CN103797621B - Bimodal pattern negative electrode active material and lithium secondary battery comprising it - Google Patents
Bimodal pattern negative electrode active material and lithium secondary battery comprising it Download PDFInfo
- Publication number
- CN103797621B CN103797621B CN201380001741.5A CN201380001741A CN103797621B CN 103797621 B CN103797621 B CN 103797621B CN 201380001741 A CN201380001741 A CN 201380001741A CN 103797621 B CN103797621 B CN 103797621B
- Authority
- CN
- China
- Prior art keywords
- active material
- negative electrode
- electrode active
- primary particle
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 present invention provides a kind of negative electrode active material, it includes the compounds of following chemical formula 1, the negative electrode active material may be implemented high-density electrode and can improve the adhesion strength and high rate capability to the electrode simultaneously, wherein the compound of the chemical formula 1 includes the first primary particle and secondary, and first primary particle is 5:95~50:50, [chemical formula 1] Li to the ratio of the secondaryxMyOzWherein M is independently selected from any one element or its two or more mixture in following element: titanium (Ti), tin (Sn), copper (Cu), lead (Pb), antimony (Sb), zinc (Zn), iron (Fe), indium (In), aluminium (Al) and zirconium (Zr)；And x, y and z are determined according to the oxidation number of M.
Description
Technical field
The present invention relates to bimodal pattern negative electrode active material and comprising its lithium secondary battery, more particularly, the present invention relates to
Negative electrode active material and lithium secondary battery comprising it, wherein the particle for constituting the negative electrode active material include primary particle and
The mixture of secondary.
Background technique
Lithium ion secondary battery is a kind of principle that battery is generated when moving between positive electrode and negative electrode by lithium ion
The secondary cell of operation.The component of lithium secondary battery can widely be divided into anode, cathode, diaphragm and electrolyte.At described group
Positive electrode active materials and negative electrode active material can have the following structure in point: the lithium in ionic condition can be in active material
Middle insertion and deintercalation, and charge and discharge can be implemented by reversible reaction.
Typically, lithium metal is used as to the negative electrode active material of lithium secondary battery.However, because due to following
And there is the danger of explosion: battery short circuit occurs due to forming dendritic crystal cognition when using lithium metal, so extensively
Carbon-based material is used as negative electrode active material to replace lithium metal by ground.
The example of carbon-based material can be crystalline carbon such as graphite and artificial graphite and amorphous carbon such as soft carbon and hard carbon.
The amorphous carbon can have high capacity, but irreversibility can be got higher during charge and discharge process.Typically graphite is used as
Crystalline carbon, and the graphite is limited with high theoretical capacity.However, even if crystalline carbon or amorphous carbon have relatively high theory
Capacity, but theoretical capacity is only about 380mAh/g.Crystalline carbon or nothing are difficult with during developing high-capacity lithium battery as a result,
Carbon shape as cathode.
Therefore, in order to develop with battery performance such as rapid charge and electric discharge and the lithium ion secondary battery of long-life,
Recently the metal oxide for using Li-Ti oxide (LTO), spinel structure has been accumulated as negative electrode active material
Pole research.
Since LTO will not generate solid electrolyte interface (SEI) layer, so LTO compares stone in terms of generating irreversible capacity
Ink is excellent, and even if still has excellent invertibity, institute for the insertion and deintercalation of lithium ion during repeating charge and discharge cycles
Stating solid electrolyte interface (SEI) layer is the graphite base negative electrode active material due to it is now commonly used in lithium ion secondary battery
Secondary response between electrolyte and generate.Further, since LTO has metastable structure, so it is that can open up
The hope material of the long-life performance of existing secondary cell.
LTO can be divided to is two classes, and wherein LTO is only made of primary particle and LTO is made of secondary, described
Secondary is formed by the reunion of primary particle.In the case where LTO is made of primary particle, closed when LTO has
It is not problem to the adhesion strength of electrode when suitable partial size, but charge-discharge characteristic can deteriorate.Therefore, in order to overcome this disadvantage simultaneously
Improve high rate capability and make preparation LTO partial size be 300nm or less in the case where, due to specific surface area increase and produce
The limitation of the raw process aspect during preparing slurry.In addition, forming secondary grain to overcome the limitation of nanometer primary particle
In the case where son, the limitation can be improved.However, needing a large amount of adhesives to keep the adhesion strength to electrode.Due to viscous
Mixture may act as the resistive element of electrode, so the total energy density of battery eventually declines.
In addition, as it is necessary to have the batteries of high-energy density for the promotion of function of the device for using battery.In order to meet
The requirement needs to increase the technology of the energy of per unit volume.It is every by improving in order to improve the energy of per unit volume
The amount of the electrode material of unit volume coating can form high-density electrode, it is possible thereby to form the battery with high-energy.
Therefore, it is necessary to a kind of, and the active material of electrode density can be improved in the amount by reducing adhesive.
Summary of the invention
Technical problem
According to an aspect of the present invention, the present invention provides the height of a kind of high rate capability that may insure battery and electrode
The negative electrode active material of density and the adhesion strength to electrode.
Technical solution
According to aspects of the present invention, a kind of bimodal pattern negative electrode active material is provided and comprising the bimodal pattern negative electrode active
The cathode and lithium secondary battery of material, wherein the particle for constituting the negative electrode active material includes the first primary particle and secondary grain
The mixture of son.
Advantageous effects
Using the negative electrode active material for wherein mixing the first primary particle and secondary with proper ratio, thus not only may be used
To obtain high-density electrode, and the adhesion strength and high rate capability to electrode can also be improved simultaneously.
