CN108155373A - Negative electrode active material and preparation method thereof, cathode pole piece and battery core - Google Patents
Negative electrode active material and preparation method thereof, cathode pole piece and battery core Download PDFInfo
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- CN108155373A CN108155373A CN201611107852.6A CN201611107852A CN108155373A CN 108155373 A CN108155373 A CN 108155373A CN 201611107852 A CN201611107852 A CN 201611107852A CN 108155373 A CN108155373 A CN 108155373A
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/362—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
- 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
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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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- 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
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Abstract
The present invention provides a kind of negative electrode active material and preparation method thereof, cathode pole piece and battery core.The negative electrode active material includes：Lithium titanate kernel；And it is coated on the clad of lithium titanate core surface.The clad is selected from lanthanum strontium manganese oxygen.The battery core of the present invention can achieve the effect that high-energy density is taken into account with big multiplying power quick charge, while have preferable high/low temperature cycle performance and hot tank security performance.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of negative electrode active material and preparation method thereof, cathode pole pieces
And battery core.
Background technology
Lithium ion battery is as the most representative energy storage device of new energy field, in mobile electron, power battery and storage
The position do not replaced is occupied in the fields such as energy power station.Especially in consumer electronics field, to the fast charging and discharging of lithium ion battery
Performance and capacity have higher requirement.But the lithium-ion electric using graphite as negative electrode active material generally used at present
Pond easily occurs the problems such as cathode analysis lithium in quick charge, and very big security risk is brought to lithium ion battery.Simultaneously just
In terms of the active material of pole, the energy density for increasing substantially lithium ion battery has encountered some bottlenecks.Therefore, how to improve
The embedding lithium ability of cathode and how using other approach (as preferably utilize the inside and outside remaining space of lithium ion battery) realize more
Big capacity seems particularly necessary.
Lithium titanate is a kind of negative electrode active material of spinelle shape structure, with charge and discharge volume change is small, electric discharge is flat
The advantages that platform is steady, safe, lithium ion deintercalation speed is fast, is one of developing direction of lithium ion battery.But lithium titanate
Charge/discharge capacity it is low, therefore energy density is limited, in addition battery core bulging problem present in lithium titanate charge and discharge process, always
It is seldom applied in consumer electronics field.
Invention content
In view of the problem of background technology, the purpose of the present invention is to provide a kind of negative electrode active material and its preparations
Method, cathode pole piece and battery core can achieve the effect that high-energy density is taken into account with big multiplying power quick charge, while have preferably
High/low temperature cycle performance and hot tank security performance.
In order to achieve the above object, in the first aspect of the present invention, the present invention provides a kind of negative electrode active material, packets
It includes：Lithium titanate kernel；And it is coated on the clad of lithium titanate core surface.The clad is selected from lanthanum strontium manganese oxygen.
In the second aspect of the present invention, the present invention provides a kind of preparation methods of negative electrode active material, are used to prepare this
Negative electrode active material described in invention first aspect, including step：(1) lanthanum salt, strontium salt, manganese salt are dissolved in deionized water respectively
In and be mixed to form mixed solution；(2) chelating agent is added in into mixed solution and buffer carries out gelation reaction to obtain lanthanum
Strontium manganese oxygen wet gel；(3) lithium titanate powdery is added in into lanthanum strontium manganese oxygen wet gel, later drying, sintering, that is, completes cathode and live
Property material preparation, wherein, obtained negative electrode active material includes lithium titanate kernel and is coated on lithium titanate core surface
Clad, the clad be selected from lanthanum strontium manganese oxygen.
In the third aspect of the present invention, the present invention provides a kind of cathode pole piece, including：Negative current collector；It is and negative
Pole diaphragm is set on negative current collector and including negative electrode active material, conductive agent and bonding agent.Wherein, the cathode is lived
Property material include the negative electrode active material according to a first aspect of the present invention.
In the fourth aspect of the present invention, the present invention provides a kind of battery core, including described according to a third aspect of the present invention
Cathode pole piece.
Relative to the prior art, beneficial effects of the present invention are：
In the negative electrode active material of the present invention, as a kind of perovskite structure material, itself has lanthanum strontium manganese oxygen
Very superior electron conduction and higher oxygen reduction activity, and it is less with electrolyte side reaction, using the metatitanic acid of its cladding
Lithium has the advantages of analysing lithium and high thermal stability without cathode, can greatly improve the high/low temperature cycle performance of battery core and hot tank peace
Full performance, while battery core is made to achieve the effect that high-energy density is taken into account with big multiplying power quick charge.
