CN108288692A - Modified positive electrode active material, method for preparing same, and lithium secondary battery - Google Patents
Modified positive electrode active material, method for preparing same, and lithium secondary battery Download PDFInfo
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- CN108288692A CN108288692A CN201710018342.XA CN201710018342A CN108288692A CN 108288692 A CN108288692 A CN 108288692A CN 201710018342 A CN201710018342 A CN 201710018342A CN 108288692 A CN108288692 A CN 108288692A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a modified anode active material, a preparation method thereof and a lithium secondary battery, wherein the modified anode active material comprises the following components: a positive electrode active material located in the core; and a coating layer coated on the surface of the positive electrode active material. The coating is a double-layer structure, including: an inner layer coated on the surface of the positive electrode active material; and an outer layer coated on the surface of the inner layer. The inner layer is selected from oxides and has a general formula of NxOyN is selected from one or more of transition metal elements and third main group elements, and y/x is more than or equal to 1/4 and less than or equal to 4. The outer layer is selected from lanthanum strontium manganese oxygen compounds with perovskite structures. The modified positive active material can prolong the cycle and storage life of the lithium secondary battery, reduce the micro-area polarization of the positive plate and the integral impedance value of the lithium secondary battery, and improve the dynamic performance of the lithium secondary battery.
Description
Technical field
The present invention relates to battery technology fields, and in particular to a kind of modified positive electrode active materials and preparation method thereof and lithium
Secondary cell.
Background technology
In order to improve the service life and storage performance of lithium rechargeable battery, usual strategy is to improve positive electrode active materials
The stability on surface and the structural stability for reinforcing positive electrode active materials itself.Currently used means are in positive-active material
Expect oxide (such as TiO of surface cladding simple structure2、Nb2O5、Al2O3、ZrO2、Y2O3、B2O3Deng), this kind of method for coating can be with
Oxidisability of the positive electrode active materials to electrolyte is reduced, but the type oxide does not have ionic conductivity and ionic conductance generally
Property or ionic conductivity and ionic conductance are excessively poor, thus can sacrifice the high power capacity and high charge-discharge of lithium rechargeable battery
Voltage platform reduces the energy density of lithium rechargeable battery to a certain extent, and this kind of method for coating also will increase
The overall impedance of lithium rechargeable battery and the dynamic performance for reducing lithium rechargeable battery.
Invention content
The problem of in view of background technology, the purpose of the present invention is to provide a kind of modified positive electrode active materials and its
Preparation method and lithium secondary battery, the modified positive electrode active materials can improve the cycle and storage life of lithium secondary battery,
The impedance value for reducing the polarization of positive plate microcell and lithium secondary battery entirety, improves the dynamic performance of lithium secondary battery.
In order to achieve the above object, in the first aspect of the present invention, the present invention provides a kind of modified positive electrode active materials,
It includes：Positive active material is located at kernel；And clad, it is coated on the surface of the positive active material.The cladding
Layer is double-layer structure, including：Internal layer is coated on the surface of the positive active material；And outer layer, it is coated on the internal layer
Surface.The internal layer is selected from oxide, general formula NxOy, the one kind or several of N in transition metal element, third major element
Kind, 1/4≤y/x≤4.The outer layer is selected from the lanthanum strontium manganese oxygen compound with perovskite structure.
In the second aspect of the present invention, the present invention provides a kind of preparation methods of modified positive electrode active materials, for making
Modification positive electrode active materials described in standby first aspect present invention, including step：(1) oxide is mixed with positive active material
After be sintered, obtain the positive active material for being coated with oxide, wherein the general formula of oxide be NxOy, it is first that N is selected from transition metal
One or more of element, third major element, 1/4≤y/x≤4；(2) positive active material and tool of oxide will be coated with
The lanthanum strontium manganese oxygen compound mixed sintering for having perovskite structure, make lanthanum strontium manganese oxygen compound be coated on the surface of oxide to get
To modified positive electrode active materials.