Detailed description of the invention
Fig. 1 is the schematic diagram for showing the negative electrode active material of embodiment of the present invention, wherein primary by proper amount of first
Particle is mixed with secondary；
Fig. 2 is the schematic diagram for showing negative electrode active material, wherein a large amount of first primary particles are mixed with secondary；With
And
Fig. 3 is the figure that show electrode density changes with the mixing ratio of the first primary particle, and first primary particle is used for
In the cathode of the embodiment 7~12 of embodiment of the present invention.
Specific embodiment
The present invention relates to the negative electrode active material of the compound comprising following chemical formula 1, the wherein compound packet of chemical formula 1
Containing the first primary particle and secondary, and the first primary particle is 5:95~50:50 to the weight ratio of secondary.
[chemical formula 1]
LixMyOz
Wherein M is the mixture independently selected from any one element or two or more elements in following element: titanium
(Ti), tin (Sn), copper (Cu), lead (Pb), antimony (Sb), zinc (Zn), iron (Fe), indium (In), aluminium (Al) and zirconium (Zr)；And x, y and z
It is determined according to the oxidation number of M.
According to an embodiment of the invention, using wherein being mixed with proper ratio to the first primary particle and secondary
The negative electrode active material of conjunction, thus not only available high-density electrode, but also can improve simultaneously to the adhesion strength of electrode and
High rate capability.
Fig. 1 is the schematic diagram for showing the negative electrode active material of embodiment of the present invention, wherein primary by proper amount of first
Particle is mixed with secondary, and Fig. 2 is the schematic diagram for showing negative electrode active material, wherein by a large amount of first primary particles and time
Grade particle mixing.
With reference to Fig. 1 and 2, in two kinds for wherein mixing proper amount of first primary particle and mixing a large amount of first primary particles
In situation, the first primary particle can fill the hole between secondary.However, as shown in fig. 1 to the first primary particle
In the case where being properly mixed with secondary, it can meet simultaneously in terms of adhesion strength and high rate capability and electrode density
Optimum performance.
According to an embodiment of the invention, average grain diameter (the D of the first primary particle50) it is 10nm~3 μm, Ke Yiwei
100nm~1 μm, and for example can be 100nm~700nm.
In the case where the average grain diameter of the first primary particle is less than 10nm, there are practical difficulties in terms of processing, and
In the case where average grain diameter is greater than 3 μm, since the diameter of the first primary particle is relatively large, so it is not expected that due to the first primary
Particle and the effect for improving high rate capability.
It is only made of the first primary particle in lithium metal oxide particle and is used as the negative electrode active material of lithium secondary battery
In the case where, the adhesion strength to electrode is not problem, but charge-discharge characteristic can deteriorate.The first primary particle can be prepared to have
Smaller diameter, to overcome above-mentioned limitation.However, in this case, since the raising of specific surface area can prepare the slurry phase
Between exist in process aspect and limit, such as lead to that increased production cost and conductivity declines due to using a large amount of adhesives.
Therefore, according to an embodiment of the invention, in order to overcome above-mentioned limit in the case where the first primary particle is used only
System, using wherein with proper ratio mixing lithium metal oxide the first primary particle and secondary negative electrode active material,
Thus not only available highdensity electrode, but also the adhesion strength and high rate capability to electrode can be improved simultaneously.
According to an embodiment of the invention, the first primary particle is 5:95~50:50 (weight to the mixing ratio of secondary
Than), and can be 5:95~40:60.
When the amount of the first primary particle is greater than above range, electrode density can be improved, but the adhesion strength to electrode and two
The high rate capability of primary cell can decline.In addition, when the amount of the first primary particle is less than above range, between secondary
Hole will not be filled up by the first primary particle, thus without realization desired effects of the invention.
Lithium metal oxide particle according to embodiments of the present invention is secondary, and more than two of them second is primary
Particle is reunited, and can be small porous particle.
According to an embodiment of the invention, when more than two second primary particles occur to reunite to form secondary,
It is non-aggregated and the case where individually included that specific surface area is relatively shorter than wherein the second primary particle.As a result, to the adhesion strength of electrode
It can be more preferable.
In the present invention, the interior porosity of secondary is 3%~15%, and its average grain diameter (D50) can for 5 μm~
30 μm, and its specific surface area (Brunauer-Emmett-Teller (Brunauer-Emmett-Teller) (BET)) can be 1m2/g
~15m2/g。
In the case where the interior porosity of secondary is less than 3%, it is contemplated that following fact and exist in terms of processing real
Border is difficult: forming secondary by the reunion of the second primary particle.It is greater than 15% in the interior porosity of wherein secondary
In the case where, keep the amount of adhesive required for the appropriate adhesion strength to electrode will increase, thus conductivity decline and capacity
It reduces.
According to an embodiment of the invention, the interior porosity of secondary can be defined as:
The volume in interior porosity=per unit mass hole/(than the volume in volume+per unit mass hole)
The measurement of interior porosity is not particularly limited.According to an embodiment of the invention, for example by using adsorbed gas
Body such as nitrogen and BELSORP (BET instrument) the measurement internal void manufactured by Japanese Bayer Corp (BEL Japan, Inc)
Rate.
Similarly, the specific surface area (BET) of secondary can be 1m2/ g~15m2/g。
In the present invention, the specific surface area of the first primary particle and secondary can be measured by BET method.For example, can
To use porosity measurement analyzer (the Belsorp-II mini manufactured by Japanese Bayer Corp) according to nitrogen adsorption-
Flow method measures specific surface area by 6 BET methods.
