CN100433423C - Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same - Google Patents

Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same Download PDF

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CN100433423C
CN100433423C CNB2005100649624A CN200510064962A CN100433423C CN 100433423 C CN100433423 C CN 100433423C CN B2005100649624 A CNB2005100649624 A CN B2005100649624A CN 200510064962 A CN200510064962 A CN 200510064962A CN 100433423 C CN100433423 C CN 100433423C
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active material
negative electrode
electrode active
secondary battery
lithium secondary
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CN1848489A (en
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沈揆允
金相珍
金俊燮
金性洙
新田芳明
李相旻
金翰秀
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Samsung SDI Co Ltd
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract

A negative electrode for a lithium secondary battery of the present invention includes a negative active material including a plate-shaped carbon powder particle agglomerated in a primary structure in which the plate-shaped particle is oriented in a plane direction and laminated. Fine carbon powder particles are then agglomerated to form a secondary structure on the surface of the primary structure such that the resulting particles include fine pores formed on the surface.

Description

The negative electrode active material of lithium secondary battery and comprise its negative pole and lithium secondary battery
Technical field
The present invention relates to a kind of negative electrode active material that is used for lithium secondary battery, and comprise its negative pole and lithium secondary battery.More specifically, the present invention relates to a kind of negative electrode active material that is used for lithium secondary battery, and comprising its negative pole and lithium secondary battery, this negative electrode active material has good compression strength, to the wetability and the cryogenic discharging characteristic of electrolyte, and the high-density electrode plate can be provided.
Background technology
Lithium secondary battery comprises positive pole and the negative pole that contains the material that can reversibly embed lithium ion, and organic electrolyte or polyelectrolyte are injected between positive pole and the negative pole.This battery because of embed/redox reaction when deviating from lithium ion produces electric energy.
The positive active material that is used for lithium secondary battery adopts chalcogen compound, for example LiCoO 2, LiMnO 2, LiMn 2O 4, LiNiO 2, perhaps LiNi 1-xCo xO 2The metal composite of (0＜x in the formula＜1) etc.
Negative electrode active material generally includes the lithium metal, but adopts this material as the formation short circuit of understanding in the battery of negative electrode active material because of dendrite.Therefore, can replace the lithium metal with carbonaceous material.For this reason, crystalline carbon (for example native graphite or Delanium) and amorphous carbon (for example soft carbon or hard carbon) have been proposed.Although the capacity of amorphous carbon is very big, the reversible problem that embeds difficulty during it can cause discharging and recharging.When as negative electrode active material, crystalline carbon is generally the form of native graphite, because it has high power capacity, the theoretical limit capacity is 372mAh/g, significantly degenerates but the problem that it exists is the cycle life of resulting battery.
The negative electrode active material of lithium secondary battery is like this preparation: mix material with carbon element and adhesive and the conductive agent when needing, and stir them and obtain slurry.Then, be applied on the metal current collector slurry and drying, thereby form negative pole.In addition, also negative electrode active material is compressed on the collector body, to obtain the capacity of uniform battery lead plate of thickness and increase battery lead plate.Yet material with carbon element often breaks when the compacting battery lead plate, so battery lead plate loses its uniformity, this causes the reaction forfeiture uniformity with electrolyte, and causes the life-span of electrolyte plate to be reduced.And if crack growth, its marginal portion exposes with the form of broken line, the side reaction of feasible increase and electrolyte, and electrolyte significantly increases in the viscosity of low temperature under as-20 ℃, because electrolyte absorbs in the hair check by capillarity, and the electrolyte that participates in cell reaction reduces.Thereby flash-over characteristic is at low temperatures degenerated.
Summary of the invention
In one embodiment of the invention, provide a kind of negative electrode active material that is used for lithium secondary battery, and comprise that its negative pole and lithium secondary battery, described negative electrode active material can provide the battery lead plate with high density and good grain compressive strength.
In another embodiment of the present invention, negative electrode active material comprises a plurality of anode active material particles, each particle comprises a plurality of sheet carbon powder particles of assembling with primary structure, in described primary structure, sheet-like particle forms fine holes along in-plane orientation and stacked mutually on the surface of anode active material particles.
In an embodiment more of the present invention, the negative pole of lithium secondary battery comprises this negative electrode active material.
In another embodiment of the present invention, provide a kind of lithium secondary battery that comprises this negative pole.
Description of drawings
When the detailed description that reference is considered below in conjunction with accompanying drawing, the present invention and many advantages thereof become better understood, and be just apparent to the more complete understanding of the present invention and many advantages thereof, wherein:
Fig. 1 is the schematic diagram of the structure of the negative electrode active material that is used for negative plate according to the present invention;
Fig. 2 is the schematic diagram of one of embodiment of lithium secondary battery; And
Fig. 3 is the photo that uses the section of the negative pole of making according to the negative electrode active material of embodiment 1.
Embodiment
As shown in Figure 1, comprise a plurality of anode active material particles 10 according to the negative electrode active material that embodiment of the present invention provided.Each anode active material particles comprises a plurality of sheet carbon powder particles of assembling with primary structure 20, and in described primary structure, the sheet carbon powder particle is along in-plane orientation and stacked mutually.On the surface of sheet carbon powder particle, form fine holes.On the surface of sheet carbon powder particle, can assemble other fine carbon powder particle 30, to form secondary structure.
The sheet carbon powder particle forms with primary structure, and in this primary structure, the sheet carbon powder particle makes each particle be reflected by different polarizations along in-plane orientation and stacked mutually thus.Anode active material particles preferably has sphere or puppet (pseudo) sphere.The sheet carbon powder particle is that particle mean size is 10 μ m or native graphite bigger, 15～25 μ m more preferably or Delanium.Measure according to X-ray diffraction, the sheet carbon powder particle preferably has 0.2 or lower, the strength ratio on (110) plane of 0.002～0.2/(002) plane more preferably.
The fine carbon powder particle is the broken particle that produces in grinding sheet carbon powder particle process, and has 5 μ m or average length or particle mean size littler, that be preferably 0.5～3 μ m.The fine carbon powder particle can form fiber, amorphous shape, laminar or other shape.Particle mean size is to utilize after ultrasonic wave is scattered in carbon powder particle in the solvent, measures by Particle Size Analyzer (Marvern 2000).
The fine carbon powder particle can partly or entirely have impalpable structure or rapids layer structure.The fine carbon powder particle forms aggregation on the carbon powder particle of sheet, obtain the high density negative electrode active material that its surface has fine holes.Because this fine holes, the absolute reserve capacity of electrolyte increases, thereby improves high-rate characteristics and low-temperature characteristics.According to prior art, when fine holes is present in the whole active material, when preparation high-density electrode plate, just be easy to compression, and the specific surface of active material increases in the battery lead plate, causes new end face outstanding, this causes the side reaction with electrolyte.Yet, according to the present invention, because micropore exists only in the surface of anode active material particles, so even they also are not easy to break in the pressing process that forms battery lead plate, and the shape of anode active material particles is maintained.Thereby, the side reaction with electrolyte can be prevented, and battery lead plate can be made with good swelling suppression characteristic.
With reference to figure 1, except the fine carbon powder stratum granulosum, can also comprise amorphous carbon coating 40 on the carbon powder particle surface.In one embodiment of the invention, based on the carbon powder particle of 100 weight portions, the amount of amorphous carbon coating 40 is 5～30 weight portions, is preferably 5～15 weight portions.
According to an embodiment of the present invention one of anode active material particles have 4 or lower, be preferably 1～3 major axis and minor axis ratio.In embodiments of the invention, negative electrode active material is that 0.5 μ m or the littler occupied pinhole ratio of micropore are 10～40% by diameter, is preferably 15～40%, more preferably 10～35%.In another embodiment of the present invention, negative electrode active material is that 0.1 μ m or the littler occupied pinhole ratio of micropore are 12% or lower by diameter, preferred 3～10%.
Even in the pressing step of battery lead plate, the pinhole rate of the general specific activity material of pinhole rate of battery lead plate reduces manyly, but according to the pinhole rate of active material of the present invention is 2.0 times of the pinhole rates of battery lead plate or lower, be preferably 1.1～1.5 times, this porosity that shows active material after compression step does not almost change.
Diameter is that the effect of the micropore of 10～100 μ m is, improves electrolyte absorption rate and lithium ion transmission rate in the battery lead plate that scribbles negative electrode active material.If being the material with carbon element by routine, battery lead plate forms, then very little by the porosity in the occupied zone of the micropore of 10～100 μ m.In the present invention, because by diameter is that the porosity in the occupied zone of the micropore of 10～100 μ m is 30～60%, is preferably 35～50%, so be favourable for preserving electrolyte, guarantee the fluid passage, and improve lithium ion transmission and cryogenic discharging characteristic.
According to embodiment of the present invention, negative electrode active material is the high density carbon material, and it has 1.0g/cc or bulk density higher, that be preferably 1.1～1.30g/cc, and the apparent density of 0.6～1.0g/cc.In addition, bulk density is 30% or higher with the ratio of apparent density.
According to embodiment of the present invention, the specific surface of measuring according to the BET method is 2.0～4.0m 2/ g.Because the compression strength of negative electrode active material is 15MPa or higher, preferred 15～45MPa is so active material seldom damages in the pressing step of battery lead plate.
The method for preparing negative electrode active material hereinafter is described in detail in detail.
At first, remove the marginal portion or the ledge of material with carbon element by the first mechanical dynamic polishing, to obtain sphere or pseudo-sphere material.Described material with carbon element can be native graphite, Delanium, graphite precursor or similar material.Graphite precursor can be celion, the mesomorphic carbosphere of graphite (MCMB) or similar material.
In the first mechanical dynamic process of lapping,, obtain the carbon powder particle of sheet along with material with carbon element forms sphere or pseudo-spherical particle.In this process, also obtain thin carbon powder particle.Simultaneously, the intergranule with certain direction orientation in material with carbon element produces crackle, thereby the orientation of crystal grain changes fully.In addition, because wherein there is particulate impurity,, guaranteed the flowability of intergranule by cracking.
According to embodiment of the present invention, described material with carbon element by means of the second mechanical dynamic polishing, by impose very strong frictional force and shearing force between its surface, is assembled with thin carbon powder particle after this.In second accumulation process, described sheet carbon powder particle is along in-plane orientation and stacked.By friction stree very strong between the surface, the maximization of Van der Waals power between the plane surface, and maximum produce the interconnection effect.Dry then and assemble the sheet carbon powder particle, form the spherical or pseudo-spherical powder of multilayer.The fine carbon powder particle accumulates in the surface of sheet carbon powder particle with such structure secondary, makes thin carbon powder particle be coated with the surface of described sheet carbon powder particle.At this moment, thin carbon powder particle is assembled by direction at random, forms fine holes simultaneously.Accumulation process according to the present invention carries out in the atmosphere of drying.
Described mechanical dynamic polishing adopts such as strength such as compressing, impact, shearing and frictions.Process of lapping is general to adopt all these four kinds of strength, and is not limited to one or several specific power, but it depends on the drive condition of design characteristics or device.The smoothing process of particle surface mainly is to utilize compressing and impact the power that is produced, and is undertaken by first mechanically actuated operation.The representative example of lapping device comprises the rotor grinding machine, the ACM grinding machine, and pin type (pin) grinding machine, and spray (jet) grinding machine.For assembling for the second time of fine carbon powder particle and, apply shearing force and press the device of frictional force can realize mechanically fusing, mixing etc. to the adhering to of surface.
Accumulation process can also comprise the step of adding the fine carbon powder particle for the second time.In addition, accumulation process can comprise the step of adding the amorphous carbon precursor for the second time, so that fine carbon powder particle and sheet carbon powder particle are assembled.Suitable amorphous carbon precursor comprises mesophase pitch, oil-based asphalt, and carbenes, and have the heavy grade oil of low molecular wt.Based on the material with carbon element of 100 weight portions, the addition of this amorphous carbon precursor can be 5～30 weight portions.
The aggregation that derives from said process is heat-treated, obtain according to negative electrode active material of the present invention.Described heat treatment 1000 ℃ or higher, be preferably under 1200～2400 ℃ the temperature and carry out.If heat treatment is carried out being lower than under 1000 ℃ the temperature, then the impurity hetero-atom can not be removed fully.
According to one embodiment of the invention, provide the negative plate that comprises above-mentioned negative electrode active material.This negative plate is to be applied on the metal current collector by the slurry that will comprise negative electrode active material and adhesive resin, and dry then and compacting obtains.
Because negative electrode active material according to the present invention has high density and high compressive strength, so can obtain 1.5～2.0g/cc, be preferably the high-density electrode plate of 1.8～2.0g/cc.According to the present invention, even high-density electrode plate like this is applied to battery, also can obtain high-capacity battery, because kept the passage of enough Electolyte-absorptive.
Adhesive resin can be selected from any adhesive resin commonly used in the lithium secondary battery.The example comprises polyvinylidene fluoride, carboxymethyl cellulose, methylcellulose, and Sodium Polyacrylate.Metal current collector can comprise stamped metal, exmet stamped metal, goldleaf, metal foam, net metal fiber sintering thing, nickel foil, perhaps Copper Foil.
In addition, negative pole can further comprise conductive agent, for example nickel by powder, cobalt/cobalt oxide, titanium oxide or carbon according to embodiments of the present invention.Carbon can comprise that ketjen is black, acetylene black, furnace black, graphite, carbon fiber or fullerene.
According to another embodiment of the invention, lithium secondary battery comprises aforesaid negative plate.Lithium secondary battery can comprise negative pole and positive pole, electrolyte, and the dividing plate when needing.
The positive pole of lithium secondary battery can be the used any positive pole of conventional lithium secondary battery, for example, by mixed cathode active material powder and adhesive and conductive agent, and makes it form paste or sheet and the positive pole for preparing.
Suitable positive active material is selected from LiMn 2O 4, LiCoO 2, LiNiO 2, LiFeO 2, and V 2O 5In embodiments of the invention, preferred positive active material can embed lithium.The example of this material comprises TiS, MoS, organic disulfide, perhaps organic polysulfide.The example of conductive materials comprises that ketjen is black, acetylene black, furnace black, graphite, carbon fiber, and fullerene.Suitable adhesive comprises polyvinylidene fluoride, carboxymethyl cellulose, methylcellulose, Sodium Polyacrylate.
Positive pole obtains by following step: mix the slurry that comprises positive electrode active material powder, adhesive and conductive agent, be coated on the metal current collector it and drying, and compacting is to form required shape.
Dividing plate can be any single or multiple lift dividing plate commonly used in the lithium secondary battery, and it can comprise, for example, and polyethylene, polypropylene, polyvinylidene fluoride, polyamide, and glass fibre.
The electrolyte that is used for lithium secondary battery can comprise that lithium salts wherein is dissolved in any organic electrolyte of nonaqueous solvents.
Nonaqueous solvents can comprise ethylene carbonate, propylene carbonate, butylene carbonate, benzonitrile, acetonitrile, oxolane, the 2-methyltetrahydrofuran, butyrolactone, dioxolanes, 4-methyl dioxolanes, N, dinethylformamide, dimethylacetylamide, methyl-sulfoxide, dioxane, 1, the 2-dimethoxy-ethane, sulfolane (sulforane), dichloroethanes, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbonic acid first propyl ester, carbonic acid methyl isopropyl ester, ethyl butyl carbonate, dipropyl carbonate, the carbonic acid diisopropyl ester, dibutyl carbonate, diethylene glycol (DEG), dimethyl ether, and composition thereof.In addition, it can comprise any solvent commonly used in the lithium secondary battery.It is preferably the mixture among any and dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate arbitrary of propylene carbonate, ethylene carbonate and butyl carbonate.
Lithium salts can include, but are not limited to, and is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiCF 3SO 3, Li (CF 3SO 2) 3, Li (CF 3SO 2) 2N, LiC 4F 9SO 3, LiClO 4, LiAlO 4, LiAlCl 4, LiN (C xF 2x+1SO 2) (C yF 2y+1SO 2) a kind of among (x and y are natural number in the formula), LiCl and the LiI or two or more mixture.
In addition, electrolyte can comprise polyelectrolyte, it comprises organic electrolyte and polymer for example poly(ethylene oxide), PPOX, poly-acetonitrile, polyvinylidene fluoride, polymethacrylates or polymethyl methacrylate, and these materials strengthen the good swelling behavior of organic electrolyte.
Lithium secondary battery is by with negative pole, positive pole, and electrolyte, and if necessary, dividing plate is inserted in the battery case produced.Fig. 2 illustrates the perspective view according to the lithium secondary battery 1 of embodiment of the present invention.Lithium secondary battery 1 forms cylindrical, and mainly is made up of following material: negative pole 2; Anodal 3; Place the dividing plate 4 between negative pole 2 and anodal 3; Be injected into negative pole 2, the electrolyte in positive pole 3 and the dividing plate 4; Cylindrical battery container 5; And the seal 6 of sealed battery container 5.In lithium secondary battery 1, negative pole 2, anodal 3 and dividing plate 4 sequential cascades, then be coiled into spiral-shaped and be inserted in the battery case 5.
The following examples describe in further detail the present invention, but are not the restriction to scope of the present invention.
Embodiment and Comparative Examples
Embodiment 1
Flake graphite powder particles with average diameter of 30 μ m is introduced in the inserting needle grinding machine and grinding in advance.Remove the ledge and the marginal portion of flake graphite powder particles, have the aggregation of shape spherical or pseudo-sphere with formation.The flake graphite powder particles of gained then is introduced into into mechanical fusion process and further grinds.The flake graphite in powder grain orientation is at in-plane and stacked, and the fine graphite powders particle is placed on the flake graphite in powder particle surface then, thereby obtains at 1000 ℃ of heat treated down second gathering material with carbon elements.
The negative electrode active material of gained mixes with the polyvinylidene fluoride as adhesive (PVdF) of 6 weight portions, and is dispersed in the N-methyl pyrrolidone, thus the slurry of preparation negative pole.Slurry is applied on the copper collector and with roll-type press (roll press) compacting, thus make have 1.5g/cc, the negative pole of the battery lead plate density of 1.6g/cc, 1.65g/cc, 1.85g/cc and 2.0g/cc.
Use described negative pole and lithium metal as counterelectrode, constitute coin-like half cells.1.0M LiPF 6Be dissolved in ethylene carbonate, the mixed solution in dimethyl carbonate and the ethylene methyl esters (volume ratio 3: 3: 4) is as electrolyte.
Embodiment 2
Prepare battery in similarly to Example 1 mode, different is, described second aggregation is by adding the aggregation that obtains based on 100 weight portions in embodiment 1, and the mesophase pitch of 10 weight portions obtains.
Comparative Examples 1
Prepare battery in similarly to Example 1 mode, different is, negative electrode active material obtains by following step: native graphite powder particles, pitch and graphitization catalyst with average diameter of 15 μ m are mixed with silicon dioxide, and formation mixture, the mixture that grinding obtains, and the amorphous granular of carbonization or the gathering of graphitization gained, to make graphite aggregated particle as negative electrode active material.
Comparative Examples 2
Prepare battery in similarly to Example 1 mode, different is, negative electrode active material obtains by following step: carbonization coke granule, pitch and graphitization catalyst are mixed with silicon dioxide, and be shaped and grind the mixture that obtains and form unbodied asperities.Then, by it is carried out high-temperature process, the amorphous granular of gained is carbonized or graphitization.
Comparative Examples 3
Prepare battery in similarly to Example 1 mode, different is that negative electrode active material is amorphous Delanium.
Measurement the results are shown in table 1 according to embodiment 1 and 2 and the compression strength of the negative electrode active material of Comparative Examples 1～3.Described compression strength is measured as follows: make the anode active material particles layer become one deck and the compression of exerting pressure, measure particle generation breakaway poing.
In addition, at room temperature, under the constant current constant voltage condition to derive from embodiment 1 and 2 and the battery of Comparative Examples 1～3 charge with 0.2C.Initial discharge capacity and charging and discharging efficient have been measured according to battery lead plate density.The results are shown in table 1.
Table 1
Figure C20051006496200131
As shown in table 1, in the compressive strength rate Comparative Examples 1～3 of embodiment 1 and 2 anode active material particles bigger improvement is arranged.Therefore, embodiment 1 and 2 active material have guaranteed electrolyte infiltration lane fully in the high-density electrode plate.The true confirmation, when relatively comprising the discharge capacity of the cell of the high-density electrode plate that surpasses 1.8g/cc, embodiment 1 and 2 initial discharge capacity and efficient are higher than Comparative Examples 1～3.
The negative plate of embodiment 1 is to use the epoxy resin casting and is cut, thereby checks its cross section easily.Fig. 3 is the photo with the plate of optics microscope photographing, shows to show a kind of active material particle that has round various platy layers.
Embodiment 4
LiCoO with 94 weight portions as positive active material 2, the super-P conductive agent of polyvinylidene fluoride as adhesive of 2 weight portions (PVdF) and 4 weight portions prepares anode sizing agent by dispersed mixture after mixing in the N-methyl pyrrolidone.Slurry is applied on the aluminium foil and with roll press and compresses, thereby preparation has the positive pole of active body (active material layer) density of 3.4g/cc.
Polyethylene separator is placed between the negative pole anodal and the battery lead plate density with 1.60g/cc of preparation in embodiment 1 for preparing above, constitutes the electrode group.Prepared electrode group is coiled and is pressurizeed, and puts battery case then into.Thereby electrolyte is injected into and forms battery in the shell.1.0M LiPF6 is dissolved in ethylene carbonate, the mixed solution in dimethyl carbonate and the ethylene methyl esters (volume ratio 3: 3: 4) is as electrolyte.
Embodiment 5
Prepare battery in similarly to Example 4 mode, different is, second aggregation is by adding the aggregation that obtains based on 100 weight portions in embodiment 4, and the mesophase pitch of 10 weight portions obtains.
Comparative Examples 4
Prepare battery in similarly to Example 4 mode, different is, negative electrode active material is to obtain by following step: natural graphite particles, pitch and graphitization catalyst with average diameter of 15 μ m are mixed and shaping mixt with silicon dioxide, the mixture that grinding obtains, and the amorphous granular of the gathering of carbonization or graphitization gained, thereby obtain graphite aggregated particle as negative electrode active material.
Comparative Examples 5
Prepare battery in similarly to Example 4 mode, different is that negative electrode active material is to obtain by following step: carbonization coke granule, pitch and graphitization catalyst are mixed and be shaped and grind the mixture that obtains forming amorphous asperities with silicon dioxide.Then, by it is carried out high-temperature process, resulting amorphous granular is carbonized or graphitization.
Comparative Examples 6
Prepare battery in similarly to Example 4 mode, different is that negative electrode active material is amorphous Delanium.
Determine with porosimeter (making) with the negative electrode active material of Comparative Examples 4～6 and the mercury porosity of negative plate according to embodiment 5, the results are shown in table 2 by Micromeritics Inc..In addition, at room temperature with 0.5C to deriving from the battery charge of embodiment 2 and Comparative Examples 1～3, and with 1C it is discharged, thereby determines its flash-over characteristic at low temperatures at-20 ℃.The flash-over characteristic at low temperatures that is shown in table 2 is by representing based on the percentage of discharge capacity at room temperature with discharge capacity at low temperatures.The results are shown in following table 2.
Table 2
Embodiment 5 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6
Porosity (%) with 0.5 μ m or more areolate active material particle 25 7.0 10 10
Porosity (%) with 0.5 μ m or more areolate battery lead plate 27 23 36 12
By the occupied porosity in the space of 10～100 μ m (%) 58 24 25 50
Flash-over characteristic under-20 ℃ of low temperature 60％ 30％ 40％ 60％
As shown in table 2, after the negative pole of compression according to Comparative Examples 4 and 5, thereby the fine particle of finding to be gathered into a particle splits and produces thin space, is compressed and be evenly dispersed in intragranular carbon granule, thereby, increase the quantity of 0.5 μ m or littler micropore.Even these spaces have the porosity identical with embodiment 5, do not have uniformity by the described active material of compression resulting battery lead plate to the battery lead plate, and therefore the electrolyte reaction is also inhomogeneous, causes that reduce the useful life of battery lead plate.Micropore according to 0.5 μ m of the battery lead plate of Comparative Examples 4 and 5 newly forms on the crackle of the grinding that derives from compression process, so that the end face of graphite comes out.Thereby in environment for example-20 ℃, the viscosity of side reaction increase and electrolyte significantly increases.Therefore,, in hair check, be difficult to produce capillarity, and be difficult to cause suitable cell reaction for electrolyte.As a result, flash-over characteristic is at low temperatures degenerated.Yet the battery lead plate of embodiment 5 has the porosity of 0.5 good μ m or littler active material, and this porosity is well kept.In addition, the porosity of 10～100 μ m is very high, so that it is fabulous to preserve the speed of the performance of electrolyte and transmission lithium ion on according to the battery lead plate of embodiment 5, thereby the low-temperature characteristics that shows is very good.
Negative electrode active material of the present invention has high density and good grain compressive strength, and high-density electrode plate and high-capacity battery are provided.Creative lithium secondary battery anode is used the negative electrode active material with the fine holes that only grows up on its surface.Therefore, it seldom breaks in compression process, keeps the shape of active material and prevents that side reaction from taking place.It also brings good swelling suppression characteristic to battery.In addition, cycle life characteristics and cryogenic discharging characteristic improve.

Claims (37)

1. negative electrode active material that is used for lithium secondary battery comprises:
Assemble a plurality of sheet carbon powder particles that form a plurality of anode active material particles, in described anode active material particles, described sheet carbon powder particle is along in-plane orientation and stacked; And
Be positioned at the lip-deep fine holes of the sheet carbon powder particle of gathering.
2. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein on the surface of the sheet carbon powder particle of described gathering, also assembling has thin carbon powder particle powder.
3. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said negative electrode active material has 15MPa or bigger compression strength.
4. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said negative electrode active material has 10～40% micro-porosity, and this micro-porosity is equivalent to the porosity in the occupied zone of 0.5 μ m or littler micropore.
5. according to the negative electrode active material that is used for lithium secondary battery of claim 3, wherein said negative electrode active material has 15～40% micro-porosity, and this micro-porosity is equivalent to the porosity in the occupied zone of 0.5 μ m or littler micropore.
6. according to the negative electrode active material that is used for lithium secondary battery of claim 4, wherein said negative electrode active material has 15～35% micro-porosity, and this micro-porosity is equivalent to the porosity in the occupied zone of 0.5 μ m or littler micropore.
7. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said negative electrode active material has 12% or littler micro-porosity, and this micro-porosity is equivalent to the porosity in the occupied zone of 0.1 μ m or littler micropore.
8. according to the negative electrode active material that is used for lithium secondary battery of claim 7, wherein said negative electrode active material has 3～10% micro-porosity, and this micro-porosity is equivalent to the porosity in the occupied zone of 0.1 μ m or littler micropore.
9. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said negative electrode active material has 30～60% porosity, and it is the porosity in occupied zone, the hole of 10～100 μ m that this porosity is equivalent to.
10. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said sheet carbon powder particle is native graphite or Delanium.
11. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein according to X-ray diffraction analysis, described sheet carbon powder particle has 0.2 or lower 110 planes and the strength ratio on 002 plane.
12. according to the negative electrode active material that is used for lithium secondary battery of claim 2, wherein said fine carbon powder particle comprises the fine graphite particle of the average grain diameter with 5 μ m.
13., further comprise being positioned at the lip-deep amorphous carbon coating of described sheet carbon powder particle according to the negative electrode active material that is used for lithium secondary battery of claim 1.
14. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said anode active material particles has 4 or lower major axis and minor axis ratio.
15. according to the negative electrode active material that is used for lithium secondary battery of claim 14, wherein said anode active material particles has 1～3 major axis and minor axis ratio.
16. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein said negative electrode active material has 1.0g/cc or higher bulk density and the apparent density of 0.6～1.0g/cc.
17. according to the negative electrode active material that is used for lithium secondary battery of claim 1, the bulk density of wherein said negative electrode active material is 30% or bigger with the apparent density ratio.
18. according to the negative electrode active material that is used for lithium secondary battery of claim 1, wherein this negative electrode active material is 2.0～4.0m according to the specific area of BET method mensuration 2/ g.
19. the negative pole of a lithium secondary battery, it comprises battery lead plate and negative electrode active material, and this negative electrode active material comprises:
Assemble a plurality of sheet carbon powder particles that form a plurality of anode active material particles, in this negative electrode active material, described sheet-like particle is along in-plane orientation and stacked; And
Be formed at the lip-deep fine holes of described sheet carbon powder particle.
20. according to the negative pole of the lithium secondary battery of claim 19, wherein also assembling on the surface of described sheet carbon powder particle has thin carbon powder particle.
21. according to the negative pole of the lithium secondary battery of claim 19, wherein said negative electrode active material has 15MPa or bigger compression strength.
22. according to the negative pole of the lithium secondary battery of claim 19, wherein said negative electrode active material has 10～40% pinhole rate, this pinhole rate is equivalent to the porosity in the occupied zone of 0.5 μ m or littler micropore.
23. according to the negative pole of the lithium secondary battery of claim 19, wherein said negative electrode active material has 12% or lower pinhole rate, this pinhole rate is equivalent to the porosity in the occupied zone of 0.1 μ m or littler micropore.
24. according to the negative pole of the lithium secondary battery of claim 19, the pinhole rate of wherein said negative electrode active material is 2 times of the pinhole rates of battery lead plate or lower.
25. according to the negative pole of the lithium secondary battery of claim 19, wherein said negative electrode active material has 30～60% porosity, this porosity is equivalent to the porosity in the occupied zone of the micropore of 10～100 μ m.
26. according to the negative pole of the lithium secondary battery of claim 19, wherein said sheet carbon powder particle is native graphite or Delanium.
27. according to the negative pole of the lithium secondary battery of claim 19, wherein according to X-ray diffraction analysis, described sheet carbon powder particle has 0.2 or lower 110 planes and the strength ratio on 002 plane.
28. according to the negative pole of the lithium secondary battery of claim 20, the wherein said second fine carbon powder particle is the fine graphite particle with average grain diameter of 5 μ m.
29. the negative pole according to the lithium secondary battery of claim 19 further comprises being positioned at the lip-deep amorphous carbon coating of described sheet carbon powder particle.
30. according to the negative pole of the lithium secondary battery of claim 19, wherein said anode active material particles has 4 or lower major axis and minor axis ratio.
31. according to the negative pole of the lithium secondary battery of claim 19, wherein said negative electrode active material has 1.0g/cc or higher bulk density and the apparent density of 0.6～1.0g/cc.
32. according to the negative pole of the lithium secondary battery of claim 19, the specific area that wherein said negative electrode active material is measured according to the BET method is 2.0～4.0m 2/ g.
33. according to the negative pole of the lithium secondary battery of claim 32, wherein said negative pole has the battery lead plate density of 1.5～2.0g/cc.
34. a method for preparing the negative electrode active material of lithium secondary battery comprises:
The mechanical lapping material with carbon element, and make the material with carbon element that is ground be configured as spherical or pseudo-spherical shape, form a plurality of fine carbon powder particles simultaneously;
Make described fine carbon powder particle aggregation to material with carbon element, the particle that obtains assembling; And
The particle that heating is assembled obtains negative electrode active material.
35. the method according to the negative electrode active material of the preparation lithium secondary battery of claim 34 also is included in the step of adding the amorphous carbon precursor in the described agglomeration step.
36. according to the method for the negative electrode active material of the preparation lithium secondary battery of claim 34, wherein based on the material with carbon element of 100 weight portions, described amorphous carbon precursor adds with the amount of 5～30 weight portions.
37. a lithium secondary battery comprises the positive pole that contains positive active material, contains the negative pole of negative electrode active material, and contains the electrolyte of lithium salts and nonaqueous solvents, wherein said negative electrode active material comprises:
A plurality of sheet carbon powder particles of assembling with primary structure, in described primary structure, described sheet carbon granule is along in-plane orientation and stacked; And
Be formed at the fine holes on the surface of described carbon powder particle.
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