CN103797621A - Bimodal-type anode active material and lithium secondary battery including the same - Google Patents
Bimodal-type anode active material and lithium secondary battery including the same Download PDFInfo
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- CN103797621A CN103797621A CN201380001741.5A CN201380001741A CN103797621A CN 103797621 A CN103797621 A CN 103797621A CN 201380001741 A CN201380001741 A CN 201380001741A CN 103797621 A CN103797621 A CN 103797621A
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- primary particle
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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
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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
- H01M4/13—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides an anode active material including a compound shown as the formula 1. The anode active material is capable of achieving a high-density electrode and improving both the adhesiveness and high-rate capability of the electrode. The compound shown as the formula 1 comprises first primary particles and secondary particles, wherein the weight ratio of the first primary particles to the secondary particles is 5:95 to 50:50. The formula 1 is LixMyO2, where the M is any one element independently selected from the group consisting of titanium (Ti), stannum (Sn), copper (Cu), lead (Pb), stibium (Sb), zinc (Zn), ferrum (Fe), indium (In), aluminum (Al) and zirconium (Zr), or a mixture containing at least two elements thereof; and the x, the y and the z are determined depending on the oxidation number of the M.
Description
Technical field
The lithium secondary battery that the present invention relates to bimodal pattern negative active core-shell material and comprise it, more particularly, the present invention relates to negative active core-shell material and the lithium secondary battery that comprises it, wherein form the mixture that the particle of described negative active core-shell material comprises primary particle and secondary.
Background technology
Lithium rechargeable battery is the secondary cell that a kind of principle that produces battery while moving between positive pole and negative pole by lithium ion is moved.The component of lithium secondary battery can be divided into positive pole, negative pole, barrier film and electrolyte widely.In described component, positive electrode active materials and negative active core-shell material can have following structure: the lithium in ionic condition can embed and deintercalation in active material, and can implement to discharge and recharge by reversible reaction.
Typically, lithium metal is used as to the negative active core-shell material of lithium secondary battery.But, due to because following former thereby have the danger of blast: in the time using lithium metal, know from experience battery short circuit occur owing to forming dendritic crystal, so widely by carbon-based material as negative active core-shell material to replace lithium metal.
The example of carbon-based material can be crystalline carbon as graphite and Delanium, and amorphous carbon is as soft carbon and hard carbon.Described amorphous carbon can have high power capacity, but irreversibility can uprise during charge and discharge process.Typically graphite is used as to crystalline carbon, and described graphite has high theoretical capacity restriction.But even if crystalline carbon or amorphous carbon have relatively high theoretical capacity, but theoretical capacity is only about 380mAh/g.Thus, during exploitation high-capacity lithium battery, be difficult to use crystalline carbon or amorphous carbon as negative pole.
Therefore, to there is battery performance as rapid charge and electric discharge and long-life lithium rechargeable battery in order developing, recently the metal oxide that uses Li-Ti oxide (LTO), spinel structure have been carried out to active research as negative active core-shell material.
Because LTO can not produce solid electrolyte interface (SEI) layer, so LTO is producing aspect irreversible capacity than graphite excellence, even and repeating still there is excellent invertibity for embedding and the deintercalation of lithium ion during charge and discharge cycles, described solid electrolyte interface (SEI) layer is because the secondary response between the graphite-based negative active core-shell material and the electrolyte that are generally used for now in lithium rechargeable battery produces.In addition, because LTO has metastable structure, so it is the hope material that can represent the long-life performance of secondary cell.
LTO can be divided into two classes, wherein LTO is only made up of primary particle, and LTO is made up of secondary, and described secondary is to form by the reunion of primary particle.In situation about being formed by primary particle at LTO, in the time that LTO has suitable particle diameter, be not problem to the adhesion of electrode, but charge-discharge characteristic can be deteriorated.Therefore, being in the situation below 300nm in order to overcome this shortcoming and to improve high rate capability and make the particle diameter of LTO of preparation, because the increase of specific area is created in the restriction of preparing process aspect during slurry.In addition, form in the situation of secondary in the restriction in order to overcome nanometer primary particle, can improve described restriction.But, in order to keep the adhesion to electrode, need a large amount of adhesives.Because adhesive can serve as the resistive element of electrode, so the total energy density of battery finally can decline.
In addition, along with using the lifting of function of device of battery, need to there is the battery of high-energy-density.In order to meet this requirement, the technology of the energy of the per unit volume that need to be able to raise.In order to improve the energy of per unit volume, the amount of the electrode material being coated with by raising per unit volume can form high-density electrode, can form thus and have high-octane battery.
Therefore, need a kind of active material that can improve electrode density by reducing the amount of adhesive.