Average grain diameter (the D of secondary50) it is 5 μm~30 μm, and can be 5 μm~12 μm.Constitute the of secondary
Average grain diameter (the D of two primary particles50) it is 100nm~1 μm, and can be 100nm~700nm.
It in the present invention, can be by average grain diameter (D50) it is defined as the partial size in accumulation particle diameter distribution at 50%.Example
Such as, the first and second primary particle according to embodiments of the present invention and secondary can be measured by using laser diffractometry
Average grain diameter (D50).Laser diffractometry can usually measure submicron order to several millimeters of partial size, and high repeat may be implemented
Property and high-resolution result.
Typically, because the conductivity of lithium metal oxide is low, advantageously have small average grain diameter to apply
In the battery of quick charge.However, in this case, due to the increase of specific surface area as described above, so needing a large amount of bondings
Agent is to keep suitable electrode adhesion strength.
That is, in the case where the average grain diameter of secondary is less than 5 μm, since the specific surface area of negative electrode active material increases
Greatly, so electrode conductivity as a result can occur in order to keep the amount of adhesive required for desired electrode adhesion strength will increase
Decline.In the case where the average grain diameter of secondary is greater than 30 μm, quick charge characteristic can be deteriorated.
It therefore, is 5 μm~30 μm comprising average grain diameter in high density negative electrode active material according to embodiments of the present invention
Secondary in the case where, in order to keep the amount of adhesive required for electrode adhesion strength that can not only decline, but also pass through increasing
Add area that can also improve quick charge characteristic, wherein being possible with directly reacting for lithium (Li) ion.
In the case where the average grain diameter of the second primary particle is less than 100nm, it is less than the mistake of 100nm in preparation average grain diameter
It has difficulties in journey, and because the porosity of the secondary not only formed by the reunion of the second primary particle declines, and
And lithium ion is difficult to penetrate into secondary, so the second primary particle in discharge and recharge reaction in secondary will not sink
It forms sediment.In the case where the average grain diameter of the second primary particle is greater than 1 μm, the formative of secondary can decline, and be difficult to control
It is granulated.
According to an embodiment of the invention, the compound of chemical formula 1 may include selected from one of following substance or more
Kind Li-Ti oxide: Li4Ti5O12、Li2TiO3、Li2Ti3O7And the compound of following chemical formula 2:
[chemical formula 2]
Lix’Tiy’O4
Wherein 0.5≤x '≤3, and 1≤y '≤2.5.
In addition, the compound of chemical formula 2 can be LiTi2O4。
In the method for preparing negative electrode active material according to an embodiment of the present invention, lithium gold is prepared by typical method first
Belong to the first primary particle of oxide, and lithium gold can be formed by individual prilling after preparing the second primary particle
Belong to the secondary of oxide particle.However typically, using preparing the second primary particle by single technique and while to the
The method that two primary particles are reunited can prepare secondary.Thereafter, the first primary particle and secondary by that will prepare
Uniform particle mixing can prepare negative electrode active material according to the present invention.
In the method for preparing negative electrode active material according to an embodiment of the present invention, lithium salts and metal oxide are added to
Volatile solvent is stirred and is sintered.Then, by grinding and sieving available first primary particle.
Specifically, lithium salts is dissolved in volatile solvent, is then added to it while agitating as metal oxide
Titanium oxide.Then, about 500 DEG C~about 1000 DEG C at a temperature of the solution thus prepared sintering is about 1 hour~about 15 small
When.Thereafter, the first primary particle can be prepared by grinding and sieving.
Herein, volatile solvent can be such as water, acetone or alcohol.
In addition, lithium salts can be the mixture of any one substance or two or more substances in following substance: hydrogen
Lithia, lithia and lithium carbonate.
In addition, in the method for preparing negative electrode active material according to an embodiment of the present invention, the method for preparing secondary
It may include: to prepare precursor solution by adding lithium salts and metal oxide into volatile solvent and stir；By the precursor
Solution is supplied to the interior of spray dryer；And the precursor solution is sprayed and is dried in the interior.
In this case, by selecting and being used to prepare identical material in the first primary particle, lithium salts, gold can be used
Belong to oxide and volatile solvent.
According to an embodiment of the invention, after preparing the second primary particle, it, can be with shape by individual prilling
At the secondary of lithium metal oxide particle.It however typically, can use and the second primary particle prepared by single technique
And the method reunited simultaneously to the second primary particle prepares secondary.
The example of the above method may include spray drying process.Hereinafter, spray drying process will be used as example to root
It is illustrated according to the method for embodiment of the present invention preparation secondary.
Preparation method according to embodiments of the present invention may include being supplied to precursor solution to be included in spray dryer
In interior.
Typically used as spray dryer can be used as above-mentioned spray dryer, it is dry that ullrasonic spraying can be used for example
Device, air nozzle spray dryer, ultrasonic nozzle spray dryer, filter expansion aerosol generator or electrostatic spray are dry
Device.However, this cannot be limited the invention to.
According to an embodiment of the invention, precursor solution to indoor feed rate can be 10ml/ minutes~1000ml/
Minute.In the case where feed rate is less than 10ml/ minutes, the average grain diameter of the second primary particle of reunion can decline, thus
It is difficult to form high density secondary.In the case where feed rate is greater than 1000ml/ minutes, due to the average grain of secondary
Diameter opposite can increase, so being difficult to realize desired high rate capability.
In addition, the method for preparing secondary according to an embodiment of the present invention may include spraying precursor solution indoors simultaneously
It is dry.
Precursor solution can be sprayed by the disk rotated at high speeds indoors, and can be sprayed in same indoor implementation and
It is dry.