In the third aspect of the present invention, the present invention provides a kind of lithium secondary batteries comprising according to first party of the present invention
Modification positive electrode active materials described in face.
Compared with the existing technology, beneficial effects of the present invention are：
The modification positive electrode active materials of the present invention have the clad of double-layer structure, preferably can not only stablize kernel just
The structural stability of pole active material, improves the cycle and storage life of lithium secondary battery, and can play the work of electronic conductor
With the impedance value of the polarization of reduction positive plate microcell and lithium secondary battery entirety improves the dynamic performance of lithium secondary battery.
Description of the drawings
Fig. 1 is the room temperature DC impedance curve graph of embodiment 1 and comparative example 1.
Fig. 2 is the low temperature direct impedance plot of embodiment 1 and comparative example 1.
Fig. 3 is the high temperature cyclic performance curve graph of embodiment 1 and comparative example 1.
Fig. 4 is the high-temperature storage performance curve graph of embodiment 1 and comparative example 1.
Specific implementation mode
The following detailed description of modified positive electrode active materials according to the present invention and preparation method thereof and lithium secondary battery.
Illustrate modification positive electrode active materials according to a first aspect of the present invention first.
Modification positive electrode active materials according to a first aspect of the present invention include：Positive active material is located at kernel；And packet
Coating is coated on the surface of the positive active material.The clad is double-layer structure, including：Internal layer, be coated on it is described just
The surface of pole active material；And outer layer, it is coated on the surface of the internal layer.The internal layer is selected from oxide, general formula NxOy, N
Selected from one or more of transition metal element, third major element, 1/4≤y/x≤4.The outer layer, which is selected from, has calcium titanium
The lanthanum strontium manganese oxygen compound (being abbreviated as LSM) of mine structure.
In the modification positive electrode active materials described according to a first aspect of the present invention, the oxide positioned at internal layer plays stabilization
Positioned at the positive active material of kernel structural stability, reduce electrolyte and kernel positive active material surface reaction activity
The effect of point, the lanthanum strontium manganese oxygen compound for being located at outer layer has perovskite structure, and has metallic conduction characteristic, compensates for simple
The clad of the defect of Oxide Electron electrical conductance and the ionic conductance difference of structure, this double-layer structure can not only be preferably steady
The structural stability for determining the positive active material of kernel, improves the cycle and storage life of lithium secondary battery, and can play electricity
The effect of sub- conductor reduces the impedance value of the polarization of positive plate microcell and lithium secondary battery entirety, improves the dynamic of lithium secondary battery
Mechanical property.
In the modification positive electrode active materials described according to a first aspect of the present invention, it is preferable that N be selected from Ti, Nb, Al, Zr,
Y, one or more of B.
In the modification positive electrode active materials described according to a first aspect of the present invention, it is preferable that 1/3≤y/x≤3.
In the modification positive electrode active materials described according to a first aspect of the present invention, specifically, the oxide can be selected from
TiO2、Nb2O5、Al2O3、ZrO2、Y2O3、B2O3One or more of.
In the modification positive electrode active materials described according to a first aspect of the present invention, the general formula of the lanthanum strontium manganese oxygen compound
Can be La1-xSrxMnO3, wherein 0 x≤0.33 ＜.
In the modification positive electrode active materials described according to a first aspect of the present invention, the lanthanum strontium manganese oxygen compound can be selected from
La0.7Sr0.3MnO3、La0.8Sr0.2MnO3、La0.67Sr0.33MnO3One or more of.
In the modification positive electrode active materials described according to a first aspect of the present invention, the quality of outer layer can be interior in clad
The quality of the positive active material of core is 0.2%~2.5%, when content is excessive, is easy to influence the deintercalation channel of lithium ion, directly
Influence capacity performance, power-performance and the high rate performance of lithium secondary battery.
In the modification positive electrode active materials described according to a first aspect of the present invention, the mass ratio of the internal layer and outer layer can
It is 1:10~1:1.
