in molecule
The metal and polyanion group of HMW.And the CeF of the present invention3CeF in/C positive electrode material3F containing low molecule amount,
And Ce3+Can occur polyelectron reaction.Although CeF3Electronic conductivity it is relatively low, but by CeF3Nano particle in situ growth
In in the hole of porous carbon, CeF can be improved3Electronic conductivity, while the duct of porous carbon can limit CeF3The life of nano particle
It is long, and limit CeF3Expansion/contraction of the nano particle in charge and discharge process.Therefore, the CeF of gained3/ C positive electrode material has height
Initial charge capacity and discharge capacity first；The CeF of gained3/ C positive electrode material has good electrochemical reaction invertibity,
Therefore with high initial coulomb efficiency；The CeF of gained3/ C positive electrode material has high voltage and high density, its de-/embedding lithium electricity
Nearly its theoretical value 3.2V of crimping, density is 6.2gcm-3, far above LiCoO2(5.05gcm-3)、LiFePO4(3.52gcm-3) and
LiMn2O4(4.29gcm-3), therefore CeF3The energy density of/C positive electrode material may be up to 8.1KWh/L, far above LiCoO2、
LiFePO4And LiMn2O4。
Meanwhile, it can also be seen that with the CeF of the present invention from embodiment 1-6 and comparative example 1-3 contrast3/ C positive pole materials
Lithium ion battery prepared by material has the security performance that high energy density is become reconciled.The lithium ion battery of the present invention is being overcharged and high
Without combustion phenomena after temperature test, and LiCoO is applied in comparative example 12Lithium ion battery prepared by positive electrode is being overcharged and high
Burnt after temperature test.Because in CeF3In, Ce-F keys are strong covalent bond, and dissociation energy is up to 582KJ/mol, is far above
LiCoO2The dissociation energy 384KJ/mol of middle Co-O keys, therefore CeF3With high heat endurance.Meanwhile, CeF of the invention3/ C is just
Pole material is free of O, is not in that the accumulation of heat that oxygen and then aggravation inside lithium ion cell are discharged because of heating is even resulted in
There is the problem of thermal runaway or blast.
As can be seen that smaller, the resulting CeF in the aperture of porous carbon from the contrast of embodiment 1 and embodiment 23Grain
Footpath is smaller, so that the initial charge capacity of positive electrode, first discharge capacity, first coulombic efficiency and capability retention are got over
It is high.This is due to CeF3Nano particle in situ is grown in the hole of porous carbon, and the duct of porous carbon can limit CeF3Nano particle
Growth, and limit CeF3Expansion/contraction of the nano particle in charge and discharge process, so as to improve CeF3Electronic conductivity, finally
Improve the chemical property of positive electrode, therefore the aperture of porous carbon is smaller, the chemical property of positive electrode is better.
Due to CeF3It is insoluble in organic solvent, therefore without the various technological parameters of accuracy controlling reaction system.This hair
The preparation method of bright positive electrode is simple and feasible, easy to operate, the CeF of gained3The purity of/C positive electrode material is high, chemical property
It is excellent, it is adapted to industrialization production.In addition, the CeF of the present invention3/ C positive electrode material is without using noble metals such as Co, and CeF3Cost only
For LiCoO21/20~1/10, therefore cost is relatively low.
Claims (12)
1. a kind of positive electrode of lithium ion battery, it is characterised in that
The positive electrode is by CeF3It is composited with carbon, the chemical formula of the positive electrode is CeF3/ C, the carbon is porous
Carbon, the CeF3In the hole of the porous carbon.
2. the positive electrode of lithium ion battery according to claim 1, it is characterised in that the CeF3Particle diameter be 0.1nm
~50nm.
3. the positive electrode of lithium ion battery according to claim 2, it is characterised in that the CeF3Particle diameter be 0.1nm
~20nm.
4. the positive electrode of lithium ion battery according to claim 1, it is characterised in that the aperture of the porous carbon is
0.1nm~50nm.
5. the positive electrode of lithium ion battery according to claim 4, it is characterised in that the aperture of the porous carbon is
0.1nm~20nm.
6. the positive electrode of lithium ion battery according to claim 1, it is characterised in that the specific surface area of the porous carbon
≥20m2/g。
7. the positive electrode of lithium ion battery according to claim 6, it is characterised in that the specific surface area of the porous carbon
≥100m2/g。
8. the positive electrode of lithium ion battery according to claim 1, it is characterised in that the porous carbon is selected from carbon nanometer
One or more in pipe, Super-P, acetylene black, Ketjen black carbon blacks, XC-72 carbon blacks, ordered mesopore carbon CMK-3.
9. a kind of preparation method of the positive electrode of lithium ion battery, for preparing according to any one of claim 1-8
Lithium ion battery positive electrode, including step：
(1) cerium source is added in organic solvent, heating promotes the dissolving of cerium source, obtains certain density cerium source solution；
(2) a certain amount of porous carbon source is added into cerium source solution, then ultrasonic disperse makes porous carbon source be dispersed in cerium source
In solution, the first mixture is obtained；
(3) vacuumized after the first mixture is heated up；
(4) under continuous agitation, Fluorine source is added into the first mixture and obtains the second mixture；
(5) the second mixture is stood, then obtains CeF through separation, absolute ethyl alcohol washing3/C。
10. the preparation method of the positive electrode of lithium ion battery according to claim 9, it is characterised in that
The cerium source is selected from Ce3+Chloride, bromide, nitrate, sulfate, acetate, the one or more in oxalates；
The porous carbon source is selected from CNT, Super-P, acetylene black, Ketjen black carbon blacks, in order XC-72 carbon blacks, Jie
One or more in the carbon CMK-3 of hole；
The Fluorine source is selected from alkali metal fluoride, alkali earth metal fluoride, HF, NH4One or more in F.
11. the preparation method of the positive electrode of lithium ion battery according to claim 9, it is characterised in that
The porous carbon source and the mol ratio in the cerium source are (30~1.5):1；
The Fluorine source and the mol ratio in the cerium source are (0.9~3.1):1.
12. a kind of lithium ion battery, including：
Positive plate, includes positive electrode；
Negative plate；
Barrier film, between positive plate and negative plate；And
Electrolyte；
Characterized in that,
The positive electrode is the positive electrode of the lithium ion battery any one of claim 1-8.
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