In addition, passing through the flow velocity of the condition such as carrier gas of control spray drying, residence time in the reactor and internal pressure
Average grain diameter and interior porosity of the invention may be implemented in power.
According to an embodiment of the invention, can control the interior porosity of secondary by adjusting drying temperature, and
Can 20 DEG C~300 DEG C at a temperature of implement drying.However, for high density secondary, it can be in alap temperature
Degree is lower to implement drying.
According to an embodiment of the invention, by the first primary particle and secondary under the weight ratio of 5:95~50:50
It is mixed, can also be mixed under the weight ratio of 5:95~40:60, thus, it is possible to which the high rate performance for preparing battery is high
And the density of electrode is high and ensure negative electrode active material to the adhesion strength of electrode.In this case, in order to as well as possible
The first primary particle and secondary are mixed, by using typical polishing as at the beginning of planetary mill uniformly can mix first
Grade particle and secondary.
Total weight based on negative electrode active material can include real according to the present invention with the amount of 50 weight of weight %~100 %
Apply the lithium metal oxide comprising the first primary particle and secondary of scheme.Total weight lithium gold based on negative electrode active material
The case where amount for belonging to oxide is 100 weight % refers to the case where wherein negative electrode active material is only made of lithium metal oxide.
In secondary cell according to embodiments of the present invention, other than lithium metal oxide, negative electrode active material is also
May include selected from least one of following substance active material: carbon-based material is typically used in negative electrode active material；It crosses
Cross metal oxide；Silicon (Si) sill；And Sn sill.However, cannot be by the type limited to this of negative electrode active material.
The present invention also provides a kind of negative electrode active material feed composition comprising negative electrode active material, conductive agent and adhesive,
It can include negative electrode active material, conductive agent and adhesive with the weight ratio of 80:3:7~90:9:13.
The present invention also provides a kind of cathode comprising the negative electrode active material feed composition and include the lithium two of the cathode
Primary cell.
By the solvent of negative electrode active material feed composition containing a negative electrode active material and such as N-Methyl pyrrolidone (NMP)
Mixing, to be coated with negative electrode current collector, then by the negative electrode current collector being dried and roll-in can prepare cathode.
Negative electrode current collector is not particularly limited, as long as chemical change will not occur in the battery and have high conductivity i.e. for it
It can.The example of negative electrode current collector can be with are as follows: copper；Stainless steel；Aluminium；Nickel；Titanium；It is sintered carbon；It is carried out at surface through carbon, nickel, titanium or silver
The copper or stainless steel of reason；Aluminium-cadmium alloy etc..Tiny irregularity can be also formed on negative electrode current collector surface, to improve
The adhesion strength of negative electrode active material, and can be made with the diversified forms of such as film, piece, foil, net, porous body, foam or non-woven fabrics
With the negative electrode current collector.
Conductive agent is not particularly limited, as long as chemical change will not occur in the battery and have conductivity for it.It leads
The example of electric agent can be with are as follows: graphite such as natural graphite and artificial graphite；Carbon black class material for example acetylene black, Ketjen black, channel black,
Furnace black, lampblack and thermal crack black；Conductive fiber such as carbon fiber and metallic fiber；Metal powder such as carbon fluoride powder, aluminium powder
And nickel by powder；Conductive whiskers such as ZnOw and potassium titanate crystal whisker；Conductive metal oxide such as titanium oxide；Such as with conductive material
Polyphenylene derivatives etc..
The example of adhesive can for polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch,
Hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, ethylene-propylene-
Diene terpolymer (EPDM), the EPDM of sulfonation, butadiene-styrene rubber, fluorubber and various copolymers etc..
For example, being coated using anode sizing agent containing a positive electrode active material to anode current collector, then by just
The anode that can be prepared include in lithium secondary battery of the present invention is dried in pole current-collector.If desired, the anode sizing agent
It may include said components.
Particularly as positive electrode active materials, lithium secondary battery be can be used: lamellar compound such as lithium and cobalt oxides
(LiCoO2) or lithium nickel oxide (LiNiO2) or using one or more Transition metal substituteds compound；Lithium manganese oxide is such as
Li1+xMn2-xO4(wherein x is 0~0.33), LiMnO3、LiMn2O3And LiMnO2；Lithium Cu oxide (Li2CuO2)；The oxidation of vanadium
Object such as LiV3O8、LiFe3O4、V2O5And Cu2V2O7；By chemical formula LiNi1-xMxO2(wherein M be cobalt (Co), manganese (Mn), Al, Cu,
Fe, magnesium (Mg), boron (B) or gallium (Ga), and x be 0.01~0.3) indicate the site nickel (Ni) type lithium nickel oxide；By chemical formula
LiMn2-xMxO2(wherein M is Co, Ni, Fe, chromium (Cr), Zn or tantalum (Ta), and x is 0.01~0.1) or Li2Mn3MO8(wherein M is
Fe, Co, Ni, Cu or Zn) indicate complex Li-Mn-oxide；The LiMn that part Li is replaced by alkaline-earth metal ions2O4；Curing
Compounds；Or Fe2(MoO4)3.However, it is possible to use LiNixMn2-xO4(wherein x is 0.01~0.6), and can be used for example
LiNi0.5Mn1.5O4Or LiNi0.4Mn1.6O4.I.e., in the present invention it is possible to will have due to the high potential of negative electrode active material
The spinel lithium manganese composite oxide LiNi of opposite high potentialxMn2-xO4(wherein x is 0.01~0.6) is used as positive electrode active materials.
The present invention also provides as the battery module of element cell and include the battery module comprising lithium secondary battery
Battery pack.
