CN1319195C - Composite particle and, utilizing the same, negative electrode material for lithium-ion secondary battery, negative electrode and lithium-ion secondary battery - Google Patents
Composite particle and, utilizing the same, negative electrode material for lithium-ion secondary battery, negative electrode and lithium-ion secondary battery Download PDFInfo
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- CN1319195C CN1319195C CNB200480002917XA CN200480002917A CN1319195C CN 1319195 C CN1319195 C CN 1319195C CN B200480002917X A CNB200480002917X A CN B200480002917XA CN 200480002917 A CN200480002917 A CN 200480002917A CN 1319195 C CN1319195 C CN 1319195C
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Abstract
Composite particles comprising a metal alloyable with lithium and a graphite material and/or carbon material, wherein at least portion of the metal is in contact with at least one material selected from the group consisting of graphite materials and carbon materials and wherein the ratio of void around the metal to total void is 20% or more. There are further provided, utilizing the composite particles, a negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery. When these composite particles are used in a negative electrode material for lithium ion secondary battery, there can be accomplished three characteristics of large discharge capacity, excellent cycle performance and excellent initial charge discharge efficiency among the properties of lithium ion secondary battery.
Description
Technical field
The present invention relates to can with the metal of lithium alloyage and the compound particle of graphite material and/or the formation of compoundization of material with carbon element, use negative material, negative pole and the lithium rechargeable battery of the lithium rechargeable battery of this compound particle.
Background technology
Lithium rechargeable battery is compared with other secondary cell, owing to have high voltage, a high-energy-density, so extensively popularize as the power supply of electronic equipment.In recent years, the miniaturization of electronic equipment or high performance fast development, more and more higher for the requirement of the energy density of further raising lithium rechargeable battery.
Now, lithium rechargeable battery uses LiCoO usually
2Be positive pole, use graphite to be negative pole.Yet though the invertibity that discharges and recharges of graphite electrode is excellent, its discharge capacity has reached and has approached suitable intercalation compound (LiC
6) the value of theoretical value (372mAh/g).Therefore, in order further to improve the energy density of battery, be necessary to develop the discharge capacity negative material bigger than graphite.
The lithium metal ion has the maximum discharge capacity as negative material.But because in when charging, lithium is separated out with dendritic crystalline ground, the negative pole variation has the problem that the battery charging and discharging cycle lacks.In addition, the lithium that dendritic crystalline is separated out connects dividing plate and arrives positive pole, and battery also might short circuit.
Therefore, research replaces lithium ion as negative material with metal or the metallic compound that lithium forms alloy.The discharge capacity of these alloy anodes is less than lithium metal, but considerably beyond graphite.But because the alloying volume can expand, active material produces powdered, peels off, and the periodic property of lithium rechargeable battery does not also reach practical degree.
In order to solve the shortcoming of aforementioned alloy anode, the negative pole that is compounded to form of research and development metal or metallic compound and graphite material and/or material with carbon element.
In order to absorb the expansion that alloying produces, it is effective making the interior existence of composite material that free crack be arranged.But,, can cause the intensity of composite material and conductivity low if the space is too much.Just, the pore volume of composite material and the anti-damageability of material itself become the relation of antinomy with conductivity, and satisfy both more equably is unusual difficulties.
For example, in No. 3369589 communique of special permission, disclose and a kind ofly can be used as the electrode material use by forming the composite material that metallics, graphite material and the material with carbon element of alloy form with alkali metal such as lithium.In this composite material, the effect that this material with carbon element plays combination or covers metallics and graphite material.The D wave band 1360cm on the surface of this material with carbon element of measuring by the raman spectroscopy method of using argon laser
-1Peak intensity ID and G-band 1580cm
-1The ratio ID/IG (R value) of peak intensity IG is shown as more than 0.4.This represents that this material with carbon element does not have graphitization.But even this composite material, material with carbon element also can be penetrated into composite inner, so the destruction of the composite material that the volumetric expansion when being difficult to avoid this metallics and lithium alloyage causes still can cause periodic property low.
On the other hand, open in the 2000-173612 communique, disclose a kind of part or all surperficial negative material that forms of going up that fibrous carbon is fixed on siliceous particle surface the spy.Even this technology is that the silicon particle shrinks, and also can guarantee the interparticle conductivity of silicon by fibrous carbon when discharge.But though this structure can be kept conductivity, the expansion of the metal that produces in the time of can not absorbing charging can cause the low of periodic property.
In No. 3466576 communique of special permission, the negative material that a kind of porousness particle that is formed by siliceous particle and carbon contg particle with the charcoal covering obtains is disclosed.In addition, this carbon contg particle is equivalent to a kind of graphite material.In the example of this technology, although can be with negative material porous energetically, because the volumetric expansion when silicon and lithium alloyage, the structural deterioration that can produce negative material still can not obtain satisfiable periodic property.In addition, because carbon contg particle (graphite material) is the following smaller value of 1 μ m, so electrolyte is easy to generate decomposition reaction, the efficiency for charge-discharge at initial stage is also low.
As mentioned above, in the prior art, be difficult to make absorb expansion and keep all excellences of conductivity two aspects.
According to above-mentioned technical background, a kind of lithium rechargeable battery is provided in the present invention, this secondary cell will contain can be used for the negative material of lithium rechargeable battery with the compound particle of these 3 kinds of compositions of metal, graphite material and material with carbon element of lithium alloyage the time, discharge capacity is bigger, and can realize that excellent periodic property and excellent initial discharge and recharge rate.In other words, the object of the present invention is to provide the NEW TYPE OF COMPOSITE particle of these 3 kinds of performances that can satisfy lithium rechargeable battery, the negative material that uses the lithium rechargeable battery of this compound particle, negative pole and lithium rechargeable battery.
Summary of the invention
The present invention provides a kind of compound particle that contains metal, graphite material and material with carbon element, wherein can contact with at least a kind of material that is selected from graphite material and material with carbon element, and the space around this metal is more than the 20vol% with respect to whole spaces with at least a portion of the metal of lithium alloyage.In addition, this graphite material of this compound particle is preferably at least a kind of material that is selected from flaky graphite and fibrous graphite.
In addition, in these compound particles, when this graphite material is flakey, the peak intensity that is preferably the D wave band in the Raman spectrum with respect to the ratio of the peak intensity of G-band for less than 0.4 material.
In addition, in these compound particles, this graphite material is preferably the average interplanar of X-ray diffraction every d
002Be the fibrous graphite below the 0.34nm.
In addition, at least a portion that any above-mentioned compound particle is preferably this metal contacts with fibrous graphite material, and at least a portion of their outer surface covers with material with carbon element.In addition, this compound particle more preferably further contains flaky graphite.
In addition, the metal in above-mentioned any compound particle is preferably silicon.
In addition, the average grain diameter of the metal of any above-mentioned compound particle is preferably 0.01～10 μ m.
In addition, the metal of above-mentioned any compound particle is preferably noncrystal.
In addition, the specific area of any above-mentioned compound particle is preferably 20m
2Below/the g.
In addition, the average grain diameter of above-mentioned any compound particle is preferably 1～50 μ m.
In addition, in this application, also provide the anode material for lithium-ion secondary battery that contains above-mentioned any compound particle.In addition, also provide the lithium ion secondary battery cathode that uses this ion secondary battery cathode material lithium.In addition, also provide the lithium rechargeable battery that uses this lithium ion secondary battery cathode.
In addition, in this application, a kind of invention of compound particle also is provided, this compound particle be by material with carbon element can with the metal and the incorporate compound particle of graphite material of lithium alloyage, it is characterized in that: this compound particle has the space, and with respect to whole spaces of this compound particle, the ratio in the space of peripheral metal is more than 20%.