Summary of the invention
Technical problem
According to an aspect of the present invention, the invention provides a kind of negative active core-shell material that can guarantee the high rate capability of battery and the high density of electrode and the adhesion to electrode.
Technical scheme
According to aspects of the present invention, provide a kind of bimodal pattern negative active core-shell material and the negative pole that comprises described bimodal pattern negative active core-shell material and lithium secondary battery, wherein form the mixture that the particle of described negative active core-shell material comprises the first primary particle and secondary.
Advantageous effects
Use the negative active core-shell material that wherein mixes the first primary particle and secondary with proper ratio, not only can obtain thus high-density electrode, and can also improve adhesion and the high rate capability to electrode simultaneously.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that shows the negative active core-shell material of embodiment of the present invention, wherein the first primary particle of appropriate amount is mixed with secondary;
Fig. 2 is the schematic diagram that shows negative active core-shell material, wherein a large amount of the first primary particles is mixed with secondary; And
Fig. 3 is the figure that show electrode density changes with the mixing ratio of the first primary particle, and described the first primary particle is for the negative pole of the embodiment 7～12 of embodiment of the present invention.
Embodiment
The present invention relates to the negative active core-shell material of the compound that comprises following Chemical formula 1, wherein the compound of Chemical formula 1 comprises 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]
Li
xM
yO
z
Wherein M is independently selected from any one element in following element or the mixture of two or more elements: titanium (Ti), tin (Sn), copper (Cu), plumbous (Pb), antimony (Sb), zinc (Zn), iron (Fe), indium (In), aluminium (Al) and zirconium (Zr); And x, y and z determine according to the oxidation number of M.
According to embodiment of the present invention, use the negative active core-shell material wherein with proper ratio, the first primary particle and secondary being mixed, not only can obtain thus high-density electrode, but also can improve adhesion and the high rate capability to electrode simultaneously.
Fig. 1 is the schematic diagram of negative active core-shell material that shows embodiment of the present invention, wherein the first primary particle of appropriate amount is mixed with secondary, and Fig. 2 is the schematic diagram of demonstration negative active core-shell material, wherein a large amount of the first primary particles is mixed with secondary.
With reference to Fig. 1 and 2, mix therein the first primary particle of appropriate amount and mix in two kinds of situations of a large amount of the first primary particles, the first primary particle can be filled the hole between secondary.But, in as shown in fig. 1 to the first primary particle and the suitable situation of mixing of secondary, can meet aspect adhesion and high rate capability and the optimum performance of electrode density simultaneously.
According to embodiment of the present invention, the average grain diameter (D of the first primary particle
50) be 10nm～3 μ m, can be 100nm～1 μ m, and can be for example 100nm～700nm.
Be less than in the situation of 10nm in the average grain diameter of the first primary particle, aspect processing, there is practical difficulty, and be greater than in the situation of 3 μ m in average grain diameter, because the diameter of the first primary particle is relatively large, so can not expect and improve the effect of high rate capability due to the first primary particle.
Only being made up of the first primary particle and being used as in the situation of negative active core-shell material of lithium secondary battery at lithium metal oxide particle, be not problem, but charge-discharge characteristic can be deteriorated to the adhesion of electrode.Can prepare the first primary particle to there is less diameter, thereby overcome above-mentioned restriction.But, in this case, because the raising meeting of specific area exists restriction at process aspect during preparing slurry, as caused production cost to improve and conductance decline due to a large amount of adhesives of use.
Therefore, according to embodiment of the present invention, in order to overcome above-mentioned restriction in the situation that only uses the first primary particle, use wherein and mix the first primary particle of lithium metal oxide and the negative active core-shell material of secondary with proper ratio, not only can obtain thus highdensity electrode, but also can improve adhesion and the high rate capability to electrode simultaneously.
According to embodiment of the present invention, the first primary particle is 5:95～50:50 (weight ratio) to the mixing ratio of secondary, and can be 5:95～40:60.
In the time that the amount of the first primary particle is greater than above-mentioned scope, electrode density can improve, but adhesion to electrode and the high rate capability of secondary cell can decline.In addition, in the time that the amount of the first primary particle is less than above-mentioned scope, the Kong Buhui between secondary is filled up by the first primary particle, can not realize thus desired effects of the present invention.
Lithium metal oxide particle is secondary according to embodiments of the present invention, and wherein plural the second primary particle is reunited, and can be small porous particle.
According to embodiment of the present invention, in the time that more than two the second primary particle occurs to reunite with formation secondary, specific area is less than the situation that wherein the second primary particle is not reunited and comprised separately relatively.Thus, can be better to the adhesion of electrode.
In the present invention, the interior porosity of secondary is 3%～15%, and its average grain diameter (D
50) can be 5 μ m～30 μ m, and its specific area (Brunauer-Emmett-Teller (Brunauer-Emmett-Teller) is (BET)) can be 1m
2/ g～15m
2/ g.
In the interior porosity of secondary is less than 3% situation, considers the following fact and aspect processing, have practical difficulty: the reunion by the second primary particle forms secondary.The interior porosity of secondary is greater than in 15% situation therein, keeps the amount of the needed adhesive of suitable adhesion to electrode to increase, and conductance declines and volume lowering thus.
According to embodiment of the present invention, the interior porosity of secondary can be defined as follows:
Volume/(volume in the hole of specific volume+per unit mass) in the hole of interior porosity=per unit mass
The measurement of interior porosity is not particularly limited.According to embodiment of the present invention, for example, measure interior porosity by the BELSORP (BET instrument) that uses adsorbed gas to manufacture as nitrogen with by Japanese Bayer Corp (BEL Japan, Inc).
Similarly, the specific area of secondary (BET) can be 1m
2/ g～15m
2/ g.
In the present invention, can measure by BET method the specific area of the first primary particle and secondary.For example, can use porosity measurement analyzer (the Belsorp-II mini being manufactured by Japanese Bayer Corp) to measure specific area according to nitrogen adsorption-flow method by 6 BET methods.
Average grain diameter (the D of secondary
50) be 5 μ m～30 μ m, and can be 5 μ m～12 μ m.Form the average grain diameter (D of the second primary particle of secondary
50) be 100nm～1 μ m, and can be 100nm～700nm.
In the present invention, can be by average grain diameter (D
50) be defined as in accumulation particle diameter distributes at the particle diameter at 50% place.For example,, by using laser diffractometry can measure the average grain diameter (D of the first and second primary particles and secondary according to embodiments of the present invention
50).Laser diffractometry can be measured the particle diameter that submicron order arrives several millimeters conventionally, and can realize high duplication and high-resolution result.
Typically, because the conductance of lithium metal oxide is low, so advantageously there is little average grain diameter to be applied to the battery of quick charge.But, in this case, due to the increase of specific area as mentioned above, so need a large amount of adhesives to keep suitable electrode sticking power.
That is, be less than in the situation of 5 μ m in the average grain diameter of secondary, because the specific area of negative active core-shell material increases, so for the amount that keeps the needed adhesive of electrode sticking power of expecting can increase, the decline of result meeting generating electrodes conductance.Be greater than in the situation of 30 μ m in the average grain diameter of secondary, quick charge characteristic can be deteriorated.
Therefore, comprise in the situation of secondary that average grain diameter is 5 μ m～30 μ m at high density negative active core-shell material according to embodiments of the present invention, for the amount that keeps the needed adhesive of electrode sticking power not only can decline, and can also improve quick charge characteristic by increasing area, be wherein possible with direct reaction of lithium (Li) ion.
Be less than in the situation of 100nm in the average grain diameter of the second primary particle, in being less than the process of 100nm, preparation average grain diameter has difficulties, and because the porosity of the secondary not only forming by the reunion of the second primary particle declines, and lithium ion is difficult to infiltrate in secondary, so can not precipitate discharging and recharging the second primary particle in secondary in reaction.Be greater than in the situation of 1 μ m in the average grain diameter of the second primary particle, the formative of secondary can decline, and is difficult to control granulation.
According to embodiment of the present invention, the compound of Chemical formula 1 can comprise one or more Li-Ti oxides that are selected from following material: Li
4ti
5o
12, Li
2tiO
3, Li
2ti
3o
7and the compound of following Chemical formula 2:
[Chemical formula 2]
Li
x’Ti
y’O
4
Wherein 0.5≤x '≤3, and 1≤y '≤2.5.
In addition, the compound of Chemical formula 2 can be LiTi
2o
4.
Preparing according to an embodiment of the present invention in the method for negative active core-shell material, first prepare the first primary particle of lithium metal oxide by typical method, and after preparation the second primary particle, can form the secondary of lithium metal oxide particle by independent prilling.But, typically utilize the method for preparing the second primary particle and the second primary particle being reunited simultaneously by single technique, can prepare secondary.Thereafter, by the first primary particle and the even mixing of secondary of preparation can be prepared according to negative active core-shell material of the present invention.
Preparing according to an embodiment of the present invention in the method for negative active core-shell material, add lithium salts and metal oxide to volatile solvent, stir and sintering.Then, can obtain the first primary particle by grinding and sieving.
Particularly, lithium salts is dissolved in volatile solvent, then in stirring, adds the titanium oxide as metal oxide to it.Then, at the temperature of approximately 500 ℃～approximately 1000 ℃ by the solution sintering approximately 1 hour～approximately 15 hours of preparation thus.Thereafter, by grinding and sieving and can prepare the first primary particle.
Herein, volatile solvent can be for example water, acetone or alcohol.
In addition, lithium salts can be for being selected from any one material in following material or the mixture of two or more materials: lithium hydroxide, lithia and lithium carbonate.
In addition, preparing according to an embodiment of the present invention in the method for negative active core-shell material, the method for preparing secondary can comprise: prepare precursor solution and stir by add lithium salts and metal oxide in volatile solvent; Described precursor solution is supplied to the indoor of spray dryer; And indoor described precursor solution is sprayed and is dried described.
In this case, by selecting and material for the preparation of identical in the first primary particle, can use lithium salts, metal oxide and volatile solvent.
According to embodiment of the present invention, after preparation the second primary particle, by independent prilling, can form the secondary of lithium metal oxide particle.But, typically can utilize by single technique and prepare the second primary particle and the method for simultaneously the second primary particle being reunited is prepared secondary.
The example of said method can comprise spray drying process.Hereinafter, will use spray drying process as an example the method for preparing according to an embodiment of the present invention secondary to be described.
Preparation method can comprise precursor solution is supplied to and is included in indoor in spray dryer according to embodiments of the present invention.
The spray dryer that typical case can be used as above-mentioned spray dryer, for example, can use ullrasonic spraying drier, air nozzle spray dryer, ultrasonic nozzle spray dryer, filter expansion aerosol generator or electrostatic spray drier.But, the present invention can not be limited to this.
According to embodiment of the present invention, precursor solution can be 10ml/ minute～1000ml/ minute to indoor feed rate.In feed rate is less than the situation of 10ml/ minute, the average grain diameter of the second primary particle of reunion can decline, and is difficult to thus form high density secondary.In feed rate is greater than the situation of 1000ml/ minute, because the average grain diameter of secondary can increase relatively, so be difficult to realize the high rate capability of expecting.
In addition the method for, preparing according to an embodiment of the present invention secondary can be included in the indoor precursor solution dry that sprays.
By can spray precursor solution at the indoor dish rotating under high speed, and can spray and be dried in same indoor enforcement.
In addition, by controlling spray-dired condition as the flow velocity of carrier gas, the time of staying and internal pressure in reactor, can realize average grain diameter of the present invention and interior porosity.
According to embodiment of the present invention, by regulating baking temperature can control the interior porosity of secondary, and can at the temperature of 20 ℃～300 ℃, implement dry.But, for high density secondary, can at alap temperature, implement dry.
According to embodiment of the present invention, the first primary particle and secondary are mixed under the weight ratio of 5:95～50:50, also can under the weight ratio of 5:95～40:60, mix, thus, can prepare the high rate performance density high and electrode of battery high and guarantee the negative active core-shell material of the adhesion to electrode.In this case, in order to mix as well as possible the first primary particle and secondary, by using typical polishing can evenly mix the first primary particle and secondary as planetary mill.
Based on the total weight of negative active core-shell material, can comprise the lithium metal oxide that comprises according to embodiments of the present invention the first primary particle and secondary with the amount of 50 % by weight～100 % by weight.The amount of the total weight lithium metal oxide based on negative active core-shell material is that the situation of 100 % by weight refers to the situation that wherein negative active core-shell material is only made up of lithium metal oxide.
In secondary cell according to embodiments of the present invention, except lithium metal oxide, negative active core-shell material also can comprise at least one active material being selected from following material: carbon-based material, and it is typically for negative active core-shell material; Transition metal oxide; Silicon (Si) sill; And Sn sill.But, can not be by the class limitations of negative active core-shell material in this.
The present invention also provides a kind of negative electrode active material feed composition that comprises negative active core-shell material, conductive agent and adhesive, can comprise negative active core-shell material, conductive agent and adhesive with the weight ratio of 80:3:7～90:9:13.
The lithium secondary battery that the present invention also provides a kind of negative pole that comprises described negative electrode active material feed composition and comprises described negative pole.
By the negative electrode active material feed composition that comprises negative active core-shell material with such as the solvent of 1-METHYLPYRROLIDONE (NMP), to be coated with anode collector, then can prepare negative pole by described anode collector be dried with roll-in.
Anode collector is not particularly limited, as long as it chemical change can not occur in battery and has high conductivity.The example of anode collector can be: copper; Stainless steel; Aluminium; Nickel; Titanium; Sintered carbon; Carry out surface-treated copper or stainless steel through carbon, nickel, titanium or silver; Aluminium-cadmium alloy etc.Also can on anode collector surface, form tiny irregular place, thereby improve the adhesion of negative active core-shell material, and can be to use described anode collector such as the various ways of film, sheet, paper tinsel, net, porous body, foam or nonwoven fabrics.
Conductive agent is not particularly limited, as long as it chemical change can not occur in battery and has conductivity.The example of conductive agent can be: graphite is as native graphite and Delanium; Carbon black class material is as acetylene black, Ketjen black, channel black, furnace black, dim and thermals; Conductive fiber is as carbon fiber and metallic fiber; Metal dust is as carbon fluoride powder, aluminium powder and nickel by powder; Conductive whiskers is as ZnOw and potassium titanate crystal whisker; Conducting metal oxide is as titanium oxide; With electric conducting material as polyphenylene derivative etc.
The example of adhesive can be EPDM, butadiene-styrene rubber, fluorubber and the various copolymers etc. of polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, PVP, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonation.
For example, utilize the anode sizing agent that comprises positive electrode active materials to be coated with cathode collector, then by cathode collector is dried and can prepares the positive pole being included in lithium secondary battery of the present invention.If needed, described anode sizing agent can comprise said components.
Especially, as positive electrode active materials, lithium secondary battery can use: lamellar compound is as lithium and cobalt oxides (LiCoO
2) or lithium nickel oxide (LiNiO
2) or utilize the compound of one or more Transition metal substituted; Lithium manganese oxide is as Li
1+xmn
2-xo
4(wherein x is 0～0.33), LiMnO
3, LiMn
2o
3and LiMnO
2; Lithium Cu oxide (Li
2cuO
2); The oxide of vanadium is as LiV
3o
8, LiFe
3o
4, V
2o
5and Cu
2v
2o
7; By chemical formula LiNi
1-xm
xo
2nickel (Ni) the site type lithium nickel oxide that (wherein M is cobalt (Co), manganese (Mn), Al, Cu, Fe, magnesium (Mg), boron (B) or gallium (Ga), and x is 0.01～0.3) represents; By chemical formula LiMn
2-xm
xo
2(wherein M is Co, Ni, Fe, chromium (Cr), Zn or tantalum (Ta), and x is 0.01～0.1) or Li
2mn
3mO
8the complex Li-Mn-oxide that (wherein M is Fe, Co, Ni, Cu or Zn) represents; The LiMn that part Li is replaced by alkaline-earth metal ions
2o
4; Di-sulphide compounds; Or Fe
2(MoO
4)
3.But, can use LiNi
xmn
2-xo
4(wherein x is 0.01～0.6), and can use for example LiNi
0.5mn
1.5o
4or LiNi
0.4mn
1.6o
4., in the present invention, can the spinel lithium manganese composite oxide LiNi of relative high potential will be there is due to the high potential of negative active core-shell material
xmn
2-xo
4(wherein x is 0.01～0.6) is as positive electrode active materials.
The present invention also provides and comprises lithium secondary battery as the battery module of element cell and the battery pack that comprises described battery module.
Typical case can select as the battery case for the present invention for any battery case of this area.The shape of lithium secondary battery does not limit with the variation of its purposes, for example, can use the column type, prismatic, bag type or the Coin shape that utilize tank.
Not only can be for being used as in the battery unit of midget plant power supply according to lithium secondary battery of the present invention, the element cell in the medium-sized and large-sized battery module that also can be used as comprising multiple battery units.Medium-sized and preferred embodiment large-scale plant can be motor vehicle, hybrid electric vehicle, plug-in hybrid electric vehicle or power storage system, but medium-sized and large-scale plant can not be limited to this.
Hereinafter, will more fully illustrate the present invention according to specific embodiments.But the present invention can and should not be construed as with much multi-form enforcement and be restricted to described embodiment herein.
Embodiment
Preparation example 1: preparation the first primary particle
Under the mol ratio of 4:5 to LiOHH
2o and TiO
2(anatase) mixes.Mixture is dissolved in pure water, then solution is stirred, and at 750 ℃ sintering approximately 3 hours.By grinding and sieving and prepared average grain diameter (D
50) be the first primary particle of 700nm.
Preparation example 2: preparation secondary
Under the mol ratio of 4:5 to LiOHH
2o and TiO
2(anatase) mixes.Mixture is dissolved in pure water, then solution is stirred.In this case, the ratio of the total weight of the weight that the ratio of total solid material is defined as to the total solid content being included in solution to solution, and by solids content being adjusted to 30% and stir, prepared precursor solution.Precursor solution is supplied to the indoor of spray dryer (being manufactured by Ai Yin System Co., Ltd (EIN SYSTEMS, Co., Ltd.)).Then, at the indoor precursor solution dry that sprays.Under the condition of feed rate that comprises the baking temperature ,～20mbar internal pressure of 130 ℃ and 30ml/ minute, implement spraying dry, then by the precursor obtaining is thus carried out to sintering in air at 800 ℃, prepared the Li with 5.4 μ m average grain diameters and 3.5% interior porosity
4ti
5o
12secondary.
Embodiment 1
By using planetary mill with the weight ratio of 5:95, the first primary particle of preparing in preparation example 1 and 2 and secondary to be carried out mixing to prepare negative active core-shell material.
Embodiment 2
Except mixing the first primary particle and secondary with the weight ratio of 10:90, prepare negative active core-shell material in the mode identical with embodiment 1.
Embodiment 3
Except mixing the first primary particle and secondary with the weight ratio of 20:80, prepare negative active core-shell material in the mode identical with embodiment 1.
Embodiment 4
Except mixing the first primary particle and secondary with the weight ratio of 30:70, prepare negative active core-shell material in the mode identical with embodiment 1.
Embodiment 5
Except mixing the first primary particle and secondary with the weight ratio of 40:60, prepare negative active core-shell material in the mode identical with embodiment 1.
Embodiment 6
Except mixing the first primary particle and secondary with the weight ratio of 50:50, prepare negative active core-shell material in the mode identical with embodiment 1.
Comparative example 1
Prepare negative active core-shell material by only using the first primary particle obtaining in preparation example 1.
Comparative example 2
Prepare negative active core-shell material by only using the secondary obtaining in preparation example 2.
Comparative example 3
Except mixing the first primary particle and secondary with the weight ratio of 60:40, prepare negative active core-shell material in the mode identical with embodiment 1.
Comparative example 4
Except mixing the first primary particle and secondary with the weight ratio of 3:97, prepare negative active core-shell material in the mode identical with embodiment 1.
Embodiment 7
< prepares negative pole >
Using the weight ratio of 84:6:10 by the negative active core-shell material of the embodiment as negative active core-shell material 1, as the carbon black (Super P) of conductive agent with mix as the PVdF of adhesive, then mixture is added to METHYLPYRROLIDONE as solvent to prepare slurry.Utilize the thickness of the slurry of preparing to copper collector surface-coated to 65 μ m, then dry and roll-in.Then, prepared negative pole by being die-cut into preliminary dimension.
< prepares lithium secondary battery >
Volume ratio with 30:70 has carried out mixing to prepare nonaqueous electrolyte solvent to ethylene carbonate (EC) and diethyl carbonate (DEC), and adds LiPF to it
6with preparation 1M LiPF
6non-aqueous electrolytic solution.
In addition, lithium paper tinsel is anodal with doing electrode, and polyalkene diaphragm is arranged between two electrodes.Then, prepared coin-like half cells by injecting electrolyte solution.
Embodiment 8～12 and comparative example 5～8
By use the negative active core-shell material obtaining in embodiment 2～6 and comparative example 1～4, prepare the negative pole of the composition with following table 1.
[table 1]
| Catalogue | Negative pole composition (negative active core-shell material: conductive agent: adhesive) (weight ratio) |
| Embodiment 7 | 84 (the first primary particle 5: secondary 95): 6:10 |
| Embodiment 8 | 84 (the first primary particle 10: secondary 90): 6:10 |
| Embodiment 9 | 84 (the first primary particle 20: secondary 80): 6:10 |
| Embodiment 10 | 84 (the first primary particle 30: secondary 70): 6:10 |
| Embodiment 11 | 84 (the first primary particle 40: secondary 60): 6:10 |
| Embodiment 12 | 84 (the first primary particle 50: secondary 50): 6:10 |
| Comparative example 5 | 84 (only the first primary particle): 6:10 |
| Comparative example 6 | 84 (only secondary): 6:10 |
| Comparative example 7 | 84 (the first primary particle 60: secondary 40): 6:10 |
| Comparative example 8 | 84 (the first primary particle 3: secondary 97): 6:10 |
Experimental example 1
< adhesion is measured >
Use the negative pole of preparing during the lithium secondary battery of Preparation Example 7～12 and comparative example 5～8, measured the adhesion of anticathode.Use 180 ° of known disbonded tests conventionally to implement adhesion force measurement.The results are shown in following table 2.
Experimental example 2
< high rate capability is analyzed >
In order to analyze the high rate capability of lithium secondary battery of embodiment 7～12 and comparative example 5～8, by sequentially changing respectively charging and discharging multiplying power into 0.1C, 0.2C, 0.5C, 1C, 0.2C, 2C, 0.2C, 5C, 0.2C and 10C, the high rate capability of lithium secondary battery is evaluated.In this case, end of charge voltage is set as to 1.0V, and final discharging voltage is set as to 2.5V.The high rate capability of each lithium secondary battery is expressed as to the capacity relative of measuring in the percent value of the capacity under 0.1C under 10C.
The results are shown in following table 2.
[table 2]
As shown in table 2, in as embodiment 7～12, Li-Ti oxide is used in the situation of negative pole, described Li-Ti oxide, by the first primary particle and secondary are mixed and formed, confirms, adhesion and high rate capability improve simultaneously.
But, even therein as used and wherein have in the situation of the first primary particle of mixing and the negative active core-shell material of secondary in comparative example 7 and 8, still can confirm, in the time using the primary particle of excessive or relatively small amount, can not meet adhesion and high rate capability with the embodiment of the present invention 7～12 pars simultaneously.
In as comparative example 5, the Li-Ti oxide only being formed by the first primary particle is used as in the situation of active material, confirm, adhesion obviously improves, and therein as in comparative example 6 by the Li-Ti oxide only being formed by secondary in the situation for negative pole, confirm, high rate capability declines.
According to the result of experimental example 1 and 2, can infer, representing of the first primary particle high rate capability is relevant to the following fact: compared with secondary, the first primary particle has excellent accessibility during representing high rate capability between the lithium ion in Li-Ti oxide and electrolyte.In addition, because the specific area of secondary is lower than the specific area of the Li-Ti oxide being only made up of the first primary particle, so think that it is relevant with electrode sticking power.
Experimental example 3
< electrode density >
Use the negative pole of preparing during the lithium secondary battery of Preparation Example 7～12 and comparative example 5～8, the electrode density of electrode is measured.The results are shown in following table 3, and electrode density is shown in Fig. 3 with the variation of the ratio of the first primary particle mixing.
[table 3]
| Catalogue | Electrode composition (active material: conductive agent: adhesive) | Electrode density [g/cc] |
| Embodiment 7 | 84 (the first primary particle 5: secondary 95): 6:10 | 1.89 |
| Embodiment 8 | 84 (the first primary particle 10: secondary 90): 6:10 | 1.91 |
| Embodiment 9 | 84 (the first primary particle 20: secondary 80): 6:10 | 1.93 |
| Embodiment 10 | 84 (the first primary particle 30: secondary 70): 6:10 | 1.94 |
| Embodiment 11 | 84 (the first primary particle 40: secondary 60): 6:10 | 1.95 |
| Embodiment 12 | 84 (the first primary particle 50: secondary 50): 6:10 | 1.95 |
| Comparative example 5 | 84 (only the first primary particle): 6:10 | 2.1 |
| Comparative example 6 | 84 (only secondary): 6:10 | 1.8 |
| Comparative example 7 | 84 (the first primary particle 60: secondary 40): 6:10 | 1.96 |
| Comparative example 8 | 84 (the first primary particle 3: secondary 97): 6:10 | 1.8 |
As shown in table 3, in as embodiment 7～12 by Li-Ti oxide in the situation of negative pole, in described Li-Ti oxide, compare the first primary particle with specific blend and secondary is mixed, can confirm, compared with comparative example 6～8, electrode density obviously improves.
In addition, as shown in Figure 3, reference is as the negative pole of nothing the first primary particle in comparative example 6 with if the electrode density only in comparative example 5 with the negative pole of the first primary particle is (in the figure of Fig. 3, dotted line is the calculated value of mixed electrode density), can confirm, compared with the calculated value of mixed electrode density, the electrode density of embodiment 7～12 sharply increases.
But, the increase of electrode density declines with the rising of the ratio of mixing the first primary particle, confirm thus, the electrode density of negative pole (will wherein thering is the first primary particle of mixing and the Li-Ti oxide of secondary as negative active core-shell material in described negative pole), in the time that the ratio of the first primary particle approaches 50%, with only there is the negative pole of primary particle and only there is the mean value of electrode density of the negative pole of secondary similar.
,, by thering is therein the first primary particle of mixing and the Li-Ti oxide of secondary as in the situation of negative active core-shell material, even if mix therein in the situation of a small amount of the first primary particle, still can realize the effect that improves electrode density.
About the negative pole (wherein will having the first primary particle of mixing and the Li-Ti oxide of secondary as negative active core-shell material) of embodiment 7～12, electrode density improves.Can infer, the reason of this situation is caused by the following fact: the Li-Ti oxide by utilization with the first primary particle structure is filled the hole between secondary, can improve electrode density, the hole between described secondary is by only being used secondary to form when electrode and produce as active material.
; when will wherein mixing the electrode of embodiment 7～12 of the first primary particle and secondary and the electrode of secondary cell and comparative example 7 and 8 and secondary cell relatively time; can confirm; in order to realize optimum performance aspect adhesion and high rate capability, can mix the first primary particle and secondary with proper ratio.
Industrial applicability
Wherein mix the negative active core-shell material of the first primary particle and secondary with proper ratio owing to using, so not only can obtain high-density electrode, also can improve adhesion and the high rate capability to electrode simultaneously.Thus, described negative active core-shell material is applicable to lithium secondary battery.
Claims (18)
1. a negative active core-shell material, the compound that it comprises following Chemical formula 1,
The compound of wherein said Chemical formula 1 comprises the first primary particle and secondary, and described the first primary particle is 5:95～50:50 to the weight ratio of described secondary:
[Chemical formula 1]
Li
xM
yO
z
Wherein M is independently selected from any one element in following element or the mixture of two or more elements: titanium (Ti), tin (Sn), copper (Cu), plumbous (Pb), antimony (Sb), zinc (Zn), iron (Fe), indium (In), aluminium (Al) and zirconium (Zr); And x, y and z determine according to the oxidation number of M.
2. negative active core-shell material as claimed in claim 1, wherein said the first primary particle is 5:95～40:60 to the weight ratio of described secondary.
3. negative active core-shell material as claimed in claim 1, the average grain diameter (D of wherein said the first primary particle
50) be 10nm～3 μ m.
4. negative active core-shell material as claimed in claim 3, the average grain diameter (D of wherein said the first primary particle
50) be 100nm～1 μ m.
5. negative active core-shell material as claimed in claim 1, wherein two above the second primary particles occur to reunite to form described secondary.
6. negative active core-shell material as claimed in claim 5, the average grain diameter (D of wherein said the second primary particle
50) be 100nm～1 μ m.
7. negative active core-shell material as claimed in claim 1, the average grain diameter (D of wherein said secondary
50) be 5 μ m～30 μ m.
8. negative active core-shell material as claimed in claim 7, the average grain diameter (D of wherein said secondary
50) be 5 μ m～12 μ m.
9. negative active core-shell material as claimed in claim 1, the compound of wherein said Chemical formula 1 comprises one or more Li-Ti oxides that are selected from following material: Li
4ti
5o
12, Li
2tiO
3, Li
2ti
3o
7and the compound of following Chemical formula 2:
[Chemical formula 2]
Li
x’Ti
y’O
4
Wherein 0.5≤x '≤3, and 1≤y '≤2.5.
10. negative active core-shell material as claimed in claim 9, the compound of wherein said Chemical formula 2 is LiTi
2o
4.
11. 1 kinds of negative electrode active material feed compositions, its negative active core-shell material that comprises claim 1, conductive agent and adhesive.
12. negative electrode active material feed compositions as claimed in claim 11, the weight ratio of the described negative active core-shell material that wherein comprised, described conductive agent and described adhesive is 80:3:7～90:9:13.
13. negative electrode active material feed compositions as claimed in claim 11, wherein said conductive agent is at least one material being selected from following material: graphite; Carbon black; Conductive fiber; Metal dust; Conductive whiskers; Conducting metal oxide; With polyphenylene derivative.
14. negative electrode active material feed compositions as claimed in claim 11, wherein said adhesive is at least one material being selected from following material: EPDM, butadiene-styrene rubber and the fluorubber of polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, PVP, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonation.
15. 1 kinds of negative poles, the negative electrode active material feed composition that it comprises claim 11.
16. 1 kinds of lithium secondary batteries, the negative pole that it comprises claim 15.
17. 1 kinds of battery modules, its lithium secondary battery that comprises claim 16 is as element cell.
18. 1 kinds of battery pack, the battery module that it comprises claim 17.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0076901 | 2012-07-13 | ||
| KR20120076901 | 2012-07-13 | ||
| KR10-2013-0081007 | 2013-07-10 | ||
| KR1020130081007A KR101558044B1 (en) | 2012-07-13 | 2013-07-10 | Bimodal type-anode active material and lithium secondary battery comprising the same |
| 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 true CN103797621A (en) | 2014-05-14 |
| CN103797621B CN103797621B (en) | 2019-07-23 |
Family
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|---|---|---|---|
| CN201380001741.5A Active CN103797621B (en) | 2012-07-13 | 2013-07-11 | Bimodal pattern negative electrode active material and lithium secondary battery comprising it |
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| Country | Link |
|---|---|
| JP (1) | JP5984026B2 (en) |
| KR (1) | KR101558044B1 (en) |
| CN (1) | CN103797621B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2014527267A (en) | 2014-10-09 |
| JP5984026B2 (en) | 2016-09-06 |
| CN103797621B (en) | 2019-07-23 |
| KR101558044B1 (en) | 2015-10-07 |
| KR20140009928A (en) | 2014-01-23 |
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