Any battery case being typically used in this field may select for for the battery case in the present invention.The secondary electricity of lithium
The shape in pond with its purposes variation there is no limit, can be used for example and utilize the cylindrical type of tank, prismatic, pouch-type or coin
Type.
Lithium secondary battery according to the present invention can be not only used for also can be used in the battery unit as midget plant power supply
Make the element cell in the medium-sized and large-sized battery module comprising multiple battery units.Medium-sized and large-scale plant preferred embodiment can
Think electric vehicle, hybrid electric vehicle, plug-in hybrid electric vehicle or power storage system, but cannot will be medium-sized and large-scale
Device limited to this.
Hereinafter, the present invention will be more fully described according to specific embodiment.However, the present invention can be to be permitted
More different forms are implemented and should not be construed as being limited to embodiment described herein.
Embodiment
Preparation example 1: the first primary particle of preparation
To LiOHH under the molar ratio of 4:52O and TiO2(anatase) is mixed.Mixture is dissolved in pure water,
Then solution is stirred, and is sintered at 750 DEG C about 3 hours.Average grain diameter (D is prepared for by grinding and sieving50) be
The first primary particle of 700nm.
Preparation example 2: preparation secondary
To LiOHH under the molar ratio of 4:52O and TiO2(anatase) is mixed.Mixture is dissolved in pure water,
Then solution is stirred.In this case, the ratio of total solid material is defined as comprising in total solid in the solution
Tolerant weight is prepared for precursor solution to the ratio between the total weight of solution, and by the way that solid content is adjusted to 30% and is stirred.
Precursor solution is supplied to the room of spray dryer (being manufactured by Ai Yin System Co., Ltd (EIN SYSTEMS, Co., Ltd.))
It is interior.Then, precursor solution and drying are sprayed indoors.Including 130 DEG C drying temperature ,~20mbar internal pressure and
Under conditions of 30ml/ minutes feed rates implement spray drying, then by 800 DEG C in air to thus obtained
Precursor is sintered, and is prepared for the Li with 5.4 μm of average grain diameters and 3.5% interior porosity4Ti5O12Secondary.
Embodiment 1
By using planetary mill with the weight ratio of 5:95 to the first primary particle for being prepared in preparation example 1 and 2 and
Secondary has carried out mixing to prepare negative electrode active material.
Embodiment 2
Other than mixing the first primary particle and secondary with the weight ratio of 10:90, with side same as Example 1
Formula is prepared for negative electrode active material.
Embodiment 3
Other than mixing the first primary particle and secondary with the weight ratio of 20:80, with side same as Example 1
Formula is prepared for negative electrode active material.
Embodiment 4
Other than mixing the first primary particle and secondary with the weight ratio of 30:70, with side same as Example 1
Formula is prepared for negative electrode active material.
Embodiment 5
Other than mixing the first primary particle and secondary with the weight ratio of 40:60, with side same as Example 1
Formula is prepared for negative electrode active material.
Embodiment 6
Other than mixing the first primary particle and secondary with the weight ratio of 50:50, with side same as Example 1
Formula is prepared for negative electrode active material.
Comparative example 1
Negative electrode active material is prepared for by the way that the first primary particle obtained in preparation example 1 is used only.
Comparative example 2
Negative electrode active material is prepared for by the way that secondary obtained in preparation example 2 is used only.
Comparative example 3
Other than mixing the first primary particle and secondary with the weight ratio of 60:40, with side same as Example 1
Formula is prepared for negative electrode active material.
Comparative example 4
Other than mixing the first primary particle and secondary with the weight ratio of 3:97, with side same as Example 1
Formula is prepared for negative electrode active material.
Embodiment 7
<preparing cathode>
Using the weight ratio of 84:6:10 by as the negative electrode active material of the embodiment 1 of negative electrode active material, as conductive agent
Carbon black (Super P) and the PVdF as adhesive mixed, then mixture is added to the N- first as solvent
Base -2-Pyrrolidone is to prepare slurry.65 μm of thickness is applied to a surface of copper collector using the slurry of preparation, so
Dry and roll-in afterwards.Then, cathode is prepared for by being punched into predetermined size.
<preparing lithium secondary battery>
It is non-aqueous to prepare that mixing has been carried out to ethylene carbonate (EC) and diethyl carbonate (DEC) with the volume ratio of 30:70
Electrolyte solvent, and it is added to it LiPF6To prepare 1M LiPF6Non-aqueous electrolytic solution.
In addition, it is anode that lithium foil, which is used as to electrode, and between two electrodes by polyalkene diaphragm setting.Then, lead to
It crosses injection electrolyte solution and is prepared for coin-like half cells.
Embodiment 8~12 and comparative example 5~8
By using the negative electrode active material obtained in embodiment 2~6 and comparative example 1~4, it is prepared for the following table 1
Composition cathode.
[table 1]
| Catalogue | Cathode forms (negative electrode active material: conductive agent: adhesive) (weight ratio) |
| Embodiment 7 | 84 (the first primary particles 5: secondary 95): 6:10 |
| Embodiment 8 | 84 (the first primary particles 10: secondary 90): 6:10 |
| Embodiment 9 | 84 (the first primary particles 20: secondary 80): 6:10 |
| Embodiment 10 | 84 (the first primary particles 30: secondary 70): 6:10 |
| Embodiment 11 | 84 (the first primary particles 40: secondary 60): 6:10 |
| Embodiment 12 | 84 (the first primary particles 50: secondary 50): 6:10 |
| Comparative example 5 | 84 (only the first primary particles): 6:10 |
| Comparative example 6 | 84 (only secondarys): 6:10 |
| Comparative example 7 | 84 (the first primary particles 60: secondary 40): 6:10 |
| Comparative example 8 | 84 (the first primary particles 3: secondary 97): 6:10 |
Experimental example 1
<adhesion strength measurement>
Using the cathode for preparing during the lithium secondary battery of preparation embodiment 7~12 and comparative example 5~8, measure pair
The adhesion strength of cathode.The measurement of adhesion strength is implemented using 180 ° of commonly known disbonded tests.It the results are shown in the following table 2
In.