Description of drawings
Fig. 1 is the generalized section that coin shape that expression is used to discharge and recharge experiment is estimated the structure of battery.
Fig. 2 is the generalized section of illustrative compound particle in the embodiments of the invention 1.
Embodiment
Below, the present invention is more specifically described.
As mentioned above, in metal-graphite in the past (carbon) the type composite material, can't avoid metal in the negative pole and lithium to form and the reduction of the periodic property that the expansion during alloy causes.Therefore, present inventors study in the conductivity that keeps negative pole, can also absorb the negative pole of the structure of this expansion.The result is, only increase the total void of compound particle, can not keep the conductivity of negative pole, if but around constituting metal, form the space that can absorb this expansion, then find and to prevent the powdered of compound particle and peel off while the conductivity of keeping negative pole, so far finish the present invention.
(compound particle)
Compound particle of the present invention is the compound particle that contains metal, graphite material and material with carbon element, wherein can contact with at least a kind of material that is selected from graphite material and material with carbon element, and the space around this metal is more than the 20vol% with respect to whole spaces with at least a portion of the metal of lithium alloyage.
In this compound particle, at least a portion of this metal contacts with graphite material or material with carbon element, perhaps contact with material with carbon element with graphite material, and the space around this metal also contacts with at least a portion of this metal surface.Usually, this compound particle disperses, comprises a plurality of these metallics, disperses to contain the indefinite space of a plurality of sizes.
In the present invention, the space around this metal (below, be also referred to as space on every side) relatively the ratio in whole spaces of compound particle be more than the 20vol%.When not enough 20vol%, the expansion in the time of can not absorbing this metal and lithium formation alloy.Voidage is more than the 40vol% around preferred, and more effective voidage on every side is more than the 50vol%.In addition, the upper limit of voidage on every side of metal also can be 100% of a theory.At this moment, the space in the compound particle all is and this metal part branch state of contact.The application does not get rid of this situation.But for common particle of the present invention, the suitable higher limit of voidage is meant 80～90vol% on every side.
In addition, in compound particle of the present invention, the ratio that whole voidages occupy whole volumes is preferably 3～50vol%.Usually, if be more than the 3vol%, then can fully absorb the volumetric expansion that alloying produces; If be below the 50vol%, then can fully guarantee the intensity of compound particle, be preferably 30～50vol% especially.
The volume in whole spaces of compound particle of the present invention for example can be measured by the compound particle that the mercury porosimeter exposes section to pulverizing and obtains.And, can calculate the voidage (plot ratio) of the integral body of compound particle thus.
With respect to compound particle overall clearance of the present invention, the ratio in the space of metal is tried to achieve according to following method on every side.By selected any 50 compound particles of scanning electron microscope, the shooting multiplying power is 400 times a section photograph.Obtain according to this section photograph the total value of whole void area of each compound particle and each metal around the total value in space.Use the value of these 50 compound particles, try to achieve around the metal void area with respect to the ratio (area occupation ratio) of whole void area, again with the arithmetic mean of per 1 compound particle as voidage around the metal of the present invention.According to this section photograph, can judge whether at least 1 part of this metal contacts with graphite material and/or material with carbon element.
In addition, the weight of compound particle is formed, and for metal, is with the compound particle ashing time, carries out the elementary analysis of emission spectrometry, is scaled the value of metal concentration.
Graphite material and material with carbon element are taken pictures after being to use petrographic microscope that the section of compound particle is amplified to 1000 times, are target with any 10 particles, judge according to the difference in appearance that crystalline height causes.In addition, both ratios are the mean value of the ratio of the occupied area of the graphite material of particle inside and material with carbon element.
In addition, the occupied area ratio of graphite material and material with carbon element can use transmission electron microscope to observe and try to achieve behind the section thin slice of preparation compound particle.Here, though what try to achieve is the area ratio of graphite material and material with carbon element, because the density of graphite material and material with carbon element does not have bigger difference, so in the present invention, aforementioned area ratio of trying to achieve and part by weight are roughly the same.
In the compound particle of the present invention, owing to aforementioned interspace is present in around the aforementioned metal, so can improve the periodic property of lithium rechargeable battery.This is because when charging, and the expansion of this metal is absorbed by this space, suppresses to contain the structural deterioration of the negative material of this compound particle.Just, for example,, also can keep form, keep in touch between each compound particle, not have injury set electrical as the compound particle of this negative material integral body even when the powdered of metal own.Therefore, deduction can suppress the periodic property reduction.
It is flakey or fibrous that compound particle of the present invention is preferably the graphite material that constitutes this compound particle.
If this graphite material is a flakey, then in compound particle, form the space easily, particularly can improve periodic property etc.In addition, when compound particle of the present invention is flakey at this graphite material, the peak intensity (ID) of the D wave band in the Raman spectrum of this compound particle with respect to the ratio (ID/IG) of the peak intensity (IG) of G-band preferably less than 0.4.Use the Raman spectrum of wavelength, can judge the crystallinity of the outer surface of compound particle with respect to the ratio (ID/IG) of the peak intensity (IG) of G-band according to the peak intensity (ID) of D wave band as the argon laser mensuration compound particle of 514.5nm.This ID/IG is than so-called " R value ", and the R value of compound particle of the present invention is preferably less than 0.4.In addition, common G-band is 1580
-1In observe, the D wave band is 1360
-1In observe, according to evaluated error respectively ± 20
-1The zone in observe.By satisfying the structure of aforementioned compound particle, can obtain the R value less than 0.4 compound particle.The surface crystallization of this compound particle is higher, and so the excellences such as efficiency for charge-discharge at periodic property and initial stage are preferred especially.In addition, the preferred scope of R value is 0.15～0.38, more preferably 0.2～0.3.
In addition, the R value is shown as more than 0.4, for example is to use flaky graphite graphite material in addition as graphite material, and the edge surface of graphite exposes the situation of outer surface etc.
On the other hand, if this graphite material is fibrous, the then interior raisings such as conductivity raising, particularly periodic property of compound particle.In addition, when compound particle of the present invention was fibrous at this graphite material, the average lattice plane of the X-ray diffraction of this fibrous graphite is d at interval
002Be preferably below the 0.34nm.The crystallinity height of this fibrous graphite, discharge capacity is big, so preferred especially.In addition, it is x-ray source that lattice plane mensuration at interval is to use the CuK alpha ray, uses high purity silicon to be standard substance, measures the diffraction maximum of (002) face of graphite metallic substance, calculates d according to its peak position
002Computational methods are according to the shake method of method (JSPS the 117th committee formulate assay method), specifically according to " carbon fiber bar " (large space between muscles Shan Lang work, the 733rd～742 page (1986) compiled society modern age) etc. the value measured of the method for record.
In addition, in compound particle of the present invention, at least a portion that is preferably this metal contacts with fibrous graphite material, and their at least a portion outer surface covers with material with carbon element." covering " described here is that just part or all of outer surface covers with material with carbon element around the compound particle.Therefore, as long as satisfy this key element, the part of material with carbon element just can enter the three-dimensional inside that is formed by fibrous graphite, contacts this metal.For example, also comprise metal is kept in the fibrous graphite of complexing, cover the structure etc. of the part of its outer surface again with material with carbon element.This compound particle can be kept conductivity when keeping absorbing the space of expanding, so excellences such as periodic property are preferred especially.In addition, this compound particle more preferably contains lepidiod graphite.Reason is, flaky graphite forms the space easily, and compares with fibrous graphite, and specific area is less, can improve periodic property and initial charge.This flaky graphite enters this compound particle with the state that surrounds the fibrous graphite that keeps metal.