Specific embodiment
The following detailed description of negative electrode active material according to the present invention and preparation method thereof, cathode pole piece and battery core.
Illustrate negative electrode active material according to a first aspect of the present invention first.
Negative electrode active material according to a first aspect of the present invention includes：Lithium titanate kernel；And it is coated on lithium titanate kernel
The clad on surface.The clad is selected from lanthanum strontium manganese oxygen (LSM).
In the negative electrode active material described according to a first aspect of the present invention, negative electrode active material can be only by lithium titanate kernel
And it is coated on the clad composition of lithium titanate core surface.The clad is selected from lanthanum strontium manganese oxygen (LSM).
In the negative electrode active material described according to a first aspect of the present invention, lanthanum strontium manganese oxygen is as a kind of perovskite structure
Material, itself has very superior electron conduction and higher oxygen reduction activity, and less with electrolyte side reaction, adopts
With the lithium titanate of its cladding, has the advantages of analysing lithium and high thermal stability without cathode, the high/low temperature that can greatly improve battery core is followed
Ring performance and hot tank security performance, while battery core is made to achieve the effect that high-energy density is taken into account with big multiplying power quick charge.
In the negative electrode active material described according to a first aspect of the present invention, the general formula of the lanthanum strontium manganese oxygen can be
LaxSryMnzO3, wherein, 0.5≤x≤0.9,0.1≤y≤0.5 and x+y+z=2.Preferably, 0.67≤x≤0.8,0.2≤y
≤ 0.33 and x+y+z=2.This is because lanthanum strontium manganese oxygen is perovskite structure, itself has very superior electronic conduction
Property and higher oxygen reduction activity.When the ratio of lanthanum (La) and strontium (Sr) is changed in a certain range (0.5≤x≤
0.9th, 0.1≤y≤0.5), the saturation magnetization first increases and then decreases of lanthanum strontium manganese oxygen.When strontium content control 0.2≤y≤
When 0.33, the best performance of lanthanum strontium manganese oxygen；The substitution of lanthanum can cause the variation of manganese ion electric field difference, therefore when the content of lanthanum controls
In 0.67≤x≤0.8, the structure of lanthanum strontium manganese oxygen is stablized the most.
In the negative electrode active material described according to a first aspect of the present invention, the lanthanum strontium manganese oxygen may be selected from
La0.7Sr0.3MnO3、La0.8Sr0.2MnO3、La0.67Sr0.33MnO3One or more of.
In the negative electrode active material described according to a first aspect of the present invention, the quality of clad can be lithium titanate kernel
The 0.1%~10% of quality.I.e. the quality of lanthanum strontium manganese oxygen is the 0.1%~10% of the quality of lithium titanate kernel.Lanthanum strontium manganese oxygen
When mass percentage is less than 0.1%, lithium titanate kernel can not be coated complete, it is impossible to which playing improves negative terminal surface stability
Effect, when the mass percentage of lanthanum strontium manganese oxygen is higher than 10%, since lanthanum strontium manganese oxygen can not store lithium ion, ion-conductance in itself
Conductance is relatively low, therefore the content of lanthanum strontium manganese oxygen can excessively reduce the energy density of battery core.
In the negative electrode active material described according to a first aspect of the present invention, the thickness of clad can be 0.03 μm~3 μm.