Experimental example 2
<high rate capability analysis>
In order to analyze embodiment 7~12 and comparative example 5~8 lithium secondary battery high rate capability, pass through sequentially will
It is charged and discharged multiplying power and is changed to 0.1C, 0.2C, 0.5C, 1C, 0.2C, 2C, 0.2C, 5C, 0.2C and 10C respectively to lithium secondary battery
High rate capability evaluated.In this case, end of charge voltage is set as 1.0V, and final discharging voltage is set
It is set to 2.5V.The high rate capability of each lithium secondary battery is expressed as the capacity measured at 10C relative at 0.1C
The percent value of capacity.
It the results are shown in the following table 2.
[table 2]
As shown in table 2, in the case where Li-Ti oxide being used in cathode in such as embodiment 7~12, the lithium
Titanium oxide is formed and mixing to the first primary particle and secondary, it has been confirmed that adhesion strength and high power
Rate performance improves simultaneously.
However, even if wherein as used first primary particle and secondary wherein with mixing in comparative example 7 and 8
In the case where the negative electrode active material of particle, can still it confirm, it, cannot be simultaneously when using the primary particle of excess or relatively small amount
Meet the adhesion strength and high rate capability with 7~12 phase same level of the embodiment of the present invention.
The case where in such as comparative example 5 by only active material is used as by the Li-Ti oxide that the first primary particle is formed
In, it has been confirmed that adhesion strength significantly improves, and in the lithium titanyl wherein as will be only formed by secondary in comparative example 6
In the case where object is used in cathode, it has been confirmed that high rate capability declines.
According to experimental example 1 and 2 as a result, it is inferred that the first primary particle high rate capability show and following fact
Related: compared with secondary, the first primary particle is during showing high rate capability in Li-Ti oxide and electrolyte
There is excellent accessibility between lithium ion.Further, since the specific surface area of secondary is lower than only by the first primary particle structure
At Li-Ti oxide specific surface area, it is believed that it is related with electrode adhesion strength.
Experimental example 3
<electrode density>
Using the cathode prepared during the lithium secondary battery of preparation embodiment 7~12 and comparative example 5~8, to electrode
Electrode density is measured.It the results are shown in the following table 3, and by electrode density with the ratio of the first primary particle of mixing
Variation it is shown in Figure 3.
[table 3]
| Catalogue | Electrode forms (active material: conductive agent: adhesive) | Electrode density [g/cc] |
| Embodiment 7 | 84 (the first primary particles 5: secondary 95): 6:10 | 1.89 |
| Embodiment 8 | 84 (the first primary particles 10: secondary 90): 6:10 | 1.91 |
| Embodiment 9 | 84 (the first primary particles 20: secondary 80): 6:10 | 1.93 |
| Embodiment 10 | 84 (the first primary particles 30: secondary 70): 6:10 | 1.94 |
| Embodiment 11 | 84 (the first primary particles 40: secondary 60): 6:10 | 1.95 |
| Embodiment 12 | 84 (the first primary particles 50: secondary 50): 6:10 | 1.95 |
| Comparative example 5 | 84 (only the first primary particles): 6:10 | 2.1 |
| Comparative example 6 | 84 (only secondarys): 6:10 | 1.8 |
| Comparative example 7 | 84 (the first primary particles 60: secondary 40): 6:10 | 1.96 |
| Comparative example 8 | 84 (the first primary particles 3: secondary 97): 6:10 | 1.8 |
As shown in table 3, in the case where Li-Ti oxide being used in cathode in such as embodiment 7~12, described
The first primary particle is compared with specific blend in Li-Ti oxide and secondary is mixed, it has been confirmed that with comparative example 6
~8 compare, and electrode density significantly improves.
In addition, as shown in Figure 3, with reference to the cathode in such as comparative example 6 without the first primary particle and as only having in comparative example 5
There is the electrode density (in the graph in fig. 3, the calculated value that dotted line is mixed electrode density) of the cathode of the first primary particle, it can be true
Recognize, compared with the calculated value of mixed electrode density, the electrode density of embodiment 7~12 be increased dramatically.
However, the increase of electrode density declines with the raising of the ratio of the first primary particle of mixing, thus really
Recognize, the Li-Ti oxide of first primary particle wherein with mixing and secondary (is used as in the cathode and bears by cathode
Pole active material) electrode density, when the ratio of the first primary particle is close to 50%, with only with primary particle cathode and
Only the average value of the electrode density of the cathode with secondary is similar.
That is, the Li-Ti oxide of first primary particle wherein with mixing and secondary is used as negative electrode active
In the case where material, even if can still realize the effect for improving electrode density in the case where wherein mixing a small amount of first primary particle
Fruit.
Cathode about embodiment 7~12 is (wherein by the lithium titanyl of first primary particle and secondary with mixing
Compound is used as negative electrode active material), electrode density improves.It is inferred that the reason of situation be by the fact that caused by: it is logical
It crosses using the hole between the Li-Ti oxide filling secondary with the first primary particle structure, electrode density can be improved,
Hole between the secondary is generated when forming electrode as active material by the way that secondary is used only.