The shape of compound particle of the present invention is uncertain, and there is no particular limitation.The average grain diameter of compound particle is preferably 1 μ m～50 μ m.Reason is, in this scope, when making electrode, has enough contacts between compound particle, can guarantee conductivity, and periodic property is excellent especially.Be preferably 3 μ m～30 μ m.In addition, usually, be about 3～50 μ m as the preferred size of the general applications of anticathode material.
The specific area of compound particle is preferably 20m
2Below/the g.Reason is, defines the response area with electrolyte, the initial charge excellence.0.5m more preferably
2/ g～20m
2/ g.Be preferably 1m especially
2/ g～10m
2/ g.Specific area is measured by nitrogen adsorption BET method.
The mean aspect ratio of compound particle of the present invention is preferably below 5, is preferably below 3 especially.
(can with the metal of lithium alloyage)
Can with the metal of lithium alloyage, for example can list Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd, Sb, Ge, Ni etc.In addition, also can be 2 kinds or multiple alloy of these metals.Can also further contain above-mentioned element in addition in the alloy.In addition, metal partly or entirely can be compounds such as oxide, nitride, carbide.As preferred metal is silicon (Si), tin (Sn), is preferably silicon especially.In addition, this metal can be that crystal also can be noncrystal, more preferably noncrystal.Reason is that expansion isotropically produces, and is smaller to the influence of compound particle.
The shape of this metal is not particularly limited, and can be granular, spherical, sheet, flakey, needle-like, thread etc. any.Can film like be present on the surface of graphite material and material with carbon element.Wherein, preferably granular or spherical particle.
The average grain diameter of this metal is preferably 0.01 μ m～10 μ m.If be more than the 0.01 μ m, then this metal is dispersed enough.On the other hand, if be below the 10 μ m, then absorb the expansion of this metal easily.Be preferably especially below the 1 μ m.Here, described average grain diameter is meant in percentage by volume, and the cumulative frequency of measuring with laser diffraction formula hondrometer is 50% particle diameter.
Metal preferably enters compound particle inside, rather than inserts outer surface.Metal is present in inner, guarantees easily and the contact of graphite material and/or material with carbon element, improves conductivity, shows the high power capacity that is consistent with the metal addition.
(material with carbon element)
Material with carbon element has conductivity, be as in conjunction with or cover metal and graphite material material indispensable composition, make by heat treatment precursor under the temperature of 1500 ℃ of final less thaies.In this application, also material with carbon element is called carbonaceous material.Material with carbon element has conductivity so long as do not contain volatile ingredient in fact, can absorb or break away from the material of lithium ion, just without limits.The kind of the precursor of material with carbon element in this application, is preferably used the different precursor of carbon yield of the material with carbon element after 2 kinds or the multiple carbonization without limits.Here, described carbon yield is the fixed carbon method according to JIS K2425, is heated to 800 ℃, and the remaining composition during described in fact all carbonizations is represented with percentage.Described carbon yield difference is meant that the difference between the carbon yield between several material with carbon elements is more than several %, is preferably more than 10%.
As the material with carbon element precursor can list coal tar, tar light oil, tar middle matter cut, heavy tar, naphtalene oil, fear the tar asphalt class of petroleum-type such as oil, coal tar asphalt, coal tar, mesophase pitch, the crosslinked petroleum asphalt of oxygen, heavy oil or matchmaker's class, perhaps heat-curing resin classes such as type thermoplastic resin, phenolic resins, urea resin, maleic acid resin, coumarone resin, xylene resin, furane resins such as polyvinyl alcohol.From suppressing the viewpoints such as reduction of discharge capacity simultaneously, be preferably the tar asphalt class especially.
2 kinds or multiple precursor that carbon yield is different, for example can use carbon yield is that 10～50% phenolic resins and carbon yield are 50～90% coal tar asphalt.
The precursor of the material with carbon element (material with carbon element A) that carbon yield is relatively low is owing to producing more space in the material with carbon element after heating, so mainly play the effect that forms metal space on every side.On the other hand, the precursor of the material with carbon element (material with carbon element B) that carbon yield is higher relatively, the space that produces in the material with carbon element after the heating is less, can form fine and close material with carbon element, forms the top layer of compound particle, the effect of surrounding compound particle so mainly play.The result is to use the irreversible capacity of the lithium rechargeable battery of the negative material that contains it may reduce (initial charge raising).Therefore, in the manufacture process of compound particle of the present invention, preferred earlier with precursor and the metal of material with carbon element A and graphite material mixes, after compoundization, mix the precursor of material with carbon element B, compoundization.
(graphite material)
Graphite material is so long as can absorb and discharge the material of lithium ion, and just there is no particular limitation.Particularly, part or all of material formed by graphite.For example, be more than 1500 ℃ tar, pitch class to be heat-treated Delanium that (graphitization) obtain and native graphite etc. last.In this application, graphite material is also referred to as the graphite material.More specifically, the material with carbon element that can illustration tar asphalt class of petroleum-type or coal class etc. be had easy graphitization character, the middle phase roasting body and the mesophasespherule of heat treatment polycondensation.Also can with the coke class more than 1500 ℃, be preferably 2800～3300 ℃ of following graphitization processing and obtain.
The shape of graphite material can be spherical, block, sheet, flakey, fibrous etc. any.Particularly, be preferably flakey or be similar to lepidiod material and fibrous material.Its reason as mentioned above.In addition, also can be aforesaid various mixture, shot-like particle, covering, laminate.In addition, also can be the material that has carried out various chemical treatments, heat treatment, oxidation processes, physical treatment etc. in liquid phase, gas phase, the solid phase.
The average grain diameter of graphite material is 1～30 μ m, is preferably 3～15 μ m especially.Reason is, can easily make the compound particle with aforementioned suitable average grain diameter.
In compound particle of the present invention, when using the flaky graphite material, this flaky graphite material is preferably random configuration.Particularly, be preferably the state of cabbage shape, concentric circles assortment.The basal surface of flaky graphite (with the face of edge surface quadrature) is preferably towards the outer surface side of compound particle, and more preferably basal surface partly exposes the outer surface of compound particle.
In compound particle of the present invention, when using fibrous graphite material, this fibrous graphite material can be the state of cohesion, also can be that the state of dispersion is untied in cohesion, is preferably the flocculence cohesion especially to include the state of metallic.Fibrous graphite material is because specific area is bigger, so when the material with carbon element precursor that will have flowability mixes with compound particle, this flowability precursor adsorption is to the surface of this fibrous carbon material that constitutes compound particle, and be difficult to be penetrated into compound particle inside, have the effect of guaranteeing to have the space easily in the compound particle inside that covers.
Fibrous graphite material can obtain by its precursor is heat-treated under final 1500～3300 ℃.So long as can obtain the material of fibrous graphite material, just without limits, being preferably especially can graphited fibrous carbon material as this precursor.For example, can list carbon nano-fiber, carbon nano-tube and vapor deposition carbon fiber etc.This precursor is preferably minor axis long (diameter) and is 1～500nm, is preferably 10～200nm especially.In addition, the length-width ratio of this precursor is preferably more than 5, is preferably 10～300 especially.Here, described length-width ratio is meant fibre length/minor axis length.
(manufacturing of compound particle)
Below, the manufacture method of illustration compound particle of the present invention.In the method for the invention, the multiple material with carbon element precursor that use can be different relatively with metal, graphite material and the carbon yield of lithium alloyage at least is as raw material.Just, for example, can list and to mix with the precursor (precursor A) of the relatively low material with carbon element (material with carbon element A) of the metal of lithium alloyage and graphite material and carbon yield, in the compound particle of gained, the precursor (precursor B) that mixes the higher relatively material with carbon element of carbon yield (material with carbon element B) again, the method for heating.In this manufacture method, heat treatment preferably becomes under the temperature of state that essence do not contain volatile matter at the material with carbon element A that makes compound particle and material with carbon element B and carries out.
At this moment, if the suitable composition of metal, graphite material and material with carbon element represent with weight percent, be in the scope of metal/graphite material/material with carbon element=1～50wt%/30～95wt%/4～50wt%.If this ratio of components in this scope, uses in lithium rechargeable battery when containing the negative material of this compound particle, can improve the discharge capacity of this battery, perhaps obtain improveing the effect of the periodic property of this battery.Preferably mix with the scope of 2～30wt%/60～93wt%/5～30wt%.Particularly, be the scope of metal/graphite material/material with carbon element A/ material with carbon element B=1～50wt%/35～95wt%/2～50wt%/2～40wt%, preferably at 2～30wt%/60～93wt%/3～30wt%/2～30wt%.But, in end article, can't distinguish by precursor A, B and derive and next material with carbon element A, B.
This precursor by more than 600 ℃, be preferably under the temperature more than 800 ℃ heat-treat, carbonization, give conductivity to material with carbon element.This heat treatment can be divided into several stages, carries out repeatedly, also can carry out in the presence of catalyst.In addition, also can under any of oxidizing atmosphere, non-oxidizing atmosphere, carry out.
But, when using silicon, because more than 1500 ℃ the time, carbon and silicon can react and generate SiC, so heating-up temperature is preferably less than 1500 ℃ as metal.Usually, be preferably 1000～1200 ℃.In addition, preferably use suitable dispersant.Dispersant preferably with precursor A or precursor B softening after, below Undec temperature, remove.
In addition, in the arbitrary stage before and after the heat treatment, preferably remove micro mist etc. and carry out granularity and regulate by suitable pulverizing, screening, classification.In addition, under lower temperature, heat-treat, can have under the flexible state, apply operation of rotating complex and the operation of giving high shear force at aforementioned complex.So, complex becomes the shape of subglobular, and particularly when using flaky graphite as a kind of graphite material, this flaky graphite is configuration circularly with one heart easily, so preferred.As the device that can carry out this operation; can use the comminutor of GRANUREX (manufacturing of Off ロ イ Application ト industry company), stirring granulating machine (ニ ユ one グ ラ マ シ Application) (manufacturing of (strain) セ イ シ Application enterprise), vibrations comminutors (ア グ ロ マ ス one) (manufacturing of ホ ソ カ ワ ミ Network ロ Application company) etc., the shearing processing unit (plant)s of compression such as rolls, hybrid system ((strain) nara machinery is made manufacturing), mechanical microsystem ((strain) nara machinery is made manufacturing), mechanical fusing system (manufacturing of ホ ス カ ワ ミ Network ロ Application company) etc.
In addition, before carrying out last heat treatment, can cover the identical or different material with carbon element precursor of multilayer at the outer surface of this complex.
As other manufacture method, can illustration on graphite material, adhere to the precursor of material with carbon element in advance, after this metal mixed, heat-treating methods.Perhaps, can adopt in graphite material, bury underground or cover this metal after, mix heat-treating methods with the precursor of material with carbon element.At this moment, as in gas phase, the organic compound of this metal or this metal is adhered to the method for graphite material, can list CVD methods such as PVD such as vacuum vapour deposition, sputtering method, ion plating, molecular beam epitaxy (Physical Vapor Deposition) method, atmospheric pressure cvd (Chemical Vapor Depositon) method, decompression CVD method, plasma CVD method, MO (Magneto-optic) CVD method, optical cvd method.
In addition, when using flaky graphite, can in the space, inject the precursor of material with carbon element and the aqueous mixture of metal in advance with behind this flaky graphite spheroidization, dipping, the method for the precursor after-baking of mixing material with carbon element etc.
In addition, when using fibrous graphite, can adopt with this metal and this fibrous graphite integrated in advance after, the method for mixing material with carbon element precursor after-baking etc.In the integrated of this metal and this fibrous graphite and heat treatment stages afterwards etc., can coexist with flaky graphite.As making this metal and the incorporate method of this fibrous graphite, for example can adopt the mechanochemistry of mechanical energy such as giving compression, shearing, impact, friction to handle, and after in the organic solvent that has disperseed fibrous graphite material, dropping into this metallic, remove the method for organic solvent etc.
When using compound particle of the present invention to make negative material, negative pole, coexistences such as electric conducting material can be when making negative material commonly used, material modified, additive.For example, can add various graphite materials such as native graphite, Delanium, middle phase roasting body graphitization thing, middle phase corpus fibrosum graphitization thing, and material with carbon element such as non-crystal hard carbon, the conductions such as carbon fiber of carbon black and vapor deposition help material, organic substances such as phenolic resins, metals such as silicon, metallic compounds such as tin oxide.With respect to compound particle, the total amount of their addition is generally 0.1～50 weight %.
The present invention relates to contain the anode material for lithium-ion secondary battery of aforementioned compound particle, and the lithium rechargeable battery that uses this negative material.
(negative pole)
Lithium ion secondary battery cathode of the present invention can be according to the manufacturing process manufacturing of common negative pole, so long as can chemistry, electrochemically obtain the method for stable negative pole just without any qualification.When making negative pole, preferably use in compound particle of the present invention to add adhesive and previously prepared cathode agent.Be preferably the material that electrolyte is demonstrated chemistry and electrochemical stability as adhesive.For example, can use fluorine-type resin powder such as polytetrafluoroethylene, polyvinylidene fluoride, toners such as polyethylene, polyvinyl alcohol, carboxymethyl cellulose etc.Also they can be used simultaneously.Adhesive uses with the ratio about 1～20wt% in the total amount of cathode agent usually.
If carry out more specifically illustration, at first, compound particle of the present invention is adjusted to desirable granularity by classification etc., mix with adhesive, the mixture of gained is distributed in the solvent, become pasty state, the preparation cathode agent.Just, compound particle of the present invention and adhesive are mixed with water, isopropyl alcohol, N-methyl pyrrolidone, dimethyl formamide equal solvent, obtain slurry, use known mixer, mixer, mixing dose, kneader etc. to mix the slurry of gained, preparation paste.This paste is applied on the one or both sides of collector plate, drying has obtained the negative pole of cathode agent even and bonding securely.The thickness of anode mixture layer is 10～200 μ m, be preferably 20～100 μ m.
In addition, negative pole of the present invention also can pass through after compound particle of the present invention and the toner dry mixed such as polyethylene, polyvinyl alcohol, hot press molding manufacturing in mould.
After forming anode mixture layer, carry out pressure weldings such as hot extrusion, can further improve the bonding strength of anode mixture layer and collector body.
There is no particular limitation for the shape of the collector body that uses during negative pole is made.Be preferably paper tinsel shape, mesh-like etc.Material as mesh-like can list wire netting etc.Material as current-collecting member is preferably copper, stainless steel, nickel etc.The thickness of collector body when being the paper tinsel shape, is preferably about 5～20 μ m.
In addition, negative pole of the present invention can also contain can with the compound particle of metal, graphite material and the material with carbon element of lithium alloyage in, further add metallic compounds such as metals such as organic substances such as material with carbon elements such as native graphite layer graphite material and non-crystal hard carbon, phenolic resins, silicon, tin oxide etc.
(lithium rechargeable battery)
Lithium rechargeable battery normally is the main composition key element of battery with negative pole, positive pole and nonaqueous electrolyte.Because anodal and negative pole becomes the carrier of lithium ion respectively, so become following structure: when charging, lithium ion is adsorbed onto in the negative pole, during discharge, breaks away from from negative pole.
Lithium rechargeable battery of the present invention is except using negative material of the present invention as the negative material, and there is no particular limitation, and other cell device such as positive pole, electrolyte, dividing plate can be prepared according to the element of common lithium rechargeable battery.
(positive pole)
Anodal for example can being applied on the collector body surface by the anode mixture with positive electrode and adhesive and conductive agent formation forms.The preferred selection of anodal material (positive active material) can absorb and break away from the fully material of the lithium of amount, can be the lithium-containing compounds such as transition metal oxide, transition metal chalkogenide, barium oxide and lithium compound thereof that contain lithium, formula M xMo
6S
8-YChevrel phase compound shown in (in the formula, M is at least a kind of transition metal, and X is 0≤X≤4, and Y is the interior numerical value of scope of 0≤Y≤1), activated carbon, activated carbon fiber etc.Barium oxide is V
2O
5, V
6O
13, V
2O
4, V
3O
8Shown material.
The transition metal oxide that contains lithium is the composite oxides of lithium and transition metal, can be the material that lithium and 2 kinds or multiple transition metal form homogeneous phase.Composite oxides can use separately, also can be with 2 kinds or multiple being used in combination.The transition metal oxide that contains lithium can be LiM particularly
1 1-xM
2 xO
2(in the formula, M
1, M
2Be at least a kind of transition metal, X is the interior numerical value of scope of 0≤X≤1) or LiM
1 2-YM
2 YO
4(in the formula, M
1, M
2Be at least a kind of transition metal, Y is the interior numerical value of scope of 0≤Y≤2) shown in.
M
1, M
2Shown transition metal is Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn etc., is preferably Co, Fe, Mn, Ti, Cr, V, Al etc.Preferred example is LiCoO
2, LiNiO
2, LiMnO
2, LiNi
0.9Co
0.1O
2, LiNi
0.5Mn
0.5O
2Deng.
The transition metal oxide that contains lithium, for example be as initiation material with lithium, transition metal oxide, hydroxide, salt etc., according to the composition of the metal oxide of being hoped these initiation materials are mixed, by under oxygen atmosphere, 600～1000 ℃ roasting temperature obtains.
Positive active material can use aforesaid compound separately, also can use 2 kinds or multiple simultaneously.For example, can in positive pole, add carbonate such as lithium carbonate.In addition, when forming positive pole, can suitably use various additives such as existing known conductive agent and adhesive.
Anodal can be by by with aforementioned positive electrode, adhesive be used to give the anode mixture that the conductive agent of anodal conductivity forms, be applied to formation anode mixture layer on the two sides of collector body and make.Can use the identical material of material that uses in the manufacturing with negative pole as adhesive.Can use known materials such as graphitization thing, carbon black as conductive agent.
There is no particular limitation for the shape of collector body, can use netted material such as paper tinsel shape or mesh-like, wire netting etc. etc.The material of collector body is aluminium, stainless steel, nickel etc.That its thickness is suitable is 10～40 μ m.
Positive pole also can with negative pole similarly, anode mixture is disperseed in solvent, become the paste shape, this paste shape anode mixture is applied on the collector body, drying forms the anode mixture layer; Also can after forming the anode mixture layer, push pressure weldings such as pressurization again.Thus, the anode mixture layer evenly and securely can be sticked on the current-collecting member.
(nonaqueous electrolyte)
The nonaqueous electrolyte that uses as lithium rechargeable battery of the present invention is the electrolytic salt that uses in the common nonaqueous electrolytic solution, for example can use LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5), LiCl, LiBr, LiCF
3SO
3, LiCH
3SO
3, LiN (CF
3SO
2)
2, LiC (CF
3SO
2)
3, LiN (CF
3CH
2OSO
2)
2, LiN (CF
3CF
2OSO
2)
2, LiN (HCF
2CF
2CH
2OSO
2)
2, LiN ((CF
3)
2CHOSO
2)
2, LiB[C
6H
3(CF
3)
2]
4, LiAlCl
4, LiSiF
6Deng lithium salts.Particularly, from the oxidation stability aspect, preferably use LiPF
6, LiBF
4
The concentration of the electrolytic salt in the electrolyte is preferably 0.1～5mol/l, more preferably 0.5～3.0mol/l.
Can use ethylene carbonate as the solvent that forms liquid nonaqueous electrolyte, propylene carbonate, dimethyl carbonate, carbonic esters such as diethyl carbonate, 1,1-or 1, the 2-dimethoxy-ethane, 1, the 2-diethoxyethane, oxolane, the 2-methyltetrahydrofuran, gamma-butyrolacton, 1, the 3-dioxolane, the 4-methyl isophthalic acid, the 3-dioxolanes, anisole, ethers such as Anaesthetie Ether, sulfolane, thioethers such as methyl sulfolane, acetonitrile, the chloro acetonitrile, nitriles such as propionitrile, trimethylborate, quanmethyl silicate, nitromethane, dimethyl formamide, the N-methyl pyrrolidone, ethyl acetate, tri-methyl ortho formate, nitrobenzene, chlorobenzoyl chloride, benzoyl bromide, thiophane, dimethyl sulfoxide (DMSO), 3-methyl-2-oxazolidone, ethylene glycol, non-proton organic solvents such as dimethylsulphide.
With nonaqueous electrolyte during, can use macromolecular compound by plasticizer (nonaqueous electrolyte) gelation as matrix as macromolecule electrolyte such as polymer solid electrolyte, polymer gel electrolytes.Macromolecular compound as this matrix can be with independent or mixing back uses such as fluorine-type resins such as ether resins such as polyethylene glycol oxide and crosslinked body thereof, polymethacrylate resin, polyacrylate resinoid, polyvinylidene fluoride (PVDF) and vinylidene difluoride-hexafluoropropylene copolymer.
Wherein, from viewpoint of oxidation-reduction stability etc., preferably use fluorine-type resins such as polyvinylidene fluoride and vinylidene difluoride-hexafluoropropylene copolymer.
Can use aforesaid electrolytic salt and nonaqueous solvents as the plasticizer that uses.When being polymer gel electrolyte, be preferably 0.1～5mol/l as the electrolytic salinity in the nonaqueous electrolytic solution of plasticizer, more preferably 0.5～2.0mol/l.
There is no particular limitation in the manufacturing of polyelectrolyte, for example can list macromolecular compound, lithium salts and the nonaqueous solvents (plasticizer) that will constitute matrix and mix, heating, the method for fusion dissolving macromolecular compound; Make macromolecular compound, lithium salts and nonaqueous solvents after mixing, make the method for mixing with organic solvent evaporation with dissolving in the organic solvent; Combination monomer, lithium salts and nonaqueous solvents are mixed,, make the polymerizable monomer polymerization, obtain the method for macromolecular compound etc. with ultraviolet ray, electron beam or molecular beam irradiation mixture.
The ratio of the nonaqueous solvents of polyelectrolyte is preferably 10～90 weight %, more preferably 30～80 weight %.If less than 10 weight %, the conductance step-down; If surpass 90 weight %, then mechanical strength dies down, and is difficult to into membranization.
(dividing plate)
In lithium rechargeable battery of the present invention, also can use dividing plate.There is no particular limitation for the material of dividing plate and structure, for example can list weave cotton cloth, micro-porous film that nonwoven fabrics, synthetic resin are made etc.The micro-porous film of synthetic resin manufacturing is suitable, and particularly the TPO micro-porous film is being suitable aspect thickness, film-strength, the membrane resistance.The micro-porous film made of polyethylene and polypropylene specifically, the perhaps micro-porous film that they are compounded to form etc.
In lithium rechargeable battery of the present invention, owing to used the mesophasespherule that does not expose end face as carbon material for negative electrode, so also can use gel electrolyte.
Use the lithium rechargeable battery of gel electrolyte to constitute by the negative pole that contains aforementioned compound particle, positive pole and gel electrolyte.For example, with negative pole, gel electrolyte, positive pole lamination successively, preserve in the battery external packing material and make.In addition, in addition, can also be at negative pole and anodal outside configuration gel electrolyte.
In addition, lithium rechargeable battery of the present invention can be an arbitrary structures, there is no particular limitation for its shape, form, and according to its purposes, lift-launch machine, desired charge/discharge capacity etc., can at random select from cylinder type, cube type, Coin shape, coin shape etc.In order to obtain the higher hermetic type battery with nonaqueous electrolyte of fail safe, to be preferably having overcharging etc. when unusual, can rise by the perception inner pressure of battery, and the battery of the device of blocking-up electric current.Be polymer solid electrolyte battery and polymer gel electrolyte battery the time, also can be the structure of enclosing laminated film.
Embodiment
Then, by embodiment and comparative example the present invention is carried out more specifically explanation, but the present invention limits by them.In addition, in embodiment and comparative example, make the evaluation of structure shown in Figure 1 and estimate with the coin shape secondary cell.Actual battery is based on purpose of the present invention, makes according to known method.In this evaluation electricity pool, be that the effect utmost point is shown as negative pole, polarity is shown as positive pole.
In embodiment and comparative example, the carbon yield of the precursor of material with carbon element is the following mensuration of fixed carbon method according to JIS K2425.
Measure the 1g material with carbon element and be put in the crucible, lid did not heat 30 minutes in 430 ℃ electric furnace.Afterwards, as dual crucible, heating is 30 minutes under 800 ℃ electric furnace, removes volatile ingredient, with the percentage of remaining composition as carbon yield.
The average grain diameter of compound particle is to use laser diffraction formula particle size distribution meter, and (セ イ シ Application company makes, and LS-5000) measures, and in percentage by volume, cumulative frequency is 50% particle diameter.
The voidage of the integral body of compound particle is tried to achieve the ratio with respect to the volume of compound particle integral body after being to use the mercury porosimeter to measure the volume in whole spaces.
Specific area is tried to achieve according to the BET method of nitrogen adsorption.
The lattice plane of X-ray diffraction is d at interval
002Measure according to preceding method.
Space around this metal is to observe with scanning electron microscope from the particle section with respect to the ratio in whole spaces of compound particle, calculates the area ratio of two-dimentional void area and tries to achieve, the mean value of the instrumentation result in the section of 50 compound particles of employing.Here, if the space directly contacts existence with the part of this metallic surface, then as the space around this metal.
In addition, the ratio of this metal in the compound particle is tried to achieve according to aforementioned luminous optical spectroscopy.The ratio of graphite material and material with carbon element is tried to achieve according to the method for using aforementioned petrographic microscope.
In addition, the R value of raman spectroscopy is used laser raman spectroscopy apparatus (NR-1800: Japanese beam split (strain) is made), is the 514.5nm argon laser at exciting light, and irradiated area is to analyze under the 50 μ m φ, with D wave band 1360cm
-1The intensity at peak is ID, G-band 1580cm
-1The ratio ID/IG of peak intensity when being IG.
(embodiment 1)
(manufacturing of compound particle)
(high-purity chemical research institute (strain) makes to make silicon metal powder, average grain diameter 2 μ m) (ベ one Network ラ イ ト company in Sumitomo makes to be dispersed in phenolic resins, carbon yield 50%) in the ethanolic solution, form slurry, use twin shaft to add heat kneading machine, with this slurry and native graphite (China ink industrial manufacturing in Yueshi in (strain), average grain diameter 10 μ m), descended mixing 1 hour at 150 ℃, obtain mixing thing.At this moment, the weight percent that is prepared as solid state component is phenolic resins 18wt%, Si powder 6wt%, native graphite 76wt%.In addition, the described solid state component of the application is before preparation solution, at normal temperatures, is shown as solid-state material.
Then, at the middle matter cut of coal tar asphalt (JFE chemistry (strain) is made, carbon yield 60%) blended tars, preparation coal tar asphalt solution.Use twin shaft to add heat kneading machine, this solution and this mixing thing were descended mixing 1 hour at 200 ℃.At this moment, the weight percent that is prepared as solid state component is that coal tar asphalt is that 30wt%, this mixing thing are 70wt%.After mixing, vacuum is removed the solvent in this mixing thing.
After the mixing thing coarse crushing with gained, heated 10 hours down, make this mixing thing for not containing the state of volatile matter in fact at 1000 ℃.Just, with phenolic resins and coal tar asphalt carbonization.The average grain diameter of the compound particle of gained is 15 μ m.Measure the voidage of weight percent, compound particle integral body of each constituent material in the compound particle of gained and the space around the metal with respect to the ratio in whole spaces of compound particle etc., the result is shown in table 1-1 and table 1-2.
In addition, use scanning electron microscope, observe structure in the particle from the section of compound particle.The result illustrates in Fig. 2.So, can judge and to contact with graphite material 11 and/or material with carbon element 13 with at least a portion of the metallic silicon 12 of lithium alloyage, and the space around this metal also contacts with at least a portion on the surface of this metal 12.In addition, mark 14 is edge surfaces of graphite material, and mark 15 is basal surfaces of graphite material.
(manufacturing of cathode agent paste)
Aforementioned compound particle of 90wt% and 10wt% polyvinylidene fluoride are joined in the N-methyl pyrrolidone, use homo-mixer, under 2000rpm, mixed 30 minutes, preparation organic solvent cathode agent.
(manufacturing of active electrode (negative pole))
Aforementioned cathode agent paste is applied on the Copper Foil with homogeneous thickness, and in a vacuum, under 90 ℃, make solvent evaporates, drying is by the pressurization of hand extruding anticathode mixture layer.With Copper Foil and anode mixture layer drawing is the cylindric of diameter 15.5mm, makes by collector body and the active electrode (negative pole) that forms with the cathode agent of this collector body driving fit.
(manufacturing of polarity)
Lithium metal foil is squeezed on the nickel screen, and drawing is that diameter is the cylindric of 15.5mm, the polarity of making the collector body that formed by nickel screen and forming with the lithium metal foil of this collector body driving fit.
(electrolyte dividing plate)
Make LiPF
6Be dissolved in the solvent that has mixed 33wt% ethylene carbonate and 67wt% carbonic acid Methylethyl ester, so that its concentration is 1mol/dm
3, the preparation nonaqueous electrolytic solution.Make gained nonaqueous electrolytic solution dipping polypropylene porous plastid, make the dividing plate of electrolyte dipping.
(evaluation battery)
Make coin shape secondary cell shown in Figure 1 as estimating battery.
Between the positive pole 4 of the negative pole 2 of driving fit collector body 7b and driving fit collector body 7a, clamp the dividing plate 5 of dipping electrolyte, lamination.Afterwards, negative electrode collector 7b side is preserved in the outer dress cup 1, positive electrode collector 7a side is preserved in the outer tinning 3, close with outer tinning 3 thereby will adorn cup 1 outward.At this moment, the edge part of dress cup 1 and outer tinning 3 by insulation spacer 6, is riveted over two edges portion airtight outside.
This is estimated battery, under 25 ℃ of temperature, carry out the following experiment that discharges and recharges, calculate discharge capacity, initial charge, periodic property.Evaluation result is as shown in table 2.
(discharge capacity initial charge)
Under the current value of 0.9mA, carry out constant-current charge, reach 0mV up to loop voltage, when loop voltage reaches 0mV, switch to constant-voltage charge, continuing to be charged to current value again is 20 μ A.Try to achieve charging capacity from the energising amount between this.Afterwards, interrupted 120 minutes.Then, under the current value of 0.9mA, carrying out constant-current discharge, is 1.5V up to loop voltage, tries to achieve discharge capacity from the energising amount between this.Calculate initial charge from following formula.In addition, in this experiment, as charging, the process of disengaging is as discharge with the sub process of adsorbing of the past graphite plasmid of lithium ion.
Initial charge (%)=(charging capacity in the discharge capacity in the 1st cycle/the 1st cycle) * 100
(periodic property)
Under the current value of 4.0mA, carry out constant-current charge, after loop voltage reaches 0mV, switch to constant-voltage charge, after continuing to be charged to current value and being 20 μ A, interrupted 120 minutes.Then, under the current value of 4.0mA, carry out constant-current discharge, reach 1.5V up to loop voltage.Repeating 20 times discharges and recharges.Use following formula computing cycle character.
Periodic property=(discharge capacity in the discharge capacity in the 20th cycle/the 1st cycle) * 100
Evaluation result to battery character (discharge capacity, initial charge and periodic property) is as shown in table 2.
Evaluation battery as shown in table 2, that the compound particle of use embodiment 1 obtains in active electrode demonstrates high discharge capacity, and has higher initial charge.In addition, demonstrate excellent periodic property.
(embodiment 2)
Except in embodiment 1, to silicon metal powder be distributed in the ethanolic solution of phenolic resins, form slurry, use twin shaft to add heat kneading machine, this slurry and native graphite at 150 ℃ following mixing 1 hour the time, are prepared, obtain mixing thing so that the weight percent of solid state component is phenolic resins 20.4wt%, Si powder 6.7wt%, native graphite 72.9wt%.In addition, continue to use twin shaft to add heat kneading machine, coal tar asphalt solution and this mixing thing were descended mixing 1 hour at 200 ℃, the weight percent that is prepared as solid state component is that coal tar asphalt is that 36.9wt%, this mixing thing are 63.1wt%.In addition, under the method and condition identical, make compound particle with embodiment 1.Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 3)
Except in embodiment 1, the Delanium (average grain diameter is 10 μ m) that uses the coke graphitization with bulk to form replaces beyond the lepidiod native graphite, under the method and condition identical with embodiment 1, makes compound particle.Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 4)
Vapor deposition carbon fiber (clear and electrician's (strain) manufacturing with the 92.7wt% graphitization processing, VGCF, the long 150nm of minor axis, mean aspect ratio is about 50) and the silicon particle of 7.3wt% (high-purity chemical research institute (strain) makes, estimate particle diameter 2 μ m) mix, put in the mechanical fusing system (manufacturing of ホ ス カ ワ ミ Network ロ Application company), give mechanical energy, carry out mechanochemistry and handle.Just, be 20m/s, processing time to be that the distance of 30 minutes, swing roller and internal part is under the condition of 5mm in the peripheral speed of swing roller, repeat to apply compression stress, shearing force, obtain the compound particle that the silicon particle is clamped by the vapor deposition carbon fiber.
Then, in 300g coal tar asphalt (JFE chemistry (strain) manufacturing), carbon yield 60%) the middle matter cut (JFE chemistry (strain) manufacturing) that mixes 300g tar in, preparation coal tar asphalt solution, use twin shaft to add heat kneading machine, coal tar asphalt solution and this compound particle of making descended mixing 1 hour at 200 ℃.At this moment, the weight percent that is adjusted to solid state component is that coal tar asphalt is that 42wt%, this compound particle are 58wt%.After mixing, become vacuum to remove matter cut the tar that desolvates, obtain the compound particle that coal tar asphalt covers from this mixing thing.After the compound particle coarse crushing with gained, at 1000 ℃ of following roastings 10 hours, the compound particle that obtains covering.When roasting, volatile ingredient is removed fully.The compound particle that is covered by this material with carbon element is spherical, and average grain diameter is 10 μ m, and specific area is 5.2m
2/ g.
Confirmed that this material with carbon element covers the outer surface of this compound particle, the silicon particle is twined by the carbon fiber of vapor deposition to be clamped, and disperses to have formed many spaces in the inner body of compound particle.Constituent weight percent in the compound particle that is capped of gained is that silicon is that 5.1wt%, fibrous graphite material are that 64.6wt%, material with carbon element are 30.3wt%.
Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 5)
In embodiment 1, use twin shaft add heat kneading machine with coal tar asphalt solution and graphite material, material with carbon element at 200 ℃ following mixing 1 hour the time, add (the China ink industrial manufacturing in Yueshi in (strain) of lepidiod native graphite, average grain diameter 5 μ m), be that coal tar asphalt is that 34wt%, compound particle are that 60wt%, native graphite are 6wt% with the percentage that is adjusted to solid state component.In addition, under the method and condition identical, make compound particle, carry out roasting then, the compound particle that obtains being capped with embodiment 1.The compound particle that is capped of gained is for block, and average grain diameter is 12 μ m, and specific area is 5.3m
2/ g.
Confirmed that this material with carbon element covers the outer surface of this compound particle, the silicon particle is twined by the carbon fiber of vapor deposition to be clamped, and disposes native graphite around it, and disperses to form many spaces in the inner body of compound particle.The weight percent of the constituent in the compound particle that is capped of gained is that silicon is that 5.1wt%, fibrous graphite are that 64.8wt%, flaky graphite material are that 6.5wt%, material with carbon element are 23.6wt%.
Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 6)
Except in embodiment 4, use twin shaft add heat kneading machine with coal tar asphalt solution and compound particle at 200 ℃ following mixing 1 hour the time, it is that 10wt%, compound particle are beyond the 90wt% that the weight percent of solid state component is adjusted to coal tar asphalt, under method and condition similarly to Example 3, make compound particle.
Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 7)
In embodiment 1, (Aldrich makes using tin powder, average grain diameter 1 μ m) replaces Si powder, in the ethanolic solution of phenolic resins, when mixing with native graphite, the weight percent that is prepared as solid state component is: phenolic resins is that 18wt%, tin powder are that 26.7wt%, native graphite are 55.3wt%.In addition, under method and condition similarly to Example 1, make compound particle.Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 8)
In embodiment 1, use and Si powder is pulverized by ball mill, making its average grain diameter is 0.5 μ m.In addition, under the method and condition identical, make compound particle with embodiment 1.Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(embodiment 9)
In embodiment 1, use sand mill to be dispersant with water, Si powder is pulverized, using average grain diameter is the Si powder of 0.3 μ m.In addition, under method and condition similarly to Example 1, make compound particle.Measure from X-ray diffraction, confirm that the Si powder of pulverizing is noncrystal.Then, make cathode agent paste, active electrode, polarity, electrolyte dividing plate and evaluation battery similarly to Example 1.Estimate the character that discharges and recharges of this evaluation battery.
(comparative example 1)
The weight percent that silicon metal powder, flakey native graphite and the coal tar asphalt that uses among the embodiment 1 is prepared as solid state component is respectively 3.8wt%, 38.5wt%, 57.7wt%, with matter cut in the tar as solvent, add heat kneading machine by twin shaft, carry out simultaneously mixing after, add the hot milling thing, remove and desolvate drying.The mixing thing of gained is pulverized,, made compound particle 1000 ℃ of following roastings 10 hours.Then, under method and condition similarly to Example 1, use this compound particle, negative pole and nonaqueous electrolyte to make lithium rechargeable battery.Measure discharge capacity, initial charge and the periodic property of this battery similarly to Example 1, evaluation result is as shown in table 2.
(comparative example 2)
In comparative example 1, silicon metal powder, flakey native graphite and coal tar asphalt are regulated the weight percent that is prepared as solid state component be respectively 3.7wt%, 38.5wt%, 62.5wt%.In addition, with comparative example 1 same method and condition under, make compound particle.Then, under method and condition similarly to Example 1, use this compound particle, negative pole and nonaqueous electrolyte, make lithium rechargeable battery.Measure discharge capacity, initial charge and the periodic property of this battery similarly to Example 1, evaluation result is as shown in table 2.
Around the silicon particle, do not exist the comparative example 1,2 in space can't obtain higher initial charge and periodic property.This can think because the structure of the expansion damage compound particle of the silicon particle in when charging, causes the low and active material of conductivity to be peeled off from collector body.
Table 1-1
| The constituent of compound particle and composition | |||||||
| Metal | Graphite material | Material with carbon element | |||||
| Kind | Average grain diameter (μ m) | Form (wt%) | Kind | Form (wt%) | The precursor kind | Form (wt%) | |
| Embodiment 1 | Crystallized silicon | 2 | 5.1 | The flakey native graphite | 65.1 | The phenolic resins coal tar asphalt | 29.8 |
| Embodiment 2 | Crystallized silicon | 2 | 5.1 | The flakey native graphite | 55.1 | The phenolic resins coal tar asphalt | 39.8 |
| Embodiment 3 | Crystallized silicon | 2 | 5.1 | The engineered stone China ink | 65.1 | The phenolic resins coal tar asphalt | 29.8 |
| Embodiment 4 | Crystallized silicon | 2 | 5.1 | Fibrous graphite | 64.6 | Coal tar asphalt | 30.3 |
| Embodiment 5 | Crystallized silicon | 2 | 5.1 | Fibrous graphite flakey native graphite | 64.8 6.5 | Coal tar asphalt | 23.6 |
| Embodiment 6 | Crystallized silicon | 2 | 6.8 | Fibrous graphite | 86.9 | Coal tar asphalt | 6.3 |
| Embodiment 7 | Crystallinity tin | 1 | 23 | The flakey native graphite | 47.2 | The phenolic resins coal tar asphalt | 29.8 |
| Embodiment 8 | Crystallized silicon | 0.5 | 5.1 | The flakey native graphite | 65.1 | The phenolic resins coal tar asphalt | 29.8 |
| Embodiment 9 | Non-crystalline silicon | 0.3 | 5.1 | The flakey native graphite | 65.1 | The phenolic resins coal tar asphalt | 29.8 |
| Comparative example 1 | Crystallized silicon | 2 | 5 | The flakey native graphite | 50 | Coal tar asphalt | 45 |
| Comparative example 2 | Crystallized silicon | 2 | 5 | The flakey native graphite | 45 | Coal tar asphalt | 50 |
Table 1-2
| The rerum natura of compound particle | ||||||
| Average grain diameter (μ m) | Specific area (m 2/g) | Raman spectroscopy (R value) | Whole voidage (%) | Voidage (%) around this metal | The lattice plane of fibrous graphite is (nm) at interval | |
| Embodiment 1 | 15 | 4 | 0.29 | 25 | 55 | - |
| Embodiment 2 | 15 | 5 | 0.28 | 22 | 25 | - |
| Embodiment 3 | 13 | 5 | 0.45 | 26 | 58 | - |
| Embodiment 4 | 10 | 14 | 0.3 | 30 | 64 | 0.3366 |
| Embodiment 5 | 12 | 9 | 0.35 | 33 | 60 | 0.3366 |
| Embodiment 6 | 10 | 23 | 0.32 | 32 | 55 | 0..3366 |
| Embodiment 7 | 15 | 4 | 0.29 | 25 | 55 | - |
| Embodiment 8 | 13 | 6 | 0.3 | 28 | 48 | - |
| Embodiment 9 | 14 | 7 | 0.31 | 31 | 50 | - |
| Comparative example 1 | 15 | 5 | 0.32 | 30 | 15 | - |
| Comparative example 2 | 15 | 5 | 0.34 | 32 | 10 | - |
Table 2
| Discharge capacity (mAh/g) | Initial charge (%) | Periodic property (%) | |
| Embodiment 1 | 487 | 87 | 90 |
| Embodiment 2 | 485 | 86 | 88 |
| Embodiment 3 | 480 | 88 | 87 |
| Embodiment 4 | 477 | 90 | 93 |
| Embodiment 5 | 480 | 92 | 94 |
| Embodiment 6 | 478 | 88 | 87 |
| Embodiment 7 | 486 | 87 | 87 |
| Embodiment 8 | 487 | 88 | 91 |
| Embodiment 9 | 487 | 87 | 92 |
| Comparative example 1 | 475 | 84 | 76 |
| Comparative example 2 | 474 | 83 | 72 |
Use contains the lithium rechargeable battery of the negative material of compound particle of the present invention as negative pole, and discharge capacity is big, initial charge and periodic property excellence.Therefore, the lithium rechargeable battery that uses negative material of the present invention to form satisfies in recent years the needs to high-energy-densityization, is being effective aspect the miniaturization of the machine that carries and the high performance.In addition, compound particle of the present invention obtains the advantage that material cost is lower easily owing to can use over the made of using as the material of compound particle so have material.
Claims (15)
1. compound particle, this compound particle contains metal, graphite material and material with carbon element, wherein can contact with at least a kind of material that is selected from graphite material and material with carbon element, and the space around this metal is more than the 20vol% with respect to whole spaces with at least a portion of the metal of lithium alloyage.
2. compound particle according to claim 1, wherein this graphite material is at least a kind of material that is selected from flaky graphite and fibrous graphite.
3. compound particle according to claim 1, wherein this graphite material is a flakey, the peak intensity of the D wave band in the Raman spectrum with respect to the ratio of the peak intensity of G-band less than 0.4.
4. compound particle according to claim 1, wherein this graphite material is the average lattice plane interval d of X-ray diffraction
002Be the fibrous graphite below the 0.34nm.
5. compound particle according to claim 1, wherein, at least 1 part of this metal contacts fibrous graphite material, and their at least 1 part outer surface is covered by material with carbon element.
6. compound particle according to claim 5, wherein this compound particle further contains flaky graphite.
7. compound particle according to claim 1 is wherein replaced this metal with silicon.
8. compound particle according to claim 1, wherein the average grain diameter of this metal is 0.01～10 μ m.
9. compound particle according to claim 1, wherein this metal is noncrystal.
10. compound particle according to claim 1, wherein the specific area of this compound particle is 20m
2Below/the g.
11. compound particle according to claim 1, wherein the average grain diameter of this compound particle is 1～50 μ m.
12. contain the anode material for lithium-ion secondary battery of each described compound particle in the claim 1～11.
13. use the lithium ion secondary battery cathode of the described anode material for lithium-ion secondary battery of claim 12.
14. use the lithium rechargeable battery of the described lithium ion secondary battery cathode of claim 13.
15. compound particle, this compound particle is to pass through the incorporate compound particle of carbonaceous material with the metal and the graphite material of lithium alloyage, it is characterized in that: this compound particle has the space, and with respect to whole spaces of this compound particle, the ratio in the space of peripheral metal is more than 20%.
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| JP083282/2004 | 2004-03-22 |
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