Secondly the preparation method of the negative electrode active material of explanation according to a second aspect of the present invention, is used to prepare the present invention first
Negative electrode active material described in aspect, including step：(1) lanthanum salt, strontium salt, manganese salt are dissolved in deionized water and mixed respectively
Form mixed solution；(2) chelating agent is added in into mixed solution and buffer progress gelation reaction is wet to obtain lanthanum strontium manganese oxygen
Gel；(3) lithium titanate powdery is added in into lanthanum strontium manganese oxygen wet gel, drying, sintering, that is, complete negative electrode active material later
It prepares, wherein, obtained negative electrode active material includes lithium titanate kernel and is coated on the clad of lithium titanate core surface,
The clad is selected from lanthanum strontium manganese oxygen.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, using this sol gel process
The lanthanum strontium manganese oxygen wet gel of synthesis, can be in order to the lanthanum strontium manganese oxygen clad coated in sintering process in lithium titanate core surface
Thickness control uniformly coats one layer of lanthanum strontium manganese oxygen clad hereinafter, being advantageously implemented at 3 μm in lithium titanate core surface.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (1), lanthanum salt,
Strontium salt, manganese salt are each independently selected from lanthanum, strontium, the carbonate of manganese, nitrate, sulfate, oxalates or acetate.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (1), mixing is molten
In liquid, lanthanum ion, strontium ion, manganese ion total concentration can be 0.5mol/L~2mol/L.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (2), chelating agent
It may be selected from one or more of citric acid, EDTA, ethylene glycol.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (2), buffer
It may be selected from one or more of ammonium hydroxide, ammonium hydrogencarbonate, ammonium chloride.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (2), reaction temperature
Degree can be 60 DEG C~85 DEG C, and pH=2~4 of reaction system, the reaction time of gelation reaction can be 5h~10h.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (3), drying temperature
Degree can be 65 DEG C~90 DEG C, and drying time can be 4h~12h, wherein, lanthanum strontium manganese oxygen wet gel becomes lanthanum-strontium manganese after drying
Oxygen xerogel.
In the preparation method of the negative electrode active material described according to a second aspect of the present invention, in step (3), sintering temperature
Degree can be 500 DEG C~700 DEG C, and sintering time can be 2h~6h.
Illustrate cathode pole piece according to a third aspect of the present invention again, including：Negative current collector；And cathode membrane,
It is set on negative current collector and including negative electrode active material, conductive agent and bonding agent.Wherein, the negative electrode active material packet
Include the negative electrode active material described according to a first aspect of the present invention.
According in the cathode pole piece described according to a third aspect of the present invention, the thickness of cathode membrane can be 10 μm~400 μ
m。
According in the cathode pole piece described according to a third aspect of the present invention, in cathode membrane, the bonding agent is optional
From Kynoar, polytetrafluoroethylene (PTFE), vinylidene-tetrafluoroethylene-propylene terpolymer, biasfluoroethylene-hexafluoropropylene-four
One or more of vinyl fluoride terpolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, fluorinated acrylate resin；It is described
Conductive agent may be selected from one kind in conductive black, superconduction carbon black, electrically conductive graphite, acetylene black, Ketjen black, graphene, carbon nanotube
It is or several.
According in the cathode pole piece described according to a third aspect of the present invention, the negative current collector can be aluminium foil.
According in the cathode pole piece described according to a third aspect of the present invention, the cathode pole piece further includes：Middle layer, if
It puts between negative current collector and cathode membrane.The middle layer includes：One in native graphite, Delanium, soft carbon, hard carbon
Kind is several；Binding agent；And optional conductive agent.At this point, the negative current collector can be copper foil.Specifically, there is the knot
The preparation process of the cathode pole piece of structure can be：Negative electrode active material is added in conductive agent, binding agent in solvent and is uniformly mixed system
It is standby into negative electrode slurry 1；By one or more of native graphite, Delanium, soft carbon, hard carbon and binding agent, optional conduction
Agent, which adds in be uniformly mixed in solvent, is prepared into negative electrode slurry 2；Negative electrode slurry 2 is uniformly coated on negative current collector copper foil,
Drying, cold pressing are spare；Continue to coat one layer of negative electrode slurry 1 later, by drying, being cold-pressed, cutting, be prepared into cathode pole piece.
Cathode pole piece caused analysis lithium when high current or low temperature charge can highly desirable be inhibited using the cathode pole piece of the structure
Problem, and the high capacity characteristics of native graphite, Delanium, soft carbon, hard carbon can be taken into account, it is close to make up lithium titanate low energy itself
The disadvantage of degree, and then improve the cycle performance and security performance of battery core entirety.
According in the cathode pole piece according to a third aspect of the present invention, the thickness of the middle layer can be 10 μm~
200μm。
According in the cathode pole piece described according to a third aspect of the present invention, in the middle layer, the bonding agent can
Selected from one or more of butadiene-styrene rubber, sodium carboxymethylcellulose；The conductive agent may be selected from conductive black, superconduction carbon black,
One or more of electrically conductive graphite, acetylene black, Ketjen black, graphene, carbon nanotube.
Battery core according to a fourth aspect of the present invention will be illustrated next, including the cathode described according to a third aspect of the present invention
Pole piece.
In the battery core described according to a fourth aspect of the present invention, it is preferable that the battery core can be special-shaped step battery core, with into
One step improves the energy density of battery core, while can more fully utilize the remaining space of battery core, meets consumer and length is treated
The use demand of electromechanical core.However, the present invention is not limited thereto, the battery core are alternatively conventional lamination type electric core or takeup type battery core.
In the battery core described according to a fourth aspect of the present invention, the quantity of step can be 1~5.Excessive numbers of steps is led
The processing cost for sending a telegraph core is excessively high, is unfavorable for the realization of industrialized production.
In the battery core described according to a fourth aspect of the present invention, the battery core is preferably lithium ion 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 cathode pole piece
By lanthanum nitrate, strontium nitrate, manganese nitrate according to La, Sr, Mn molar ratio be 0.7:0.3:1 is dissolved in deionized water
In, be made into La, Sr, Mn total ion concentration be 1mol/L mixed solution, later add in citric acid (molal quantity of citric acid with
The ratio between summation of La, Sr, Mn mole number of ions is 2.5:1) and ammonium hydrogencarbonate progress gelation reaction is wet to obtain lanthanum strontium manganese oxygen
Gel, wherein, reaction temperature is 80 DEG C, the pH=3 of reaction system, and the reaction time is 5h~10h.It is according to cladding ratio
0.1% (quality of the lanthanum strontium manganese oxygen finally obtained is the 0.1% of the quality of lithium titanate), adds in into lanthanum strontium manganese oxygen wet gel
The lithium titanate powdery of commercialization, is dried later, after solvent deionized water is fully volatilized, by obtained lanthanum strontium manganese oxygen xerogel in
It 2h is sintered at 600 DEG C to get the lithium titanate coated to lanthanum strontium manganese oxygen, completes the preparation of negative electrode active material, wherein clad
Thickness is about 0.03 μm.
By above-mentioned negative electrode active material and conductive agent conductive carbon, binding agent Kynoar according to mass ratio 97:1.5:1.5
It adds in be uniformly mixed in solvent NMP and is prepared into negative electrode slurry, negative electrode slurry is uniformly coated on negative current collector aluminium foil later
On, by drying, being cold-pressed, cutting, cathode pole piece is prepared into, the thickness of cathode membrane wherein formed after negative electrode slurry drying is
400μm。
(2) preparation of anode pole piece
By the cobalt acid lithium of positive electrode active materials commercialization, binding agent Kynoar, conductive agent acetylene black according to mass ratio
97:1:It is uniformly mixed in 2 addition solvent NMP and anode sizing agent is made, anode sizing agent is coated uniformly on plus plate current-collecting body aluminium later
On foil, by drying, being cold-pressed, cutting, it is prepared into anode pole piece.
(3) preparation of electrolyte
In water content<In the argon gas atmosphere glove box of 10ppm, by ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbon
Diethyl phthalate (DEC) is EC according to mass ratio:EMC:DEC=30:50:20 carry out mixing as organic solvent, then will be abundant
Dry lithium salts LiPF6It is dissolved in mixed organic solvents, obtains electrolyte after mixing.Wherein, LiPF6It is a concentration of
1mol/L。
(4) preparation of lithium ion battery
The cathode pole piece prepared, isolation film (porous polyethylene membrane), anode pole piece are folded in order, rolled preparation
Into naked battery core, by processes such as encapsulation, fluid injection, chemical conversion, moldings, it is 6mm*58mm*90mm's to be prepared into thickness * width * length
Soft bag lithium ionic cell.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, difference lies in：Cladding ratio is 0.5%, the thickness of clad
About 0.15 μm.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, difference lies in：Cladding ratio is 3%, and the thickness of clad is about
It is 1 μm.
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, difference lies in：Cladding ratio is 10%, the thickness of clad
About 3 μm.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, difference lies in：
(1) preparation of cathode pole piece
By lanthanum nitrate, strontium nitrate, manganese nitrate according to La, Sr, Mn molar ratio be 0.7:0.3:1 is dissolved in deionized water
In, be made into La, Sr, Mn total ion concentration be 1mol/L mixed solution, later add in citric acid (molal quantity of citric acid with
The ratio between summation of La, Sr, Mn mole number of ions is 2.5:1) and ammonium hydrogencarbonate progress gelation reaction is wet to obtain lanthanum strontium manganese oxygen
Gel, wherein, reaction temperature is 80 DEG C, the pH=3 of reaction system, and the reaction time is 5h~10h.It is 3% according to cladding ratio,
The lithium titanate powdery of commercialization is added in into lanthanum strontium manganese oxygen wet gel, is dried later, it is dry by what is obtained after solvent fully volatilizees
Gel is sintered 2h to get the lithium titanate coated to lanthanum strontium manganese oxygen at 600 DEG C, completes the preparation of negative electrode active material, wherein, packet
The thickness of coating is about 1 μm.
By above-mentioned negative electrode active material and conductive agent conductive carbon, binding agent Kynoar according to mass ratio 97:1.5:1.5
It adds in be uniformly mixed in solvent NMP and is prepared into negative electrode slurry 1；By the Delanium of commercialization and conductive agent acetylene black, binding agent
Butadiene-styrene rubber, thickener sodium carboxymethylcellulose are according to mass ratio 97:1:0.8:It is uniformly mixed in 1.2 addition solvent deionized waters
It is prepared into negative electrode slurry 2；Negative electrode slurry 2 is uniformly coated on negative current collector copper foil, drying, cold pressing are spare；Later
Continue to coat one layer of negative electrode slurry 1, by drying, be cold-pressed, cut, be prepared into cathode pole piece, wherein negative electrode slurry 2 dry after shape
Into middle layer thickness for 200 μm, the thickness of cathode membrane that negative electrode slurry 1 is formed after drying is 10 μm.
Embodiment 6
Method according to embodiment 5 prepares lithium ion battery, difference lies in：
(4) preparation of lithium ion battery
Anode pole piece and cathode pole piece are cut into the shape of requirement by the way of mechanical stamping, by the anode of well cutting
Pole piece, isolation film and cathode pole piece are alternately stacked, and hot pressing is compound, then are cut away the isolation film at abnormity with laser, shape
Into the naked battery core of level-one step abnormity.It repeats above step and prepares the naked battery core of two stage steps abnormity of different steps, then will prepare
The naked battery core of firsts and seconds step abnormity be stacked into the naked battery core of step abnormity.Then the naked battery core of special-shaped step is packed into packaging bag
Packaging realizes the assembling of naked battery core, then passes through the processes such as fluid injection, chemical conversion, molding, completes the system of special-shaped step lithium ion battery
It is standby.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery, difference lies in：
(1) preparation of cathode pole piece
By the lithium titanate powdery of commercialization and conductive agent conductive carbon, binding agent Kynoar according to mass ratio 97:1.5:
It is uniformly mixed in 1.5 addition solvent NMP and is prepared into negative electrode slurry, negative electrode slurry is uniformly coated on negative current collector copper later
On foil, by drying, being cold-pressed, cutting, it is prepared into cathode pole piece, the thickness of cathode membrane wherein formed after negative electrode slurry drying
It is 400 μm.
Comparative example 2
Method according to embodiment 1 prepares lithium ion battery, difference lies in：Cladding ratio is 12%, the thickness of clad
About 4 μm.
Comparative example 3
Method according to embodiment 1 prepares lithium ion battery, difference lies in：
(1) preparation of cathode pole piece
By the lithium titanate powdery of commercialization and conductive agent conductive carbon, binding agent Kynoar according to mass ratio 97:1.5:
It is uniformly mixed in 1.5 addition solvent NMP and is prepared into negative electrode slurry 1；By the Delanium of commercialization and conductive agent acetylene black, bonding
Agent butadiene-styrene rubber, thickener sodium carboxymethylcellulose are according to mass ratio 97:1:0.8:It is mixed in 1.2 addition solvent deionized waters equal
It is even to be prepared into negative electrode slurry 2；Negative electrode slurry 2 is uniformly coated on negative current collector copper foil, it is negative to continue one layer of coating later
Pole slurry 1 by drying, being cold-pressed, cutting, is prepared into cathode pole piece, the thickness of middle layer that wherein negative electrode slurry 2 is formed after drying
It is 200 μm to spend, and the thickness of cathode membrane that negative electrode slurry 1 is formed after drying is 10 μm.
(4) preparation of lithium ion battery
Anode pole piece and cathode pole piece are cut into the shape of requirement by the way of mechanical stamping, by the anode of well cutting
Pole piece, isolation film and cathode pole piece are alternately stacked, and hot pressing is compound, then are cut away the isolation film at abnormity with laser, shape
Into the naked battery core of level-one step abnormity.It repeats above step and prepares the naked battery core of two stage steps abnormity of different steps, then will prepare
The naked battery core of firsts and seconds step abnormity be stacked into the naked battery core of step abnormity.Then the naked battery core of special-shaped step is packed into packaging bag
Packaging realizes the assembling of naked battery core, then passes through the processes such as fluid injection, chemical conversion, molding, completes the preparation of special-shaped lithium ion battery.
Comparative example 4
Method according to embodiment 1 prepares lithium ion battery, difference lies in：
(1) preparation of cathode pole piece
By the Delanium of commercialization and conductive agent acetylene black, binding agent butadiene-styrene rubber, thickener sodium carboxymethylcellulose
According to mass ratio 97:1:0.8:It is uniformly mixed in 1.2 addition solvent deionized waters and is prepared into negative electrode slurry, later by negative electrode slurry
It is uniformly coated on negative current collector copper foil, by drying, being cold-pressed, cutting, is prepared into cathode pole piece, wherein negative electrode slurry dries
The thickness of cathode membrane formed after dry is 205 μm.
(4) preparation of lithium ion battery
Anode pole piece and cathode pole piece are cut into the shape of requirement by the way of mechanical stamping, by the anode of well cutting
Pole piece, isolation film and cathode pole piece are alternately stacked, and hot pressing is compound, then are cut away the isolation film at abnormity with laser, shape
Into the naked battery core of level-one step abnormity.It repeats above step and prepares the naked battery core of two stage steps abnormity of different steps, then will prepare
The naked battery core of firsts and seconds step abnormity be stacked into the naked battery core of step abnormity.Then the naked battery core of special-shaped step is packed into packaging bag
Packaging realizes the assembling of naked battery core, then passes through the processes such as fluid injection, chemical conversion, molding, completes the system of special-shaped step lithium ion battery
It is standby.
The performance test of lithium ion battery will be illustrated next.
(1) volume test of lithium ion battery
At 25 DEG C, constant-current charge, charge cutoff voltage 4.4V, later with 4.4V perseverances are carried out with the current density of 2.5A
Pressure charges to current density as 0.5A, then using the current density constant-current discharge of 2.5A to voltage as 3.0V, obtained discharge capacity
Capacity C as lithium ion batteryn(i.e. 100%SOC).
(2) the rate of charge test of lithium ion battery
At 25 DEG C, with 0.5CnCurrent density lithium ion battery is charged into blanking voltage as 4.4V, later with 4.4V
Constant-voltage charge to current density is 0.05Cn, then with 0.5CnCurrent density constant-current discharge to voltage be 3.0V, then with 5Cn's
Current density charges to blanking voltage as 4.4V, later using 4.4V constant-voltage charges to current density as 0.05Cn, lithium ion battery
5CnRate of charge=5CnCapacity/(5C of lower constant-current chargenCapacity+the 5C of lower constant-current chargenThe capacity of lower constant-voltage charge).
(3) the cycle performance test of lithium ion battery
Respectively at 12 DEG C and 45 DEG C, with 5CnThe density of charging current and 1CnDischarge current density to lithium ion battery
Charge and discharge cycles test is carried out, voltage range is set as 3.0V~4.4V, and the capacity after record lithium ion battery repeatedly recycles is protected
Holdup and thickness swelling.
(4) the hot tank safety test of lithium ion battery
At being placed in 25 DEG C in 12 DEG C of cycles lithium ion battery of 20 weeks, later with 0.5CnCurrent density by lithium ion
Battery is completely charged to 4.4V, be placed in 150 DEG C of insulating box and store 30min, seen whether burning.Not burn as logical
The standard of superheated header test.
The performance test results of table 1 embodiment 1-6 and comparative example 1-4
As can be seen from Table 1, the cathode pole piece that comparative example 1 is prepared using simple lithium titanate, the appearance of lithium ion battery
It measures as 3.20Ah, capacity retention ratio of the lithium ion battery after 12 DEG C of cycles 20 weeks is 91%, capacity of 45 DEG C of cycles after 500 weeks
Conservation rate is 83%, thickness swelling 23%, and 150 DEG C of hot tank experiment percent of pass are 10/10, lithium ion battery high/low temperature cycle
Capacity attenuation and high temperature thickness swelling are serious, and the rate of charge of lithium ion battery is also poor.
The lithium titanate coated by lanthanum strontium manganese oxygen is used in embodiment 1-4, lanthanum strontium manganese oxygen is as a kind of perovskite structure
Material, itself has very superior electron conduction and higher oxygen reduction activity, and less with electrolyte side reaction, adopts
With the lithium titanate of its cladding, have and followed without cathode analysis lithium and heat-staple advantage, the high/low temperature that lithium ion battery can be improved
Capacity retention ratio after ring simultaneously inhibits the thickness swelling after high temperature circulation, improves the hot tank security performance of lithium ion battery and big
Multiplying power quick charge, while lithium ion battery still keeps higher capacity.In comparative example 2, if the cladding ratio of lanthanum strontium manganese oxygen
Example is excessively high, and since lanthanum strontium manganese oxygen can not store lithium ion in itself, ionic conductivity is relatively low, therefore can reduce the appearance of lithium ion battery
Amount.
Further, in embodiment 5, using the lithium titanate of lanthanum strontium manganese oxygen cladding and the composite negative pole of Delanium formation
Pole piece, while electrical property is met, the capacity of lithium ion battery is increased dramatically.
Further, after in embodiment 6 using the design of special-shaped step lithium ion battery, the residue of lithium ion battery
Space is further utilized, and capacity further gets a promotion.In comparative example 3, using commercialized lithium titanate and artificial stone
The composite negative pole pole piece that ink is formed, although lithium ion battery has higher capacity, the big multiplying power of lithium ion battery is quick
Charging, high/low temperature cycle performance and hot tank security performance are poor.Similarly, in comparative example 4, using only commercialized people
The cathode pole piece of graphite formation is made, although lithium ion battery has higher capacity, the big multiplying power of lithium ion battery is quick
Charging, high/low temperature cycle performance and hot tank security performance are poor.
Claims (10)
1. a kind of negative electrode active material, which is characterized in that the negative electrode active material includes：
Lithium titanate kernel；And
It is coated on the clad of lithium titanate core surface；
The clad is selected from lanthanum strontium manganese oxygen.
2. negative electrode active material according to claim 1, which is characterized in that the negative electrode active material is by lithium titanate kernel
And the clad composition of lithium titanate core surface is coated on, the clad is selected from lanthanum strontium manganese oxygen.
3. negative electrode active material according to claim 1 or 2, which is characterized in that the general formula of the lanthanum strontium manganese oxygen is
LaxSryMnzO3, wherein, 0.5≤x≤0.9,0.1≤y≤0.5 and x+y+z=2, it is preferable that 0.67≤x≤0.8,0.2≤y
≤ 0.33 and x+y+z=2.
4. negative electrode active material according to claim 3, which is characterized in that the lanthanum strontium manganese oxygen is selected from La0.7Sr0.3MnO3、
La0.8Sr0.2MnO3、La0.67Sr0.33MnO3One or more of.
5. negative electrode active material according to claim 1 or 2, which is characterized in that
The quality of clad is the 0.1%~10% of the quality of lithium titanate kernel.
6. a kind of preparation method of negative electrode active material, is used to prepare the negative electrode active material described in any one of claim 1-5
Material, which is characterized in that including step：
(1) lanthanum salt, strontium salt, manganese salt are dissolved in deionized water respectively and is mixed to form mixed solution；
(2) chelating agent is added in into mixed solution and buffer carries out gelation reaction to obtain lanthanum strontium manganese oxygen wet gel；
(3) lithium titanate powdery is added in into lanthanum strontium manganese oxygen wet gel, drying, sintering, that is, complete negative electrode active material later
It prepares, wherein, obtained negative electrode active material includes lithium titanate kernel and is coated on the clad of lithium titanate core surface,
The clad is selected from lanthanum strontium manganese oxygen.
7. a kind of cathode pole piece, including：
Negative current collector；And
Cathode membrane is set on negative current collector and including negative electrode active material, conductive agent and bonding agent；
It is characterized in that, the negative electrode active material includes negative electrode active material according to any one of claims 1-5.
8. according to the cathode pole piece described in claim 7, which is characterized in that the cathode pole piece further includes：Middle layer, setting
Between negative current collector and cathode membrane, and including：
One or more of native graphite, Delanium, soft carbon, hard carbon；
Binding agent；And
Optional conductive agent.
9. a kind of battery core, which is characterized in that including the cathode pole piece according to any one of claim 7-8.
10. battery core according to claim 9, which is characterized in that the battery core is special-shaped step battery core.
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