That is, when will wherein mix the first primary particle and secondary embodiment 7~12 electrode and secondary cell with
When the electrode and secondary cell of comparative example 7 and 8 compare, it has been confirmed that in order to be realized most in terms of adhesion strength and high rate capability
Best performance can mix the first primary particle and secondary with proper ratio.
Industrial applicability
Due to using wherein with the negative electrode active material of proper ratio mixing the first primary particle and secondary, so not
Only available high-density electrode can also improve adhesion strength and high rate capability to electrode simultaneously.The negative electrode active as a result,
Material is suitable for lithium secondary battery.
Claims (14)
1. a kind of negative electrode active material, it includes
By the first primary particle of the compound that chemical formula 1 indicates；With
By the secondary for the compound that chemical formula 1 indicates, the interior porosity of the secondary is 3%~15%；
Wherein first primary particle is 30:70~40:60 to the weight ratio of the secondary,
Wherein the secondary is the aggregate of the second primary particle of more than two compounds indicated by chemical formula 1,
[chemical formula 1]
LixMyOz
Wherein M be the mixture independently selected from any one element or two or more elements in following element: Ti, Sn, Cu,
Pb, Sb, Zn, Fe, In, Al and Zr；And x, y and z are determined according to the oxidation number of M,
Wherein first primary particle and the secondary are formed separately, and are then uniformly mixed；
Wherein, the average grain diameter (D of first primary particle50) it is 10nm~3 μm, the average grain diameter (D of the secondary50)
It is 5 μm~30 μm.
2. negative electrode active material as described in claim 1 the, wherein average grain diameter (D of first primary particle50) it is 100nm
~1 μm.
3. negative electrode active material as described in claim 1 the, wherein average grain diameter (D of second primary particle50) it is 100nm
~1 μm.
4. negative electrode active material as described in claim 1 the, wherein average grain diameter (D of the secondary50) it is 5 μm~12 μ
m。
5. negative electrode active material as described in claim 1, wherein the compound of the chemical formula 1 includes in following substance
One or more Li-Ti oxides: Li4Ti5O12、Li2TiO3、Li2Ti3O7And the compound of following chemical formula 2:
[chemical formula 2]
Lix’Tiy’O4
Wherein 0.5≤x '≤3, and 1≤y '≤2.5.
6. negative electrode active material as claimed in claim 5, wherein the compound of the chemical formula 2 is LiTi2O4。
7. a kind of negative electrode active material feed composition, it includes the negative electrode active material of claim 1, conductive agent and adhesives.
8. negative electrode active material feed composition as claimed in claim 7, included in the negative electrode active material, described lead
The weight ratio of electric agent and described adhesive is 80:3:7~90:9:13.
9. negative electrode active material feed composition as claimed in claim 7, wherein the conductive agent be in following substance extremely
A kind of few substance: graphite；Carbon black；Conductive fiber；Metal powder；Conductive whiskers；Conductive metal oxide；It is derivative with polyphenylene
Object.
10. negative electrode active material feed composition as claimed in claim 7, wherein described adhesive be in following substance extremely
A kind of few substance: polyvinylidene fluoride, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, gathers polyvinyl alcohol
Vinyl pyrrolidone, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, ethylene-propylene diene terpolymer, sulfonation EPDM,
Butadiene-styrene rubber and fluorubber.
11. a kind of cathode, it includes the negative electrode active material feed compositions of claim 7.
12. a kind of lithium secondary battery, it includes the cathode of claim 11.
13. a kind of battery module, it includes the lithium secondary batteries of claim 12 as element cell.
14. a kind of battery pack, it includes the battery modules of claim 13.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120076901 | 2012-07-13 | ||
| KR10-2012-0076901 | 2012-07-13 | ||
| KR1020130081007A KR101558044B1 (en) | 2012-07-13 | 2013-07-10 | Bimodal type-anode active material and lithium secondary battery comprising the same |
| KR10-2013-0081007 | 2013-07-10 | ||
| PCT/KR2013/006222 WO2014010973A1 (en) | 2012-07-13 | 2013-07-11 | Bimodal-type anode active material and lithium secondary battery including same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103797621A CN103797621A (en) | 2014-05-14 |
| CN103797621B true CN103797621B (en) | 2019-07-23 |
Family
ID=50142910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380001741.5A Active CN103797621B (en) | 2012-07-13 | 2013-07-11 | Bimodal pattern negative electrode active material and lithium secondary battery comprising it |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5984026B2 (en) |
| KR (1) | KR101558044B1 (en) |
| CN (1) | CN103797621B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160181604A1 (en) * | 2014-09-12 | 2016-06-23 | Johnson Controls Technology Company | Systems and methods for lithium titanate oxide (lto) anode electrodes for lithium ion battery cells |
| US20160181603A1 (en) * | 2014-09-12 | 2016-06-23 | Johnson Controls Technology Company | Systems and methods for lithium titanate oxide (lto) anode electrodes for lithium ion battery cells |
| WO2016060300A1 (en) * | 2014-10-16 | 2016-04-21 | 주식회사 엘지화학 | Secondary battery anode comprising additive for improving low-temperature characteristic, and secondary battery comprising same |
| CN107530605B (en) * | 2015-04-22 | 2021-05-25 | 阿科玛股份有限公司 | Porous articles with submicron particles of polymeric binder |
| WO2017046858A1 (en) * | 2015-09-14 | 2017-03-23 | 株式会社 東芝 | Non-aqueous electrolyte cell and cell pack |