In the modification positive electrode active materials described according to a first aspect of the present invention, the optional self energy of positive active material
Receive, the material of abjection lithium ion.Preferably, the positive active material can be selected from lithium transition-metal oxide, lithium transition gold
Belong to oxide and adds other transition metal or nontransition metal or nonmetallic obtained one or more of compound.Specifically
Ground, the positive active material are selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese
One or more of oxide, lithium nickel cobalt aluminum oxide, LiFePO4.
Secondly the preparation method of the modification positive electrode active materials of explanation according to a second aspect of the present invention, is used to prepare basis
Modification positive electrode active materials described in first aspect present invention, including step：(1) after oxide being mixed with positive active material
Sintering, obtains the positive active material for being coated with oxide, wherein the general formula of oxide is NxOy, N be selected from transition metal element,
One or more of third major element, 1/4≤y/x≤4；(2) by the positive active material for being coated with oxide with have
The lanthanum strontium manganese oxygen compound mixed sintering of perovskite structure, make lanthanum strontium manganese oxygen compound be coated on the surface of oxide to get to
Modified positive electrode active materials.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, in step (1), burn
Junction temperature can be 400 DEG C~900 DEG C.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, in step (2), burn
Junction temperature can be 600 DEG C~900 DEG C.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, in one embodiment,
The preparation process of the lanthanum strontium manganese oxygen compound may include step：La salt, Sr salt, Mn salt are dissolved in deionized water and form mixing
Solution is added complexing agent progress solgel reaction and obtains xerogel later；By xerogel in 300 DEG C of ± 30 DEG C of progress self- propagatings
Sintering reaction, then sintering obtains the lanthanum strontium manganese oxygen compound with perovskite structure at 600 DEG C~1000 DEG C.Wherein, certainly
The lanthanum strontium manganese oxygen compound for spreading sintering reaction synthesis has larger specific surface area, has larger conductive sub-network, to have
There is preferable ionic conductivity, the function of replacing a certain amount of positive conductive agent (such as Super-P) can be reached.And this method
The lanthanum strontium manganese oxygen compound of synthesis is more open, shape is similar to Super-P, therefore during cladding, only need to be by lanthanum-strontium manganese
Oxygen compound can achieve the effect that be uniformly mixed with the positive active material solid phase mixing for being coated with oxide.In addition lanthanum-strontium
The presoma of manganese and oxygen compound is prepared by solgel reaction, and each element mixing is more uniform in presoma, therefore more
It is easy to prepare that granularity is small and finely dispersed lanthanum strontium manganese oxygen compound.In addition, the temperature of self- propagating sintering reaction is lower, energy
Effectively reduce production cost.And the xerogel presoma of self- propagating sintering lanthanum strontium manganese oxygen compound, sintering reaction can be made more to fill
Make the powder more uniform and delicate of the lanthanum strontium manganese oxygen compound of synthesis while dividing.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, La salt can be selected from nitric acid
Lanthanum, lanthanum chloride, lanthanum acetate.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, Sr salt can be selected from nitric acid
Strontium, strontium chloride, strontium acetate.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, Mn salt can be selected from nitric acid
Manganese, manganese sulfate, manganese chloride, manganese acetate, manganese oxalate.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, lemon can be added in complexing agent
Lemon acid or oxalic acid.
In the preparation method of the modification positive electrode active materials described according to a second aspect of the present invention, in another embodiment
In, the preparation process of the lanthanum strontium manganese oxygen compound may include step：By La2O3、SrCO3、MnO2Calcining is had after mixing
The lanthanum strontium manganese oxygen compound of perovskite structure.Wherein, calcination temperature can be 1000 DEG C~1300 DEG C.
Lithium secondary battery according to a third aspect of the present invention will be illustrated next comprising described according to a first aspect of the present invention
Modification positive electrode active materials.
Lithium secondary battery according to a third aspect of the present invention can be lithium metal secondary battery or lithium rechargeable battery.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
(1) preparation of modified positive electrode active materials
By La (NO3)3、Sr(NO3)2、Mn(NO3)2According to the amount of substance than 7:3:10 mixing, are added in deionized water and mix
Uniformly it is configured to the nitrate solution that La, Sr, Mn metal ion total concentration are 0.5mol/L.Citric acid is added as complexing agent,
The amount ratio of the substance of citric acid and nitrate is 1~2, is then stirred evenly.The pH that weak aqua ammonia adjusts solution is added, control pH exists
2.5 left and right.Ethylene glycol is added under stirring and carries out solation reaction, controls substance of the amount with citric acid of the substance of ethylene glycol
Amount it is identical, later by solution be heated to 80 DEG C carry out gelations handle to obtain wet gel.By wet gel in 120 DEG C of freeze-day with constant temperature
It is dehydrated for 24 hours, xerogel is prepared.Then obtained xerogel is carried out at 300 DEG C 1h self- propagatings sintering reaction to get to
La0.7Sr0.3MnO3Powder, it is spare.
By Al2O3With positive active material LiNi0.5Co0.25Mn0.25O2According to mass ratio 0.2:100 mixing, then 600
It is sintered 6h at DEG C, obtains being coated with Al2O3Positive active material；By above-mentioned substance and La0.7Sr0.3MnO3In mass ratio 100:
0.5 solid phase mixing, sieving then carry out 8h solid-phase sinterings to get to modified positive electrode active materials at 600 DEG C~650 DEG C.
(2) preparation of positive plate
By above-mentioned modified positive electrode active materials, binder polyvinylidene fluoride, conductive agent Super-P in mass ratio 94:3:3
It is mixed, makees solvent using N-Methyl pyrrolidone, stirred evenly through 1000~2000r/min, obtain anode sizing agent.It will just
Pole slurry is uniformly coated on two surfaces of plus plate current-collecting body aluminium foil (thickness is 14 μm), coating weight 0.300g/
1540.25mm2, it is dried in 130 DEG C of baking ovens, positive plate is obtained after being cold-pressed, being cut into, it is spare.
(3) preparation of negative plate
By negative electrode active material artificial graphite, binder SBR emulsion, thickener sodium carboxymethylcellulose and conductive agent
Super-P in mass ratio 90:2:3:5 are mixed, and are made solvent using deionized water, are stirred evenly through 1000~2000r/min,
Obtain negative electrode slurry.Negative electrode slurry is uniformly coated on two surfaces of negative current collector copper foil (thickness is 8 μm), coating
Weight is 0.150g/1540.25mm2, it is dried in 80 DEG C of baking ovens, negative plate is obtained after being cold-pressed, being cut into, it is spare.
(4) preparation of lithium rechargeable battery
Conductive lug is welded on positive plate and negative plate, and thickness is used to be separated for 12 μm of polypropylene isolation film, is folded
It sets to form naked battery core, then is encapsulated with aluminum plastic film.Electrolyte uses the lithium hexafluorophosphate electrolyte solution containing 1M, and solvent is ethylene carbonate
Ester, propene carbonate, dimethyl carbonate 1:1:The mixed solvent of 1 (volume ratio).Electrolyte is injected after encapsulation, obtain finished product lithium from
Sub- secondary cell.
Embodiment 2
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
(1) preparation of modified positive electrode active materials
La0.7Sr0.3MnO3Synthesis with embodiment 1.
By ZrO2With positive active material LiNi0.5Co0.25Mn0.25O2According to mass ratio 0.1:100 mixing, then 600
It is sintered 6h at DEG C, obtains being coated with ZrO2Positive active material；By above-mentioned substance and La0.7Sr0.3MnO3In mass ratio 100:
0.3 solid phase mixing, sieving then carry out 8h solid-phase sinterings to get to modified positive electrode active materials at 600 DEG C~650 DEG C.
Embodiment 3
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
(1) preparation of modified positive electrode active materials
By La2O3、SrCO3、MnO2Amount ratio according to substance is 3.5:3:10 be uniformly mixed obtain batch mixing, to batch mixing be added
A small amount of ethyl alcohol simultaneously mixes 1h in star-like grinder, later the pre-burning 12h at 1000 DEG C in air, and the powder after calcining is ground
Mill, sieving is to get to La0.7Sr0.3MnO3Powder.
By TiO2With positive active material LiNi0.5Co0.25Mn0.25O2According to mass ratio 0.2:100 mixing, then 600
It is sintered 6h at DEG C, obtains being coated with TiO2Positive active material；By above-mentioned substance and La0.7Sr0.3MnO3In mass ratio 100:
0.2 solid phase mixing, sieving then carry out 8h solid-phase sinterings to get to modified positive electrode active materials at 600 DEG C~650 DEG C.
Embodiment 4
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
(1) preparation of modified positive electrode active materials
La0.7Sr0.3MnO3Synthesis with embodiment 1.
By Al2O3With positive active material LiNi0.5Co0.25Mn0.25O2According to mass ratio 0.4:100 mixing, then 600
It is sintered 6h at DEG C, obtains being coated with Al2O3Positive active material；By above-mentioned substance and La0.7Sr0.3MnO3In mass ratio 100:1
Solid phase mixing, sieving then carry out 8h solid-phase sinterings to get to modified positive electrode active materials at 600 DEG C~650 DEG C.
Embodiment 5
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
(1) preparation of modified positive electrode active materials
La0.7Sr0.3MnO3Synthesis with embodiment 1.
By Al2O3With positive active material LiNi0.5Co0.25Mn0.25O2According to mass ratio 0.2:100 mixing, then 600
It is sintered 6h at DEG C, obtains being coated with Al2O3Positive active material；By above-mentioned substance and La0.7Sr0.3MnO3In mass ratio 100:2
Solid phase mixing, sieving then carry out 8h solid-phase sinterings to get to modified positive electrode active materials at 600 DEG C~650 DEG C.
Comparative example 1
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
(1) preparation of positive plate
Not to positive active material LiNi0.5Co0.25Mn0.25O2It is coated.
By conventional positive active material LiNi0.5Co0.25Mn0.25O2, binder polyvinylidene fluoride, conductive agent Super-
P in mass ratio 94:3:3 are mixed, and are made solvent using N-Methyl pyrrolidone, are stirred evenly through 1000~2000r/min, are obtained
To anode sizing agent.Anode sizing agent is uniformly coated on two surfaces of plus plate current-collecting body aluminium foil (thickness is 14 μm), coating weight
Amount is 0.300g/1540.25mm2, it is dried in 130 DEG C of baking ovens, positive plate is obtained after being cold-pressed, being cut into, it is spare.
Comparative example 2
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
By LiNi0.5Co0.25Mn0.25O2Directly coat La0.7Sr0.3MnO3, uncoated Al2O3, wherein La0.7Sr0.3MnO3With
LiNi0.5Co0.25Mn0.25O2Mass ratio be 0.5:100.
Comparative example 3
Lithium rechargeable battery is prepared according to the method for embodiment 1, difference lies in：
By LiNi0.5Co0.25Mn0.25O2Directly coat Al2O3, uncoated La0.7Sr0.3MnO3, wherein Al2O3With
LiNi0.5Co0.25Mn0.25O2Mass ratio be 0.3:100.
The test process of lithium rechargeable battery will be illustrated next.
(1) the DC impedance test of lithium rechargeable battery
Lithium rechargeable battery after forming and capacity dividing is completely put, fast charging and discharging test is then carried out, by lithium ion
Secondary cell is completely charged to 4.3V with the current density of 2.5A, is later 0.5A with 4.3V constant-voltage charges to current density, then with
The current density constant-current discharge of 2.5A calculates discharge capacity, is denoted as C to 2.8V0(i.e. 100%SOC)；By lithium rechargeable battery
25 DEG C of environment are placed in, 5min are stood, then with 1C0It is completely charged to 4.3V, then with 1C0Constant-current discharge 6min, it is 90% to adjust SOC, quiet
After setting 60min, with 4C0Constant-current discharge 30s, sampling site interval 0.1s, the room temperature DC impedance of exploitation lithium rechargeable battery.
50%SOC is (with 1C0Constant-current discharge 30min), 20%SOC is (with 1C0Constant-current discharge 48min) under room temperature DC impedance test
Journey is identical as 90%SOC.
The test process of lithium rechargeable battery low temperature direct impedance is：By the lithium rechargeable battery of 100%SOC-
120min is stood in 25 DEG C of environment, then with 1C0It is completely charged to 4.3V, then with 1C0Constant-current discharge adjusts lithium rechargeable battery
State-of-charge (90%SOC, 50%SOC, 20%SOC), then with 0.3C0Constant-current discharge 10s, sampling site interval 0.1s, exploitation
The low temperature direct impedance of lithium rechargeable battery.
(2) the high temperature cyclic performance test of lithium rechargeable battery
At 60 DEG C, by lithium rechargeable battery with 1C0Constant-current charge is to 4.3V, further with 4.3V constant-voltage charges to electricity
Stream≤0.05C0, 5min is stood, later with 1C0To 2.8V, this is repeated the above process to recycle for the first time constant-current discharge, until lithium from
The 80% of capacity, records the cycle time of lithium rechargeable battery after capacity attenuation to cycle for the first time after sub- secondary cell cycle
Number.
(3) the high-temperature storage performance test of lithium rechargeable battery
At 25 DEG C, by lithium rechargeable battery with 1C0Constant current is completely charged to 4.3V, then constant-voltage charge is to 0.05C0, postposition
It stores in 45 DEG C of insulating box, was taken out every 30 days, and use 1C0Current density be discharged to 2.8V, test 100%SOC
Under residual capacity, and with the discharge capacity C that is tested at 25 DEG C0It is compared, calculates the residue of lithium rechargeable battery
Capacity retention ratio stops test when residual capacity conservation rate is less than 80%, records the storage number of days of lithium rechargeable battery.
The performance test results of table 1 embodiment 1-5 and comparative example 1-3
| - 25 DEG C, 20%SOC DC impedances/mohm | Cycle-index | Store number of days | |
| Embodiment 1 | 708 | 840 | 250 |
| Embodiment 2 | 716 | 845 | 245 |
| Embodiment 3 | 800 | 760 | 190 |
| Embodiment 4 | 920 | 880 | 260 |
| Embodiment 5 | 683 | 860 | 260 |
| Comparative example 1 | 900 | 500 | 130 |
| Comparative example 2 | 720 | 695 | 175 |
| Comparative example 3 | 1000 | 780 | 200 |
Fig. 1 is the room temperature DC impedance curve graph of embodiment 1 and comparative example 1.Fig. 2 is the low temperature of embodiment 1 and comparative example 1
DC impedance curve graph.As can be seen that the overall impedance value of embodiment 1 is substantially reduced from Fig. 1 and Fig. 2.Fig. 3 is embodiment 1
With the high temperature cyclic performance curve graph of comparative example 1.In the case where capacity equally decays to 80%, the lithium ion two of embodiment 1
The cycle ratio comparative example 1 of primary cell improves about 300 times.Fig. 4 is the high-temperature storage performance song of embodiment 1 and comparative example 1
Line chart.Figure 4, it is seen that the double-coating of embodiment 1 handles lithium ion secondary electricity when can effectively reduce high temperature storage
The capacity attenuation in pond.This is because, the modification positive electrode active materials of the present invention have the clad of double-layer structure, it is located at internal layer
Oxide is used to stablize the structure of the positive active material of kernel, and the LSM of outer layer is used to increase the positive active material of kernel
Ionic conductivity reduces the impedance of lithium rechargeable battery, improves the cycle and storage life of lithium rechargeable battery.
In embodiment 1, embodiment 4-5, the content of the oxide of internal layer increases, and the impedance of lithium rechargeable battery increases
Add；The content of the LSM of outer layer increases, and can influence the transmission of lithium ion, reduce the volume capacity of lithium rechargeable battery, influence lithium
The cycle and storage life of ion secondary battery.
In comparative example 2, the surface of positive active material only has LSM claddings, due to LSM itself ionic conductance not
Height affects the transmission of lithium ion, causes the cycle of lithium rechargeable battery and storage life poor.
In comparative example 3, the surface of positive active material only has Al2O3Cladding, ionic conductivity is poor, cause lithium from
The impedance of sub- secondary cell is higher.
Claims (10)
1. a kind of modified positive electrode active materials, including：
Positive active material is located at kernel；And
Clad is coated on the surface of the positive active material；
It is characterized in that,
The clad is double-layer structure, including：
Internal layer is coated on the surface of the positive active material；And
Outer layer is coated on the surface of the internal layer；
The internal layer is selected from oxide, general formula NxOy, the one kind or several of N in transition metal element, third major element
Kind, 1/4≤y/x≤4；
The outer layer is selected from the lanthanum strontium manganese oxygen compound with perovskite structure.
2. modified positive electrode active materials according to claim 1, which is characterized in that the general formula of the lanthanum strontium manganese oxygen compound
For La1-xSrxMnO3, wherein 0 x≤0.33 ＜.
3. modified positive electrode active materials according to claim 1, which is characterized in that N is in Ti, Nb, Al, Zr, Y, B
One or more, 1/3≤y/x≤3.
4. modified positive electrode active materials according to claim 1, which is characterized in that the quality of outer layer is kernel in clad
Positive active material quality be 0.2%~2.5%.
5. modified positive electrode active materials according to claim 1, which is characterized in that the mass ratio of the internal layer and outer layer is
1:10~1:1.
6. a kind of preparation method of modified positive electrode active materials, it is being used to prepare modification described in any one of claim 1-5 just
Pole active material, which is characterized in that including step：
(1) it is sintered after mixing oxide with positive active material, obtains the positive active material for being coated with oxide, wherein
The general formula of oxide is NxOy, N is selected from one or more of transition metal element, third major element, 1/4≤y/x≤4；
(2) positive active material of oxide will be coated with and there is the lanthanum strontium manganese oxygen compound mixed sintering of perovskite structure,
Lanthanum strontium manganese oxygen compound is set to be coated on the surface of oxide to get to modified positive electrode active materials.
7. the preparation method of modified positive electrode active materials according to claim 6, which is characterized in that
In step (1), sintering temperature is 400 DEG C~900 DEG C；
In step (2), sintering temperature is 600 DEG C~900 DEG C.
8. the preparation method of modified positive electrode active materials according to claim 6, which is characterized in that the lanthanum strontium manganese oxygen
The preparation process for closing object includes step：
La salt, Sr salt, Mn salt are dissolved in deionized water and form mixed solution, complexing agent is added later and carries out solgel reaction
Obtain xerogel；
By xerogel in 300 DEG C of ± 30 DEG C of progress self- propagating sintering reactions, being then sintered at 600 DEG C~1000 DEG C is had
The lanthanum strontium manganese oxygen compound of perovskite structure.
9. the preparation method of modified positive electrode active materials according to claim 6, which is characterized in that the lanthanum strontium manganese oxygen
The preparation process for closing object includes step：
By La2O3、SrCO3、MnO2Calcining obtains the lanthanum strontium manganese oxygen compound with perovskite structure after mixing.
10. a kind of lithium secondary battery, which is characterized in that living including modified anode according to any one of claims 1-5
Property material.
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Application publication date: 20180717 |