CN105098137A - Lithium ion battery, and anode material and preparation method thereof - Google Patents
Lithium ion battery, and anode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lithium ion battery, and an anode material and a preparation method thereof. The anode material of the lithium ion battery is compounded by CeF3 and carbon and has a chemical formula of CeF3/C, the carbon is porous carbon, and the CeF3 is positioned in the pores of the porous carbon. The lithium ion battery comprises an anode plate, a cathode plate, an isolating membrane and electrolyte, wherein the anode plate comprises anode materials, the isolating membrane is positioned between the anode plate and the cathode plate, and the anode material is the anode material of the lithium ion battery. The anode material of the lithium ion battery has the advantages of high initial charge capacity, high initial discharge capacity, high initial coulombic efficiency and good cycle performance. The lithium ion battery has the advantages of high energy density, good safety performance and low cost.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium ion battery and positive electrode thereof and preparation method.
Background technology
In business-like battery, lithium ion battery has the advantages such as energy density is high, operating voltage is high, have extended cycle life, self-discharge rate is low, memory-less effect, volume are little and lightweight, be widely used in various portable type electronic product, and become one of first-selection of electrokinetic cell and energy-storage battery.But lithium ion battery still Shortcomings in fail safe, production cost and energy density etc., constrains the further application of lithium ion battery in advanced electronic equipment, electric automobile and energy storage field.
Usually, lithium ion battery is overcharging, under the condition such as short circuit or high temperature, heat can cause the internal temperature of lithium ion battery to raise in inside lithium ion cell accumulation, when temperature is increased to a certain degree by cause the decomposition of SEI film, the decomposition caused heat release of electrolyte and positive electrode analyse oxygen heat release etc., now heat accumulates at inside lithium ion cell further until there is thermal runaway, finally causes lithium ion battery to burn or blast.Wherein, the oxygen heat release of analysing of positive electrode is the key factor causing inside lithium ion cell thermal runaway.In addition, the energy density of lithium ion battery still can not meet the demand of portable electric pool equipment and Prospect of EVS Powered with Batteries completely.Wherein, the specific capacity that positive electrode is lower is one of key factor of promoting further of limiting lithium ion cell energy density.Meanwhile, current commercial applications positive electrode LiCoO the most widely
2due to expensive containing Elements C o, be unfavorable for that lithium ion battery is to cost degradation future development, limits the range of application of lithium ion.Therefore, the positive electrode of research and development Stability Analysis of Structures, low cost, high-energy-density is one of effective way of the performance improving lithium ion battery.
Summary of the invention
In view of Problems existing in background technology, the object of the invention is to provide a kind of lithium ion battery and positive electrode thereof and preparation method, the positive electrode of described lithium ion battery has high initial charge capacity, first discharge capacity, first coulombic efficiency and good cycle performance, and described lithium ion battery has high energy density, good security performance and low cost.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of positive electrode of lithium ion battery, described positive electrode is by CeF
3be composited with carbon, the chemical formula of described positive electrode is CeF
3/ C, described carbon is porous carbon, described CeF
3be positioned at the hole of described porous carbon.
In a second aspect of the present invention, the invention provides a kind of preparation method of positive electrode of lithium ion battery, for the preparation of positive electrode described according to a first aspect of the present invention, it comprises step: cerium source adds in organic solvent by (1), heat up and promote that cerium source is dissolved, obtain certain density cerium source solution; (2) in the solution of cerium source, add a certain amount of porous carbon source, then ultrasonic disperse makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture; (3) vacuumize after the first mixture being heated up; (4) under the condition of Keep agitation, in the first mixture, add fluorine source obtain the second mixture; (5) the second mixture is left standstill, then obtain CeF through separation, absolute ethanol washing
3/ C.
In a third aspect of the present invention, the invention provides a kind of lithium ion battery, it comprises: positive plate, comprises positive electrode; Negative plate; Barrier film, between positive plate and negative plate; And electrolyte.Wherein, described positive electrode is the positive electrode of lithium ion battery according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
(1) at CeF
3in, Ce-F key is strong covalent bond, and dissociation energy can up to 582KJ/mol, therefore CeF
3there is high thermal stability, and then the security performance of lithium ion battery can be improved.
(2) at CeF
3in, the molecular weight of F is lower, and Ce
3+polyelectron reaction can be there is; In addition, CeF
3also have high voltage and high density, its energy density is higher; Although CeF
3electronic conductivity lower, but by CeF
3nano particle in situ be grown in the hole of porous carbon, the duct of porous carbon can limit CeF
3the growth of nano particle, also can limit CeF simultaneously
3the expansion/contraction of nano particle in charge and discharge process, thus improve CeF
3the electronic conductivity of nano particle, finally improves CeF
3the chemical property of/C positive electrode material, makes it have high initial charge capacity, first discharge capacity, first coulombic efficiency and good cycle performance, and then also can improve the energy density of lithium ion battery.
(3) due to CeF
3cost lower, be only LiCoO
21/20 ~ 1/10, therefore the cost of lithium ion battery is lower.
(4) due to CeF
3insoluble in organic solvent, therefore without the need to the various technological parameters of accuracy controlling reaction system, and then CeF of the present invention
3the preparation method of/C positive electrode material is simple and feasible, easy to operate, the CeF of gained
3the purity of/C positive electrode material is high, electrochemical performance, is applicable to industrialization and produces.
Accompanying drawing explanation
Fig. 1 is the CeF that embodiment 1 obtains
3the TEM figure of/C.
Embodiment
The following detailed description of lithium ion battery according to the present invention and positive electrode thereof and preparation method and embodiment, comparative example and test result.
First the positive electrode of lithium ion battery is according to a first aspect of the present invention described.
The positive electrode of lithium ion battery is according to a first aspect of the present invention by CeF
3be composited with carbon, the chemical formula of described positive electrode is CeF
3/ C, described carbon is porous carbon, described CeF
3be positioned at the hole of described porous carbon.
At CeF
3in, Ce-F key is strong covalent bond, and dissociation energy can up to 582KJ/mol, far above LiCoO
2the dissociation energy 384KJ/mol of middle Co-O key, therefore CeF
3there is high thermal stability, namely there is high security.Meanwhile, the molecular weight of F is lower, and Ce
3+polyelectron reaction can be there is, therefore CeF
3high initial charge capacity and discharge capacity first can be had.CeF
3also have 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 calculating
3energy density can up to 8.1KWh/L, far above LiCoO
2, LiFePO
4and LiMn
2o
4.Although CeF
3electronic conductivity lower, but by CeF
3nano particle in situ be grown on (with reference to figure 1) in the hole of porous carbon, can CeF be improved
3the electronic conductivity of nano particle, the duct of porous carbon can limit CeF simultaneously
3the growth of nano particle, and limit CeF
3the expansion/contraction of nano particle in charge and discharge process, finally improves CeF
3the chemical property of/C positive electrode material.In addition, CeF
3cost lower, be only LiCoO
21/20 ~ 1/10.
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, described CeF
3particle 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 described 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 area of described porous carbon can>=20m
2/ g, preferably can be>=100m
2/ g.
In the positive electrode of lithium ion battery described according to a first aspect of the present invention, described porous carbon can be selected from one or more in carbon nano-tube, Super-P, acetylene black, Ketjenblack carbon black, XC-72 carbon black, ordered mesopore carbon CMK-3.
Secondly the preparation method of the positive electrode of lithium ion battery is according to a second aspect of the present invention described.
The preparation method of the positive electrode of lithium ion battery according to a second aspect of the present invention, for the preparation of the positive electrode of lithium ion battery described according to a first aspect of the present invention, comprise step: cerium source adds in organic solvent by (1), heat up and promote that cerium source is dissolved, obtain certain density cerium source solution; (2) in the solution of cerium source, add a certain amount of porous carbon source, then ultrasonic disperse makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture; (3) vacuumize after the first mixture being heated up; (4) under the condition of Keep agitation, in the first mixture, add fluorine source obtain the second mixture; (5) the second mixture is left standstill, then obtain CeF through separation, absolute ethanol washing
3/ C.
CeF of the present invention
3/ C positive electrode material utilizes the duct of porous carbon, can limit CeF
3the growth of nano particle, also can limit CeF simultaneously
3the expansion/contraction of nano particle in charge and discharge process, and improve CeF
3electronic conductivity, finally improve CeF
3the chemical property of/C positive electrode material.Due to CeF
3insoluble in organic solvent, the various technological parameters therefore without the need to accuracy controlling reaction system simple and quickly can obtain that purity is high, the CeF of electrochemical performance
3/ 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), described cerium source can be selected from Ce
3+chloride, bromide, nitrate, sulfate, acetate, one or more in oxalates.
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), described organic solvent one or more in polyethylene glycol, glycerine, 2-phenoxetol, diethylene glycol (DEG), methyl-sulfoxide optional.
In the preparation method of the positive electrode of lithium ion battery described according to a second aspect of the present invention, the weight average molecular weight of described polyethylene glycol 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), the temperature of described intensification 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), the concentration of described 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), described porous carbon source one or more in carbon nano-tube, Super-P, acetylene black, Ketjenblack carbon black, XC-72 carbon black, ordered mesopore carbon CMK-3 optional.
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), the mol ratio in described porous carbon source and described 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), the time of described 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), the temperature of described intensification 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), described in time of vacuumizing 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), described fluorine source can be selected from alkali metal fluoride, alkali earth metal fluoride, HF, NH
4one 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), the speed of described 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), the mol ratio in described fluorine source and described 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), the described standing time 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), described separation can be centrifugation.
Lithium ion battery is according to a third aspect of the present invention described again.
Lithium ion battery according to a third aspect of the present invention, comprising: positive plate, comprises positive electrode; Negative plate; Barrier film, between positive plate and negative plate; And electrolyte.Described positive electrode is the positive electrode of lithium ion battery according to a first aspect of the present invention.
Following explanation is according to the embodiment of lithium ion battery of the present invention and positive electrode and preparation method and comparative example.
Embodiment 1
1. prepare the positive electrode of lithium ion battery
(1) by cerium source Ce (NO
3)
3adding weight average molecular weight is in the solvent polyethylene glycol of 600, is warming up to 80 DEG C and promotes that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.01M;
(2) add and cerium source Ce (NO in the solution of cerium source
3)
3mol ratio be the porous carbon source carbon nano-tube of 1.5:1, then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, and wherein the specific area of carbon nano-tube is 1100m
2/ g, aperture 10nm≤r≤50nm;
(3) 0.5h is vacuumized after the first mixture being warming up to 150 DEG C;
(4) under the condition of 100r/min Keep agitation, add in the first mixture and cerium source Ce (NO
3)
3mol ratio be the fluorine source NaF of 0.9:1, obtain the second mixture;
(5) the second mixture is left standstill 12h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
2. prepare the positive plate of lithium ion battery
CeF prepared by step 1
3/ C positive electrode material, binding agent PVDF, conductive agent acetylene black in mass ratio 75:15:10 are dissolved in solvent NMP, stir and make anode sizing agent, then positive and negative two surfaces anode sizing agent being uniformly coated on 13 μm of thick plus plate current-collecting body Al paper tinsels are dried, obtain 130 μm of thick positive pole diaphragms, afterwards through colding pressing, cut into slices, soldering polar ear, obtain 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 be dissolved in solvent deionized water, stir and make cathode size, then positive and negative two surfaces cathode size being uniformly coated on 8 μm of thick negative current collector Copper Foils are dried, obtain 120 μm of thick cathode membrane, afterwards through colding pressing, cut into slices, soldering polar ear, obtain the negative plate of lithium ion battery.
4. prepare the electrolyte of lithium ion battery
By LiPF
6with non-aqueous organic solvent (EC:DMC=1:1, mass ratio) using the formulated solution of the mass ratio of 8:92 as the electrolyte of lithium ion battery.
5. prepare lithium ion battery
By positive plate, barrier film (thickness is the Celgard2325 polypropylene screen of 25 μm) and negative plate after the coiling, obtain naked battery core, then through terminal soldering, packaging foil encapsulation, inject electrolyte, change into, bleeding shapingly obtains lithium ion battery.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery,
(1) by cerium source Ce (NO
3)
3adding weight average molecular weight is in the solvent polyethylene glycol of 600, is warming up to 80 DEG C and promotes that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.01M;
(2) add and cerium source Ce (NO in the solution of cerium source
3)
3mol ratio be the porous carbon source carbon nano-tube of 1.5:1, then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, and wherein the specific area of carbon nano-tube is 1100m
2/ g, aperture 5nm≤r≤10nm;
(3) 0.5h is vacuumized after the first mixture being warming up to 150 DEG C;
(4) under the condition of 100r/min Keep agitation, add in the first mixture and cerium source Ce (NO
3)
3mol ratio be the fluorine source NaF of 0.9:1, obtain the second mixture;
(5) the second mixture is left standstill 12h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery,
(1) by cerium source Ce
2(SO
4)
3adding molecular weight is in the solvent polyethylene glycol of 200, is warming up to 100 DEG C and promotes that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.5M;
(2) add and cerium source Ce in the solution of cerium source
2(SO
4)
3mol ratio be the porous carbon source Ketjenblack carbon black of 30:1, then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, and wherein the specific area of Ketjenblack carbon black is 750m
2/ g, aperture 0.1nm≤r≤5nm;
(3) 5h is vacuumized after the first mixture being warming up to 210 DEG C;
(4) under the condition of 100r/min Keep agitation, add in the first mixture and cerium source Ce
2(SO
4)
3mol ratio be the fluorine source NH of 3.1:1
4f, obtains the second mixture;
(5) the second mixture is left standstill 36h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery,
(1) by cerium source CeCl
3add in solvent glycerin, be warming up to 120 DEG C and promote that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.5M;
(2) add and cerium source CeCl in the solution of cerium source
3mol ratio be the porous carbon source ordered mesopore carbon CMK-3 of 3:1, then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, and wherein the specific area of ordered mesopore carbon CMK-3 is 1500m
2/ g, aperture 2nm≤r≤6nm;
(3) 2h is vacuumized after the first mixture being warming up to 180 DEG C;
(4) under the condition of 40r/min Keep agitation, add in the first mixture and cerium source CeCl
3mol ratio be the fluorine source KF of 0.9:1, obtain the second mixture;
(5) the second mixture is left standstill 24h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery,
(1) by cerium source Ce (CH
3cOO)
3add in solvent 2-phenoxetol, be warming up to 120 DEG C and promote that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.01M;
(2) add and cerium source Ce (CH in the solution of cerium source
3cOO)
3mol ratio be the porous carbon source acetylene black of 15:1, then ultrasonic disperse 3min makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture, and wherein the specific area of acetylene black is 20m
2/ g, aperture 0.1nm≤r≤2nm;
(3) 3h is vacuumized after the first mixture being warming up to 180 DEG C;
(4) under the condition of 60r/min Keep agitation, add in the first mixture and cerium source Ce (CH
3cOO)
3mol ratio be the fluorine source HF of 1.1:1, obtain the second mixture;
(5) the second mixture is left standstill 24h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery,
(1) cerium source cerium oxalate is added in solvent diethylene glycol (DEG), be warming up to 120 DEG C and promote that cerium source is dissolved, obtain the cerium source solution that molar concentration is 0.5M;
(2) adding in the solution of cerium source with the mol ratio of cerium source cerium oxalate is the porous carbon source Super-P of 20:1, then ultrasonic disperse 60min makes porous carbon source be dispersed in the solution of cerium source, obtain the first mixture, wherein the specific area of Super-P is 1500m
2/ g, aperture 0.1≤r≤8nm;
(3) 5h is vacuumized after the first mixture being warming up to 180 DEG C;
(4) under the condition of 80r/min Keep agitation, adding in the first mixture with the mol ratio of cerium source cerium oxalate is the fluorine source NaF of 1.1:1, obtains the second mixture;
(5) the second mixture is left standstill 24h, then obtain CeF through centrifugation, absolute ethanol washing
3/ C positive electrode material.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery, by business-like LiCoO
2as positive electrode.
Comparative example 2
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery, by business-like LiFePO
4as positive electrode.
Comparative example 3
Method according to embodiment 1 prepares lithium ion battery, just in the step (i.e. step 1) of positive electrode preparing lithium ion battery, by business-like LiMn
2o
4as positive electrode.
Test process according to lithium ion battery of the present invention and positive electrode and preparation method and test result are finally described.
(1) test of the performance of positive electrode:
The initial charge capacity of A positive electrode, first discharge capacity, initial coulomb efficiency and cycle performance test
By positive electrode each in embodiment 1-6 and comparative example 1-3 and conductive agent acetylene black, binding agent PVDF in mass ratio 75:15:10 be mixed to get slurry, slurry is evenly coated on aluminium foil and obtains work electrode, be to electrode with lithium sheet, with Celgard2325 polypropylene screen for barrier film, with 1MLiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in the glove box being full of argon gas, be assembled into button cell.
(the charging/discharging voltage scope of embodiment 1-6 is 1.5V ~ 4.5V above-mentioned button cell to be carried out on Land discharge and recharge instrument charge-discharge test, the charging/discharging voltage scope of comparative example 1 is 3.0V ~ 4.2V, 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 test obtains the capability retention after initial charge capacity, the first discharge capacity of each positive electrode in embodiment 1-6 and comparative example 1-3, initial coulomb efficiency and 50 circulations thus.
B particle diameter is tested
By positive electrode dispersion each in embodiment 1-6 and comparative example 1-3 in ethanol, obtain suspension-turbid liquid, then getting a suspension-turbid liquid drops on copper mesh, after ethanol volatilization, adopts transmission electron microscope observation and measures the CeF in the particle diameter of the positive electrode of comparative example 1-3 and embodiment 1-6
3particle diameter.
(2) performance test of lithium ion battery
A energy density is tested
At 25 DEG C, with 0.5C constant current charge, to certain voltage, (embodiment 1-6 charges to 4.5V, comparative example 1-2 charges to 4.2V, comparative example 3 charges to 4.3V), under this voltage, constant voltage is reduced to 0.05C to electric current afterwards, and leave standstill 5min, finally with 0.5C constant-current discharge, to certain voltage, (embodiment 1-6 is discharged to 1.5V, comparative example 1 and comparative example 3 are discharged to 3.0V, and comparative example 2 is discharged to 2.0V).
B over-charging is tested
At 25 DEG C, with 0.5C constant current charge to 10V, constant voltage charge 2h under this voltage afterwards, observes the state of lithium ion battery.
C resistance to elevated temperatures is tested
At 25 DEG C, with 0.5C constant current charge, to certain voltage, (embodiment 1-6 charges to 4.5V, comparative example 1-2 charges to 4.2V, comparative example 3 charges to 4.3V), constant voltage charge 1h under this voltage, is then placed in baking oven by this lithium ion battery afterwards, is warming up to 150 DEG C from 25 DEG C, heating rate is 5 DEG C/min, observes the state of lithium ion battery.
Table 1 provides parameter and the performance test results of embodiment 1-6 and comparative example 1-3.
Next the performance test results of embodiment 1-6 and comparative example 1-3 is analyzed.
As can be seen from the contrast of embodiment 1-6 and comparative example 1-3, CeF of the present invention
3/ C positive electrode material has high initial charge capacity, first discharge capacity, first coulombic efficiency and capability retention.This is due to the LiCoO in comparative example 1-3
2, LiFePO
4, LiMn
2o
4can only be there is at most the redox reaction of 1 electronics in positive electrode, and contain metal and the polyanion group of HMW in molecule.And CeF of the present invention
3ceF in/C positive electrode material
3containing low-molecular-weight F, and Ce
3+polyelectron reaction can be there is.Although CeF
3electronic conductivity lower, but by CeF
3nano particle in situ be grown in the hole of porous carbon, can CeF be improved
3electronic conductivity, simultaneously the duct of porous carbon can limit CeF
3the growth of nano particle, and limit CeF
3the expansion/contraction of nano particle in charge and discharge process.Therefore, the CeF of gained
3/ C positive electrode material has high initial charge capacity and discharge capacity first; The CeF of gained
3/ C positive electrode material has good electrochemical reaction invertibity, therefore has high initial coulomb efficiency; The CeF of gained
3/ C positive electrode material has high voltage and high density, and its de-/embedding lithium voltage is close to its theoretical value 3.2V, and density is 6.2gcm
-3, far above LiCoO
2(5.05gcm
-3), LiFePO
4(3.52gcm
-3) and LiMn
2o
4(4.29gcm
-3), therefore CeF
3the energy density of/C positive electrode material can up to 8.1KWh/L, far above LiCoO
2, LiFePO
4and LiMn
2o
4.
, it can also be seen that from the contrast of embodiment 1-6 and comparative example 1-3, with CeF of the present invention meanwhile
3lithium ion battery prepared by/C positive electrode material has the security performance that high energy density is become reconciled.Lithium ion battery of the present invention overcharge with high temperature test after all without combustion phenomena, and apply LiCoO in comparative example 1
2the lithium ion battery prepared of positive electrode overcharge with high temperature test after there is burning.This is because at CeF
3in, Ce-F key is strong covalent bond, dissociation energy up to 582KJ/mol, far above LiCoO
2the dissociation energy 384KJ/mol of middle Co-O key, therefore CeF
3there is high thermal stability.Meanwhile, CeF of the present invention
3/ C positive electrode material is not containing O, and the accumulation of heat that can not there is releasing oxygen and then aggravation inside lithium ion cell because of heating even causes occurring the problem of thermal runaway or blast.
As can be seen from the contrast of embodiment 1 and embodiment 2, the aperture of porous carbon is less, the CeF obtained
3particle diameter less, thus the initial charge capacity of positive electrode, first discharge capacity, first coulombic efficiency and capability retention are all higher.This is due to CeF
3nano particle in situ is grown in the hole of porous carbon, and the duct of porous carbon can limit CeF
3the growth of nano particle, and limit CeF
3the expansion/contraction of nano particle in charge and discharge process, thus improve CeF
3electronic conductivity, finally improve the chemical property of positive electrode, therefore the aperture of porous carbon is less, and the chemical property of positive electrode is better.
Due to CeF
3insoluble in organic solvent, therefore without the need to the various technological parameters of accuracy controlling reaction system.The preparation method of positive electrode of the present invention is simple and feasible, easy to operate, the CeF of gained
3the purity of/C positive electrode material is high, electrochemical performance, is applicable to industrialization and produces.In addition, CeF of the present invention
3/ C positive electrode material does not use the noble metals such as Co, and CeF
3cost be only LiCoO
21/20 ~ 1/10, therefore cost is lower.
Claims (9)
1. a positive electrode for lithium ion battery, is characterized in that,
Described positive electrode is by CeF
3be composited with carbon, the chemical formula of described positive electrode is CeF
3/ C, described carbon is porous carbon, described CeF
3be positioned at the hole of described porous carbon.
2. the positive electrode of lithium ion battery according to claim 1, is characterized in that, described CeF
3particle diameter be 0.1nm ~ 50nm, be preferably 0.1nm ~ 20nm.
3. the positive electrode of lithium ion battery according to claim 1, is characterized in that, the aperture of described porous carbon is 0.1nm ~ 50nm, is preferably 0.1nm ~ 20nm.
4. the positive electrode of lithium ion battery according to claim 1, is characterized in that, the specific area>=20m of described porous carbon
2/ g, is preferably>=100m
2/ g.
5. the positive electrode of lithium ion battery according to claim 1, is characterized in that, described porous carbon is selected from one or more in carbon nano-tube, Super-P, acetylene black, Ketjenblack carbon black, XC-72 carbon black, ordered mesopore carbon CMK-3.
6. a preparation method for the positive electrode of lithium ion battery, for the preparation of the positive electrode of the lithium ion battery according to any one of claim 1-5, comprises step:
(1) cerium source is added in organic solvent, heat up and promote that cerium source is dissolved, obtain certain density cerium source solution;
(2) in the solution of cerium source, add a certain amount of porous carbon source, then ultrasonic disperse makes porous carbon source be dispersed in the solution of cerium source, obtains the first mixture;
(3) vacuumize after the first mixture being heated up;
(4) under the condition of Keep agitation, in the first mixture, add fluorine source obtain the second mixture;
(5) the second mixture is left standstill, then obtain CeF through separation, absolute ethanol washing
3/ C.
7. the preparation method of the positive electrode of lithium ion battery according to claim 6, is characterized in that,
Described cerium source is selected from Ce
3+chloride, bromide, nitrate, sulfate, acetate, one or more in oxalates;
Described porous carbon source is selected from one or more in carbon nano-tube, Super-P, acetylene black, Ketjenblack carbon black, XC-72 carbon black, ordered mesopore carbon CMK-3;
Described fluorine source is selected from alkali metal fluoride, alkali earth metal fluoride, HF, NH
4one or more in F.
8. the preparation method of the positive electrode of lithium ion battery according to claim 6, is characterized in that,
The mol ratio in described porous carbon source and described cerium source is (30 ~ 1.5): 1;
The mol ratio in described fluorine source and described cerium source is (0.9 ~ 3.1): 1.
9. a lithium ion battery, comprising:
Positive plate, comprises positive electrode;
Negative plate;
Barrier film, between positive plate and negative plate; And
Electrolyte;
It is characterized in that,
The positive electrode of the lithium ion battery of described positive electrode according to any one of claim 1-5.
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