| KR102095008B1 (en) | 2016-09-13 | 2020-03-30 | 주식회사 엘지화학 | Negative electrode, secondary battery, battery module and battery pack comprising the same |
| JP7038956B2 (en) * | 2017-03-21 | 2022-03-22 | エルジー エナジー ソリューション リミテッド | Negative electrode active material with high output characteristics and lithium secondary battery containing it |
| KR102223723B1 (en) | 2017-05-12 | 2021-03-05 | 주식회사 엘지화학 | Negative eletrode active material, negative electrode comprising the negative electrode material and lithium secondarty battery comprising the negative electrode |
| WO2019009432A1 (en) * | 2017-07-07 | 2019-01-10 | 株式会社村田製作所 | Secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic apparatus |
| KR102386327B1 (en) * | 2017-08-11 | 2022-04-14 | 주식회사 엘지에너지솔루션 | Method of fabricating an electrode |
| CN109428076B (en) * | 2017-09-04 | 2023-04-11 | 三星电子株式会社 | Positive active material precursor, positive active material, method for producing positive active material, positive electrode, and lithium battery |
| KR102394797B1 (en) | 2017-09-12 | 2022-05-04 | 현대자동차주식회사 | An electrode composition comprising at least two electrode active materials having different crushing strength from each other and a lithium secondary battery containing the same |
| EP4138157A1 (en) * | 2020-04-16 | 2023-02-22 | SANYO Electric Co., Ltd. | Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN112781985A (en) * | 2020-12-29 | 2021-05-11 | 宁波杉杉新材料科技有限公司 | Method for testing bonding strength of secondary particles |
| CN116364868A (en) * | 2021-12-28 | 2023-06-30 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027617A (en) * | 2008-06-04 | 2011-04-20 | 松下电器产业株式会社 | Battery pack |
| CN102292854A (en) * | 2008-11-20 | 2011-12-21 | 株式会社Lg化学 | Electrode active material for secondary battery and method for preparing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002008658A (en) * | 2000-06-27 | 2002-01-11 | Toyota Central Res & Dev Lab Inc | Lithium titanium compound oxide for lithium secondary battery electrode active material, and its manufacturing method |
| JP2006054159A (en) * | 2004-07-15 | 2006-02-23 | Sumitomo Metal Mining Co Ltd | Anode active material for non-aqueous secondary battery, and its manufacturing method |
| KR101782184B1 (en) * | 2009-12-22 | 2017-09-26 | 이시하라 산교 가부시끼가이샤 | Lithium titanate, manufacturing method therefor, slurry used in said manufacturing method, electrode active material containing said lithium titanate, and lithium secondary battery using said electrod active material |
-
2013
- 2013-07-10 KR KR1020130081007A patent/KR101558044B1/en not_active Application Discontinuation
- 2013-07-11 CN CN201380001741.5A patent/CN103797621B/en active Active
- 2013-07-11 JP JP2014524956A patent/JP5984026B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027617A (en) * | 2008-06-04 | 2011-04-20 | 松下电器产业株式会社 | Battery pack |
| CN102292854A (en) * | 2008-11-20 | 2011-12-21 | 株式会社Lg化学 | Electrode active material for secondary battery and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101558044B1 (en) | 2015-10-07 |
| CN103797621A (en) | 2014-05-14 |
| JP2014527267A (en) | 2014-10-09 |
| JP5984026B2 (en) | 2016-09-06 |
| KR20140009928A (en) | 2014-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103797621B (en) | Bimodal pattern negative electrode active material and lithium secondary battery comprising it | |
| JP5175826B2 (en) | Active material particles and use thereof | |
| CN103733394B (en) | With highdensity negative electrode active material and preparation method thereof | |
| JP4740409B2 (en) | Lithium secondary battery for electric vehicle or hybrid vehicle | |
| KR101256641B1 (en) | Positive active material for lithium secondary battery and method for thereof | |
| CN1333475C (en) | Active material for cell and preparing method | |
| EP2498323A2 (en) | Positive active material, and electrode and lithium battery containing the material | |
| US9397335B2 (en) | Bimodal type anode active material and lithium secondary battery including the same | |
| JP7292655B2 (en) | Method for producing positive electrode active material precursor for lithium secondary battery | |
| CN100466340C (en) | Non-aqueous electrolyte rechargeable battery | |
| JP2022529817A (en) | A method for producing a positive electrode active material for a lithium secondary battery and a positive electrode active material for a lithium secondary battery produced by the above method. | |
| KR20190033214A (en) | Negavive electrode for lithium secondary battery, and lithium secondary battery comprising the same | |
| CN109904404B (en) | Lithium secondary battery negative electrode active material, method for preparing the same, and lithium secondary battery comprising the same | |
| WO2015111194A1 (en) | Electrical device | |
| JP2010251194A (en) | Positive electrode for battery and method of manufacturing the same | |
| JP7216824B2 (en) | Method for producing positive electrode active material precursor for lithium secondary battery | |
| JP2023551971A (en) | Cathode active material for lithium secondary batteries using waste cathode active material and its manufacturing method | |
| WO2023115289A1 (en) | Nickel-rich material and preparation method therefor, positive electrode plate, battery and electric equipment | |
| CN108140825A (en) | Negative electrode active material, the cathode and lithium secondary battery for including it | |
| JP2023539087A (en) | Method for producing positive electrode active material for lithium secondary batteries and positive electrode active material produced thereby | |
| CN116261792A (en) | Positive electrode for lithium secondary battery and lithium secondary battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211227 Address after: Seoul, South Kerean Patentee after: LG Energy Solution,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |