CN101321695B - Graphite material, carbon material for battery electrode, and battery - Google Patents
Graphite material, carbon material for battery electrode, and battery Download PDFInfo
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- CN101321695B CN101321695B CN2006800455778A CN200680045577A CN101321695B CN 101321695 B CN101321695 B CN 101321695B CN 2006800455778 A CN2006800455778 A CN 2006800455778A CN 200680045577 A CN200680045577 A CN 200680045577A CN 101321695 B CN101321695 B CN 101321695B
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Abstract
通过将生焦炭等的在惰性气氛下从300℃加热到1000℃时的加热减量成分为5质量％～20质量％的碳原料粉碎，接着对粉碎了的碳原料进行石墨化处理，由此得到在较高地维持初次充放电时的初期效率和放电容量的状态下，由于具有比表面积和平均粒径均小的物性，因此能够制作兼有高能量密度和高电流负荷特性的电极的适合于锂离子二次电池用负极碳材料等的石墨材料。而且使用该石墨材料得到电池用电极。
By crushing a carbon raw material having a heating loss component of 5% to 20% by mass when heated from 300°C to 1000°C in an inert atmosphere, such as raw coke, and then graphitizing the crushed carbon raw material, a graphite material suitable for a negative electrode carbon material for a lithium ion secondary battery, etc., which can be used to make an electrode having both high energy density and high current load characteristics, is obtained while maintaining the initial efficiency and discharge capacity at the time of initial charge and discharge at a high level, due to the physical properties of having a small specific surface area and an average particle size. And the graphite material is used to obtain a battery electrode.
Description
Technical field
The application is based on the patented claim 2005-350138 of Japan of on December 5th, 2005 application, at the patented claim 2005-365878 of Japan of application on December 20th, 2005 and in the application of the patented claim 2005-368727 of Japan of application on December 21st, 2005, quote the disclosure of these Japan's patented claims in this application.
Background technology
Power supply as handheld device etc. mainly uses lithium secondary battery.Its functional diversities such as handheld device, power consumption constantly increases.Therefore, require to increase its cell container, improve charge simultaneously for lithium secondary battery.In addition, power tool such as electric drill and hybrid vehicle etc. improve constantly the demand of height output and jumbo secondary cell.Plumbous secondary cell, NI-G secondary cell, nickel-hydrogen secondary cell were mainly used in this field in the past, but higher to the expectation of the lithium-ion secondary cell of small-sized light and high-energy-density, were just seeking the lithium-ion secondary cell of high current load excellent.
This lithium secondary battery generally uses lithium salts such as cobalt acid lithium in positive active material, in negative electrode active material, use blackings such as graphite.
As the graphite of negative electrode active material, the mesocarbon microsphere is widely used.But the spherular ME of mesocarbon is complicated, and it is very difficult making its price low.
Graphite has natural graphite and synthetic graphite.Wherein natural graphite can obtain at an easy rate.Yet, because natural graphite is flakey, therefore together forming cream when itself and tackiness agent, when being coated on this cream on the current collector, natural graphite is orientated along a direction.When using such electrode charging, electrode only expands in a direction, and the performance as electrode is reduced.Someone once proposed the natural graphite granulation is made it to become the globular scheme, but since the compacting when making electrode cause the natural graphite of balling broken, and be orientated.In addition, because the surface of natural graphite is active, therefore gas takes place in large quantities when primary charging, initial stage efficient is low, and cycle characteristics is also bad.
Synthetic graphite by greying goods representatives such as oil, coal-tar pitch, coke also can obtain less expensively.And intensity is high, is difficult to fragmentation.But the needle coke of good crystallinity is a flakey, easily orientation.In addition, non-needle coke obtains approaching the spheric particle easily, but that loading capacity is low, initial stage efficient is not good yet is more.
Under such situation, carried out of the exploitation of the battery electrode of all spherular cheapnesss of alternative mesocarbon with graphite material.Patent documentation 1 had once proposed a kind of lithium secondary battery anode and had used carbon material; Be to being that the carbon dust of raw material is heat-treated the graphitized carbon powder for preparing with pitch under boron cpd coexistence; It is characterized in that the interplanar distance (d of the carbon wire side layer in the thermal expansivity of this carbon dust (CTE), the X-ray diffraction method
002) and the axial size of C (Lc) of crystallite, adopt the 1360cm in the Raman spectroscopy of argon laser
-1Bands of a spectrum are with respect to 1580cm
-1Strength ratio (the R=I of bands of a spectrum
1360/ I
1580) be respectively CTE≤3.0 * 10
-6/ ℃, d
002≤0.337nm, Lc>=40nm, R>=0.6.
Patent documentation 2 had once proposed a kind of lithium secondary battery anode and had used carbon material; The powder that is the green coke charcoal that will be made by at least a coke raw material among oil system or the coal measures BO is after heating, oxidation under the oxidizing gas atmosphere; Carry out the graphitized carbon powder that greying forms; It is characterized in that the interplanar distance (d of the carbon wire side layer in the X ray wide-angle diffraction method of this carbon dust
002), the axial size of C (Lc) of crystallite, thermal expansivity (CTE) and adopt the 1360cm in the Raman spectroscopy of argon laser
-1Near peak is with respect to 1580cm
-1Near the strength ratio (R=I at peak
1360/ I
1580) be respectively d
002≤0.337nm, Lc>=30nm, CTE>=3.0 * 10
-6/ ℃, R>=0.3.
In addition, the applicant had once proposed a kind of by being 3m through the specific surface area of calcined coke being pulverized and greying obtains in patent documentation 3
2Below/the g, aspect ratio is below 6, tap volume density is 0.8g/cm
3The lithium cell that above powdered graphite is processed is used carbon material.
Patent documentation 1: japanese kokai publication hei 8-31422 communique
Patent documentation 2: japanese kokai publication hei 10-326611 communique
Patent documentation 3: International Publication WO00/22687 communique
Summary of the invention
Yet the graphite material that in patent documentation 1～2, proposes can not obtain sufficient initial stage efficient, loading capacity.In addition, the graphite material that in patent documentation 3, proposes is the material that can obtain high loading capacity, cycle characteristics, efficiency for charge-discharge.The graphite material that in patent documentation 1～3, proposes is compared with the mesocarbon microsphere, and tap density is the tendency height of step-down a little.Can think that this is to result from the shape of particle, for example aspect ratio etc. is caused, but when tap density was low, electrode density can not raise, as a result the capacity step-down of battery.In addition, above-mentioned graphite material is compared with the mesocarbon microsphere, in the occasion that is identical size-grade distribution, in any case the tendency that exists specific surface area all to increase.The increase of specific surface area causes the usage quantity of tackiness agent to increase, and the tackiness agent in the electrode occupies rate and raises.Because tackiness agent is helpless to discharge and recharge, so the capacity of battery reduces as a result.
By above situation, the negative material that comminuting coke is processed gives that can only to substitute the spherular abundant performance of mesocarbon very difficult.
In addition, it has been observed by the present inventors that specifically, the D50 that makes realistic situation is that the situation about 15 μ m becomes is about 2～9 μ m, can shorten the diffusion time of lithium in the graphite, improves the current load characteristic of negative material through dwindling the particle diameter of graphite material.
Yet when the method for document 1～3 became such granularity, specific surface area became 10m
2Occasion more than the/g is many.The advantage that increase position when specific surface area has lithium ion entering graphite layers when increasing, but because chemically active part increases therefore SEI (Solide Electrolyte Interface; Solid electrolyte interface) etc. generating capacity increases, the first non-constant of efficiency for charge-discharge.In addition, when specific surface area was big, the amount of the tackiness agent of use was many, and the amount of negative material reduces in the electrode.
Must reduce the internal resistance of battery for the battery that obtains paying attention to high current load characteristic.Can consider the coating thickness of attenuate electrode as a kind of method that solves.Be the occasion of tackiness agent using SBR (styrene butadiene ribber) usually, because the relation of the viscosity of tackiness agent, the specific surface area that can be made into the graphite material of electrode can be 4～6m
2About/g.On the other hand, be the occasion of tackiness agent using PVDF (PVDF), the specific surface area of graphite material can be 2～3m
2Below/the g.Have the graphite material of such granularity and specific surface area concurrently, the mesocarbon manufacturing of saving the high price of a part is very difficult.
The objective of the invention is to provide at an easy rate a kind of initial stage efficiency ratio when discharging and recharging for the first time much higher in the past, and the little graphite material of the aspect ratio electrode active material that is suitable for lithium-ion secondary cell that also increases of loading capacity etc., particle.
The objective of the invention is to provide at an easy rate a kind of initial stage efficient and loading capacity in the time will discharging and recharging for the first time to maintain with goods in the past under the equal or state more than it than the highland; Owing to have specific surface area and aspect ratio is little, tap density is high rerum natura, so can make the graphite material that is suitable for lithium ion secondary battery cathode carbon material etc. of the electrode of high-energy-density.
In addition; The objective of the invention is to provide at an easy rate a kind of initial stage efficient and loading capacity in the time will discharging and recharging for the first time to maintain with goods in the past under the equal or state more than it than the highland; Owing to have specific surface area and a little rerum natura of median size, so can make the graphite material that is suitable for lithium ion secondary battery cathode carbon material etc. of the electrode that has high-energy-density and high current load characteristic concurrently.
Usually, the coking temperature when making petroleum coke is about 500 ℃, but the green coke charcoal that obtains thus still contains moisture, volatile matter.After this in order to remove these volatile matters, the general employing carried out the calcining about 1200 ℃, forms the method for coke.Yet when pulverizing this calcined coke, obtaining the surface has more concavo-convex, granular calcined coke that aspect ratio is big.Even with this granular calcined coke greying, the concavo-convex of its surface can not become level and smooth fully yet, and specific surface area is little unlike the imagination.
Present inventors find, do not use general calcined coke, but will be still residually have the green coke former state ground of volatile matter to pulverize, and then carry out greying, can make aspect ratio little thus, particle surface concavo-convex little, and can reduce the specific surface area after the greying.
In addition; The result that present inventors concentrate on studies repeatedly finds; Through being chosen under the inert atmosphere weight loss on heating composition when 300 ℃ are heated to 1000 ℃ at the carbon raw material of the scope of 5 quality %～20 quality %, it is not calcined and former state ground is pulverized, then heat-treat graphite material that (greying) this cheapness and easy method obtain under given conditions; Has the globular of approaching particle shape; Capacity is high during as electrode materials, and cycle characteristics is excellent, and irreversible capacity is very little.
In addition; Present inventors also find, can obtain a kind of graphite material according to this method, and the aspect ratio of its primary particle is 1.00～1.32; And, do not exist the coating layer of essence perhaps to constitute by having isotropic crystalline structure and being essentially the single particle of forming at particle surface.And find that when this graphite material was used as electrode materials, capacity was high, cycle characteristics is excellent, and irreversible capacity is very little.
In addition, present inventors also find, can obtain a kind of graphite material according to this method, and its D50% in the size distribution of the volume reference of measuring through laser diffractometry is 2～9 μ m, and specific surface area is 2～6m
2/ g, and, do not exist the coating layer of essence perhaps to constitute at particle surface by having isotropic crystalline structure and being essentially the single particle of forming.And find that when this graphite material was used as electrode materials, capacity was high, cycle characteristics is excellent, and irreversible capacity is very little.
The present invention is based on these knowledge opinions further result and the invention accomplished of investigation.
That is, the present invention includes following scheme.
(1) a kind of method for making of graphite material comprises: will be under inert atmosphere weight loss on heating composition when 300 ℃ are heated to 1200 ℃ be that the carbon raw material powder of 5 quality %～20 quality % is broken, then chippy carbon raw material is carried out graphitization processing.
(2) like the method for making of (1) described graphite material, the carbon raw material is that oil is pitch coke or carbobitumen coke.
(3) like the method for making of (1) described graphite material, the carbon raw material is the green coke charcoal.
(4) like the method for making of each described graphite material of (1)～(3), the graphitization processing temperature is 3000 ℃～3300 ℃.
(5) like the method for making of each described graphite material of (1)～(4), the carbon raw material is non-needle coke.
(6), use acheson furnace (Acheson furnace) to carry out graphitization processing like the method for making of each described graphite material of (1)～(5).
(7) a kind of graphite material is to adopt each described method for making of above-mentioned (1)～(6) to obtain.
(8) like (7) described graphite material, spectrometric at 1360cm by raman spectroscopy
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2, and, be 4.0 * 10 at 30 ℃～100 ℃ thermal expansivity (CTE)
-6/ ℃～5.0 * 10
-6/ ℃.
(9) like (7) or (8) described graphite material, in the size distribution of the volume reference of measuring through laser diffractometry, D50% is 10～25 μ m.
(10) like each described graphite material of (7)～(9), bulk volume density is 0.70g/cm
3More than, and the powder density when having carried out rapping for 400 times is 1.0g/cm
3～1.35g/cm
3
(11) like each described graphite material of (7)～(10), specific surface area is 0.8～1.8m
2/ g.
(12) like each described graphite materials of (7)～(11), the centre plane spacing d of (002) face of measuring by X-ray diffraction method
002Be 0.3362nm～0.3370nm.
(13) like each described graphite materials of (7)～(12), the aspect ratio of the particle of being calculated by optical microscope image is 1～5.
(14) a kind of graphite material, the aspect ratio of its primary particle are 1.00～1.32, and do not have the coating layer of essence at particle surface.
(15) a kind of graphite material, the aspect ratio of its primary particle are 1.00～1.32, constitute by having isotropic crystalline structure and being essentially the single particle of forming.
(16) like (14) or (15) described graphite material, be raw material with non-needle coke.
(17) like (16) described graphite material, non-needle coke is that oil is a pitch coke.
(18) like each described graphite material of (14)～(17), the R value of being measured by the LR laser raman method is 0.01～0.2, is 4.0 * 10 at 30 ℃～100 ℃ CTE
-6/ ℃～5.0 * 10
-6/ ℃.
(19) like each described graphite material of (14)～(18), in the size distribution of the volume reference of measuring through laser diffractometry, D50% is 10～25 μ m.
(20) like each described graphite materials of (14)～(19), d
002Be 0.3362nm～0.3370nm.
(21) like each described graphite material of (14)～(20), specific surface area is 0.8～1.8m
2/ g.
(22) like each described graphite material of (14)～(21), bulk volume density is 0.7g/cm
3More than, and the powder density when having carried out rapping for 400 times is 1.0g/cm
3～1.35g/cm
3
(23) a kind of graphite material, D50% is 2～9 μ m in the size distribution of the volume reference of measuring through laser diffractometry, specific surface area is 2～6m
2/ g, and do not have the coating layer of essence at particle surface.
(24) a kind of graphite material, D50% is 2～9 μ m in the size distribution of the volume reference of measuring through laser diffractometry, specific surface area is 2～6m
2/ g, and constitute by having isotropic crystalline structure and being essentially the single particle of forming.
(25) like (23) or (24) described graphite material, be raw material with non-needle coke.
(26) like (25) described graphite material, non-needle coke is that oil is a pitch coke.
(27) like each described graphite material of (23)～(26), the R value of being measured by the LR laser raman method is 0.01～0.2, is 4.0 * 10 at 30 ℃～100 ℃ CTE
-6/ ℃～5.0 * 10
-6/ ℃.
(28) like each described graphite materials of (23)～(27), d
002Be 0.3362nm～0.3370nm.
(29) like each described graphite material of (23)～(28), the aspect ratio of its primary particle is 1.00～1.32.
(30) like each described graphite material of (23)～(29), bulk volume density is 0.4g/cm
3More than, and the powder density when having carried out rapping for 400 times is 0.5g/cm
3～1g/cm
3
(31) a kind of carbon material for battery electrode comprises each described graphite materials of above-mentioned (7)～(30).
(32) like (31) described carbon material for battery electrode, also containing fiber directly is the thomel of 2～1000nm.
(33), contain thomel 0.01～20 mass parts with respect to graphite material 100 mass parts like (32) described carbon material for battery electrode.
(34) like (32) or (33) described carbon material for battery electrode, the aspect ratio of thomel is 10～15000.
(35) like each described carbon material for battery electrode of (32)～(34), thomel is a gas-phase growth of carbon fibre.
(36) like each described carbon material for battery electrode of (32)～(35), thomel is at thomel heat treated more than 2000 ℃.
(37) like each described carbon material for battery electrode of (32)～(36), thomel is the thomel that inside has hollow structure.
(38) like each described carbon material for battery electrode of (32)～(37), thomel is the thomel that contains dendritic thomel.
(39) like each described carbon material for battery electrode of (32)～(38), the centre plane spacing d of (002) face of measuring by X-ray diffraction method of thomel
002Below 0.344nm.
(40) a kind of electrode is used cream, comprises each described carbon material for battery electrode and tackiness agent of above-mentioned (31)～(39).
(41) a kind of electrode is processed with the formed body of cream by above-mentioned (40) described electrode.
(42) a kind of battery comprises above-mentioned (41) described electrode as integrant.
(43) a kind of secondary cell comprises above-mentioned (41) described electrode as integrant.
(44) a kind of power tool, each the described battery that comprises above-mentioned (41)～(43) is as integrant.
(45) a kind of automobile, each the described battery that comprises above-mentioned (41)～(43) is as integrant.
The invention effect
When using graphite material of the present invention, can under the state of keeping heavy body, high coulomb efficiency, high cycle characteristics, obtain the battery electrode of high-energy-density as carbon material for battery electrode.
In addition, method of manufacture of the present invention is excellent, the improved method of security of economy, productivity.
Description of drawings
Fig. 1 is the figure of the picture of expression when using transmission electron microscope (TEM) to observe the cross section of mesocarbon.
Fig. 2 be expression use tem observation graphite material of the present invention the cross section time the figure of picture.
Nomenclature
A: skin section (coating layer)
B: internal layer portion
C: boundary line
Embodiment
The present invention below at length is described.
(graphite material 1)
The graphite material 1 of the present invention's first mode, preferably spectrometric at 1360cm through raman spectroscopy
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2, and the R value was exposed active high edge section greater than 0.2 o'clock on the surface morely, and side reaction takes place when discharging and recharging morely.On the other hand, when stopping of coming in and going out of lithium being uprised less than 0.01 the time, the current load characteristic reduces.
Moreover LR laser raman R value is used the NRS3100 of Japanese beam split corporate system, under the condition of excitation wavelength 532nm, incident slit width 200 μ m, 15 seconds of time shutter, accumulative total 2 times, 600/mm of diffraction grating, measures.
In addition, graphite material 1 of the present invention, preferred 30 ℃～100 ℃ thermal expansivity (CTE) is 4.0 * 10
-6/ ℃～5.0 * 10
-6/ ℃.Thermal expansivity uses as one of the index of the needle-like property of expression coke.Thermal expansivity is less than 4.0 * 10
-6/ ℃ graphite material, the crystallinity of graphite is high, loading capacity is big, yet that particle shape becomes easily is tabular.And greater than 5.0 * 10
-6/ ℃ big graphite material, aspect ratio diminishes, but graphite crystal is undeveloped, and loading capacity reduces.The CTE of graphite material 1 with after the CTE of the carbon raw material stated likewise measure.
Graphite material 1 of the present invention, the centre plane spacing d of (002) face of preferably measuring by X-ray diffraction method
002Be 0.3362nm～0.3370nm.d
002Can adopt known method to measure (with reference to wild field Dao Ji, rice wall doffer, JSPS, the 117th council's sample, 117-71-A-1 (1963) through powder x-ray diffraction (XRD) method; Rice wall doffer etc., JSPS, the 117th council's sample, 117-121-C-5 (1972); Rice wall doffer, " carbon ", 1963, No.36,25～34 pages).
Graphite material 1 of the present invention, preferred aspect ratio (length of the length/minor axis of major axis) is below 6, is preferably 1～5 especially, aspect ratio can be tried to achieve by optical microscope image.Briefly, can use the FPIA3000 of シ ス メ Star Network ス system, measure through image analysis.
Graphite material 1 of the present invention, preferred specific surface area (BET method) is 2m
2Below/the g, be preferably 0.8～1.8m especially
2/ g.When specific surface area surpasses 2m
2During/g, the surfactivity of particle uprises, and owing to the decomposition of electrolytic solution etc. coulombic efficiency is reduced sometimes.
Graphite material 1 of the present invention, preferred bulk volume density is 0.70g/cm
3More than, and the powder density when having carried out rapping for 400 times is 1.0g/cm
3～1.35g/cm
3
In addition, graphite material 1 of the present invention, preferably in the size distribution of the volume reference of measuring through laser diffractometry, D50% is 10～25 μ m.
(graphite material 2)
The graphite material 2 of the present invention's second mode, the aspect ratio that is primary particle is 1.00～1.32, and does not have the graphite material of the coating layer of essence at particle surface.
In addition, graphite material 2 of the present invention, the aspect ratio that is primary particle is 1.00～1.32, by having isotropic crystalline structure, being essentially the graphite material that the single particle of forming constitutes.
Fig. 1 is the figure of the picture of expression when using transmission electron microscope (TEM) to observe the cross section of mesocarbon.Fig. 2 is the figure of the picture of expression when using tem observation graphite material 2 of the present invention.
Can know that by Fig. 1 its skin section of mesocarbon A is white in color (phase that electron rays sees through easily), the B of internal layer portion gray (phase that electron rays is difficult to see through).And, in so many words manifested the boundary line C of skin section and internal layer portion.
On the other hand, graphite material of the present invention 2 is as shown in Figure 2, does not have the boundary line of skin section and internal layer portion, from the top layer to the internal layer, presents much the same grey.That is, there is not the coating layer of essence in graphite material of the present invention at particle surface, perhaps, has isotropic crystalline structure and is essentially single composition.
Graphite material 2 of the present invention, aspect ratio (the vertical length DNmax of maximum length Dmax/ and maximum length (Dmax: 2 maximum length on the profile of particle picture; DNmax: when using 2 straight lines parallel to clip image) be 1.0～1.32 with the shortest length that vertically connects between 2 straight lines with maximum length.The FPIA3000 that aspect ratio can be used シ ス メ Star Network ス system measures through image analysis.Use by more than at least 3000, preferred more than 30000, the more preferably MV measuring, calculate of the measuring point more than 50000.
Graphite material 2 of the present invention, specific surface area (BET method) is preferably 2m
2Below/the g, 0.8～1.8m more preferably
2/ g.When specific surface area surpasses 2m
2During/g, PVDF (PVDF) be tackiness agent much less, even SBR (SBR styrene butadiene rubbers) is the tackiness agent that tackiness agent also need add a great deal of, so the active matter quality in the unit electrode volume tails off, so cell container reduces easily.In addition, owing to the increase of specific surface area makes the surfactancy increases of particle, owing to decomposition of electrolytic solution etc. reduces coulombic efficiency easily.In addition, graphite material of the present invention preferably in the size distribution of the volume reference of measuring through laser diffractometry D50% be 10～25 μ m.
The optimal way of graphite material 2 of the present invention is: spectrometric at 1360cm by raman spectroscopy
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2.When the R value greater than 0.2 the time, expose more active high edge section on the surface, easy when discharging and recharging side reaction takes place morely.And when less than 0.01 the time, stopping of coming in and going out of lithium uprised, the current load characteristic reduces easily.
Moreover LR laser raman R value is used the NRS3100 of Japanese beam split corporate system, under the condition of excitation wavelength 532nm, incident slit width 200 μ m, 15 seconds of time shutter, accumulative total 2 times, 600/mm of diffraction grating, measures.
In addition, the preferred graphite material 2 of the present invention is 4.0 * 10 at 30 ℃～100 ℃ thermal expansivity (CTE)
-6/ ℃～5.0 * 10
-6/ ℃.Thermal expansivity uses as one of the index of the needle-like property of expression coke.Thermal expansivity is less than 4.0 * 10
-6/ ℃ graphite material, the crystallinity of graphite is high, loading capacity is big, and is tabular but particle shape becomes easily.And greater than 5.0 * 10
-6/ ℃ graphite material, aspect ratio diminishes, but graphite crystal is undeveloped, the easy step-down of loading capacity.The CTE of graphite material 2 with after the CTE of the carbon raw material stated likewise measure.
Graphite material 2 of the present invention, the centre plane spacing d of (002) face of preferably measuring by X-ray diffraction method
002Be 0.3362nm～0.3370nm.d
002Can adopt powder x-ray diffraction (XRD) method to measure through known method (with reference to wild field Dao Ji, rice wall doffer, JSPS, the 117th council's sample, 117-71-A-1 (1963); Rice wall doffer etc., JSPS, the 117th council's sample, 117-121-C-5 (1972); Rice wall doffer, " carbon ", 1963, No.36,25～34 pages).
Graphite material 2 of the present invention, preferred bulk volume density is 0.7g/cm
3More than, and the powder density when having carried out rapping for 400 times is 1.0g/cm
3～1.35g/cm
3
The graphite material 2 that has a characteristic as above when use can obtain the battery electrode of high-energy-density during as carbon material for battery electrode under the state of keeping heavy body, high coulomb efficiency, high cycle characteristics.
(graphite material 3)
The graphite material 3 of Third Way of the present invention is that D50% is 2～9 μ m in the size distribution of the volume reference of measuring through laser diffractometry, and specific surface area is 2～6m
2/ g, and do not have the graphite material of the coating layer of essence at particle surface.
In addition, graphite material 3 of the present invention is that D50% is 2～9 μ m in the size distribution of the volume reference of measuring through laser diffractometry, and specific surface area is 2～6m
2/ g is by having isotropic crystalline structure and being essentially the graphite material that the single particle of forming constitutes.
Fig. 1 is the figure of the picture of expression when using transmission electron microscope (TEM) to observe the cross section of mesocarbon.Can be known that by Fig. 1 the table of mesocarbon (coating) the layer A of portion presents white (phase that electron rays sees through easily), the B of internal layer portion presents grey (phase that electron rays is difficult to see through).And, in so many words demonstrate the boundary line C of skin section and internal layer portion.
Picture during the cross section of using tem observation graphite material 3 of the present invention does not likewise have the boundary line of skin section and internal layer portion with picture shown in Figure 2, from the top layer to the internal layer, presents much the same grey.That is, graphite material of the present invention is the coating layer that does not have essence at particle surface, perhaps, has isotropic crystalline structure and is essentially the graphite material of single composition.
Graphite material 3 of the present invention, D50% is 2～9 μ m in the size distribution of the volume reference of measuring through laser diffractometry.
The specific surface area of graphite material 3 of the present invention (BET method) is 2～6m
2/ g.When specific surface area surpasses 6m
2During/g, PVDF be tackiness agent much less, even SBR is the tackiness agent that tackiness agent also need add a great deal of, so the active matter quality in the unit electrode volume tails off, so cell container reduces easily.In addition, owing to the increase of specific surface area makes the surfactancy increases of particle, owing to decomposition of electrolytic solution etc. reduces coulombic efficiency easily.
The optimal way of graphite material 3 of the present invention is: spectrometric at 1360cm by raman spectroscopy
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2.When the R value greater than 0.2 the time, expose more active high edge section on the surface, easy when discharging and recharging side reaction takes place morely.And less than 0.01 o'clock, stopping of coming in and going out of lithium uprised, the current load characteristic reduces easily.
Moreover LR laser raman R value is used the NRS3100 of Japanese beam split corporate system, under the condition of excitation wavelength 532nm, incident slit width 200 μ m, 15 seconds of time shutter, accumulative total 2 times, 600/mm of diffraction grating, measures.
Graphite material 3 of the present invention, the centre plane spacing d of (002) face of preferably measuring by X-ray diffraction method
002Be 0.3362nm～0.3370nm.d
002Can adopt powder X-ray diffraction (XRD) method to measure through known method (with reference to wild field Dao Ji, rice wall doffer, JSPS, the 117th council's sample, 117-71-A-1 (1963); Rice wall doffer etc., JSPS, the 117th council's sample, 117-121-C-5 (1972); Rice wall doffer, " carbon ", 1963, No.36,25～34 pages).
Graphite material 3 of the present invention, preferred aspect ratio (the vertical length DNmax of maximum length Dmax/ and maximum length (Dmax: 2 maximum length on the profile of particle picture; DNmax: when utilizing 2 straight lines parallel to clip image) be 1.0～1.32 with the shortest length that vertically connects between two straight lines with maximum length.The FPIA3000 that aspect ratio can be used シ ス メ Star Network ス system measures through image analysis.Use by more than at least 3000, preferred more than 30000, the more preferably MV measuring, calculate of the measuring point more than 50000.
Graphite material 3 of the present invention, preferred bulk volume density is 0.4g/cm
3More than, and the powder density when having carried out rapping for 400 times is 0.5g/cm
3～1g/cm
3
In addition, preferred graphite material 3 of the present invention is 4.0 * 10 in 30 ℃～100 ℃ thermal expansion systems (CTE)
-6/ ℃～5.0 * 10
-6/ ℃.Thermal expansivity uses as one of the index of the needle-like property of expression coke, and thermal expansivity is less than 4.0 * 10
-6/ ℃ graphite material, the crystallinity of graphite is high, loading capacity is big, and is tabular but particle shape becomes easily.And greater than 5.0 * 10
-6/ ℃ graphite material, aspect ratio diminishes, but graphite crystal is undeveloped, loading capacity reduces easily.The CTE of graphite material 3 with after the CTE of the carbon raw material stated likewise measure.
The graphite material that has a characteristic as above when use can obtain the battery electrode of high-energy-density during as carbon material for battery electrode under the state of keeping heavy body, high coulomb efficiency, high cycle characteristics.
(method for making of graphite material)
Graphite material of the present invention does not limit according to its method for making especially.Being suitable for making the method for making of graphite material of the present invention, is to comprise with the weight loss on heating composition when 300 ℃ are heated to 1200 ℃ under inert atmosphere being that the carbon raw material powder of 5 quality %～20 quality % is broken, then carries out the heat-treating methods more than 2000 ℃.
The carbon raw material that in method for making of the present invention, uses is that the weight loss on heating composition when 300 ℃ are heated to 1200 ℃ is the carbon raw material of 5 quality %～20 quality % under inert atmosphere.If the weight loss on heating composition is less than 5 quality %, then particle shape becomes tabular easily.In addition, crushed face (edge section) exposes, and specific surface area increases, and side reaction also increases.If surpass 20 quality %, then the mutual combination of the particle after the greying increases, and has influence on yld on the contrary.Thereby do not distinguish in detail as yet in the reason that specific surface area diminishes and side reaction reduces of above-mentioned scope graphite material through making the weight loss on heating composition; But infer be because; The evaporable composition generation carbonized graphiteization through 300～1200 ℃ heating; Make the crystal of the edge section of exposing constitute stabilization more thus, and particle surface become smooth, the cause that specific surface area reduces.
Moreover above-mentioned weight loss on heating composition can be measured through the commercially available device that use under 10 ℃/minute heat-up rate can be measured TG and DTA.In present embodiment etc., use the TGDTAw6300 of セ イ コ one イ Application ス Star Le メ Application ト corporate system, take by weighing the about 15mg of working sample exactly, be placed in the dish of platinum system, place device, with 200cm
3/ minute circulation argon gas is warmed up to 1400 ℃ with 10 ℃/minute and measures.(reference) as a reference used the aluminum oxide that will remove volatile matter in 3 hours 1500 ℃ of following pre-treatment with the Alpha-alumina of the pure medicine corporate system of light.
Carbon raw material with such weight loss on heating composition can be to select pitch coke or the carbobitumen coke from oil.The carbon raw material that uses among special the present invention is preferably a kind of green coke charcoal that is selected from as petroleum coke.The green coke charcoal is because crystal is undeveloped, so englobement when pulverizing, and specific surface area diminishes easily.Therefore, the acicular coke of the preferred right and wrong of carbon raw material used in the present invention, special non-needle coke of preferably not carrying out heat treated.
Petroleum coke is black and the porous solid residue that obtains through the cracking of oil or asphalt oil or destructive distillation.Petroleum coke has fluid coke (fluid coke) and postpones coke (delayed coke) according to coking method.But fluid coke is a powdery, for being used for the degree of oneself fuel of refinery, less has purposes, and what be commonly referred to as petroleum coke is to postpone coke.Postpone coke green coke charcoal (raw coke) and calcined coke (calcined coke) are arranged.The green coke charcoal is the coke from the former state state of coker collection, and calcined coke is with the further calcining once more of green coke charcoal, has removed the coke of volatile matter.Because the green coke charcoal causes that the possibility of dust explosion is high,, pulverize after the calcining of green coke charcoal removed volatile matter therefore in order to obtain the petroleum coke of finely particulate.In addition, electrode etc. was general in the past uses calcined coke.Because the ash rate coal coke of green coke charcoal is few, the carbon material, foundry goods that therefore only is used to carbide industry with coke, alloy iron with coke etc.Use such green coke charcoal among the present invention.
The carbon raw material that uses in the present invention, (CTE) is preferably 4.8 * 10 at 30～100 ℃ thermal expansivity
-6/ ℃～6.0 * 10
-6/ ℃.The CTE of carbon raw material can adopt following method to measure.At first, use vibrating mill that the 500g carbon raw material powder is broken into below 28 orders.With this sample screening, the mixed with 28～60 order 60g, 60～200 order 32g, the following 8g of 200 orders makes total amount become 100g.Should cooperate sample 100g to put into stainless steel vessel, add binder pitch 25g, and use 125 ℃ oil bath to heat 20 minutes, mix equably.With this mixture cooling, use vibrating mill to pulverize, whole amounts are become below 28 orders, 30g puts into 125 ℃ pressure forming machine with this sample, at gauge pressure 450kg/cm
2Under pressurize and carried out moulding in 5 minutes.The moulding article are put into the magnetic crucible, use firing furnace to be warmed up to 1000 ℃ from room temperature, kept 1 hour, cool off at 1000 ℃ with 5 hours.Use accurate stapling machine that this is burnt till article and be cut into 4.3 * 4.3 * 20.0mm, obtain test piece (test piece).Use TMA (thermo-mechanical analysis device) for example the TMA/SS350 etc. of NSK electronics system 30～100 ℃ thermal expansion measurement is carried out in this test piece, calculate CTE.
Then, pulverize this carbon raw material.The pulverizing of carbon raw material can be used known aeropulverizer, hammer mill, roller mill, needle mill (pin mill), vibrating mill etc.The pulverizing of carbon raw material is preferably carried out under the low state of thermal process as far as possible.When being heated owing to pulverizing, above-mentioned 300～1200 ℃ of evaporable compositions minimizings, might can not get above-mentioned effect.
Chippy carbon raw material preferably carries out classification and makes that mean particle size is 10～25 microns.If the tendency that mean particle size greatly then exists electrode density to be difficult to raise if instead mean particle size is little, then causes side reaction easily when discharging and recharging.Granularity uses the CILUS of laser diffraction formula to measure.
Can about 500 ℃～1200 ℃, carry out easy fired before the graphitization processing that chippy carbon raw material is stated after carrying out.Through this easy fired the gas in the graphitization processing of next carrying out is reduced.Moreover this easy fired must carry out under non-oxidizing atmosphere.
Then, chippy carbon raw material is carried out graphitization processing.Graphitization processing is difficult at the carbon raw material carry out to good under the atmosphere of oxidation.For example, can enumerate: the method for under atmosphere such as argon gas, heat-treating; The method (non-oxide graphitization technique) of using acheson furnace to heat-treat; Or the like, wherein from the viewpoint of cost, preferred non-oxide graphitization technique.
The lower limit of graphitization processing temperature is generally 2000 ℃, is preferably 2500 ℃, further is preferably 2900 ℃, most preferably is 3000 ℃.The upper limit of graphitization processing temperature is not special to be limited, but the viewpoint of the high discharge capacity that is easy to get calmly is preferably 3300 ℃.
In method for making of the present invention, preferably not broken or pulverizing after graphitization processing with graphite material.Reason is if after graphitization processing, carry out fragmentation or pulverizing, then can damage the slick surface that become, worries that performance reduces.
The graphite material that adopts such method can obtain having structure shown in Figure 2.
(carbon material for battery electrode)
Carbon material for battery electrode of the present invention is the carbon material that contains graphite material of the present invention, carbon material for battery electrode, and the negative electrode active material and the negative pole electro-conductive material that for example can be used as lithium secondary battery use.
Carbon material for battery electrode of the present invention preferably also contains the carbon material of thomel.Thomel preferably contains 0.01～20 mass parts with respect to above-mentioned graphite material 100 mass parts.
As thomel, for example can enumerate organic system thomels such as PAN based carbon fiber, pitch-based carbon fiber, Zantrel based carbon fiber; Gas-phase growth of carbon fibre etc.Wherein, the gas-phase growth of carbon fibre that preferred especially crystallinity is high, heat conductance is high.Gas-phase growth of carbon fibre; It for example is raw material with the organic cpds; To import in the pyritous Reaktionsofen with carrier gas as the organo-transition metal compound of catalyzer and generate, thereby then heat-treat manufacturing (with reference to japanese kokai publication sho 60-54998 communique, No. 2778434 communiques of Japanese Patent etc.).Its fiber directly is preferably 2～1000nm, 0.01～0.5 μ m more preferably, and aspect ratio is preferably 10～15000.
Become the organic cpds of the raw material of thomel, can enumerate gas and their mixtures such as toluene, benzene, naphthalene, ethene, second are fast, ethane, Sweet natural gas, carbon monoxide.Wherein, aromatic hydrocarbonss such as preferred toluene, benzene.
Organo-transition metal compound is the compound that contains the transition metal that becomes catalyzer.As transition metal, can enumerate the metal of periodic table of elements IVa, Va, VIa, VIIa, VIII family.As organo-transition metal compound, compounds such as preferred ferrocene, nickelocene.
The thomel that uses among the present invention can be that the macrofiber that adopts vapor phase process etc. to obtain is pulverized or the broken thomel that forms.In addition, thomel also can be the thomel that is gathered into wadding (flock) shape.
The thomel that uses among the present invention, the preferably thomel of the non-cohesive pyrolysate that derives from organic cpds etc. or the high thomel of crystallinity of carbon structure on its surface.
The thomel of non-cohesive pyrolysate or the high thomel of the crystallinity of carbon structure, can through for example under inert gas atmosphere with thomel, preferably gas-phase growth of carbon fibre is burnt till (thermal treatment) and obtains.Specifically, the thomel of non-cohesive pyrolysate can obtain through under about 800～1500 ℃, in rare gas elementes such as argon, heat-treating.And the high thomel of the crystallinity of carbon structure, can through preferably more than 2000 ℃, more preferably 2000～3000 ℃, in rare gas elementes such as argon, heat-treat and obtain.
The thomel that uses among the present invention preferably contains the thomel of dendritic fiber.In addition, fiber all can have the position with the hollow structure that is interconnected.Therefore, the carbon-coating of the cylindrical portions may of formation fiber is continuous.So-called hollow structure so long as exist carbon-coating to be rolled into get final product of structure cylindraceous, comprises the structure that is not cylinder completely, the structure with place of incision partly, the structure that range upon range of two-layer carbon-coating is combined into 1 layer etc.In addition, the cross section of cylinder is not limited to round completely, comprises ellipse, polygonal cross section.
In addition, preferred thomel used in the present invention, the centre plane spacing d of (002) face of measuring by X-ray diffraction method
002Be preferably below the 0.344nm, more preferably below the 0.339nm, be preferably below the 0.338nm especially.In addition, preferably the axial thickness Lc of crystalline C is the thomel below the 40nm.
(electrode is used cream)
Electrode of the present invention is the cream that contains above-mentioned carbon material for battery electrode and tackiness agent with cream.This electrode can be through carrying out mixing obtaining with above-mentioned carbon material for battery electrode and tackiness agent with cream.The mixing known devices such as propeller-type mixer (ribon mixer), screw type kneader, high-speed stirring mixer (ス パ Le タ Application ミ キ サ one), LADY GEL mixing machine (レ デ イ ゲ ミ キ サ one), planetary stirring machine, omnipotent stirrer that use.Electrode can be molded into shapes such as sheet, particle (pellet) shape with cream.
As the tackiness agent that uses in cream at electrode, the fluorine that can enumerate PVDF and tetrafluoroethylene etc. is a tackiness agent; The rubber of SBR (SBR styrene butadiene rubbers) etc. is known tackiness agents such as tackiness agent.
The usage quantity of tackiness agent is generally 1～30 mass parts with respect to carbon material for battery electrode 100 mass parts, is preferably 3～20 mass parts especially.
Carry out to use solvent when mixing.Can enumerate the known solvent that is suitable for each tackiness agent as solvent, if for example fluorine be tackiness agent then solvent can enumerate toluene, N-Methyl pyrrolidone etc.; If rubber is tackiness agent, then solvent can be enumerated water etc.; Can enumerate N, Virahol etc. in addition.In the occasion that makes water as the tackiness agent of solvent, preferred and use tackifier.The amount of solvent is adjusted the feasible viscosity that is coated on easily on the current collector that becomes.
(electrode)
Electrode of the present invention is the electrode of being processed with the formed body of cream by above-mentioned electrode.Electrode of the present invention for example can be through being coated on above-mentioned electrode on the current collector with cream, carries out drying, extrusion forming and obtain.
As current collector, for example can enumerate paper tinsel, net of aluminium, nickel, copper, stainless steel etc. etc.The coating thickness of cream is generally 50～200 μ m.When coating thickness is excessive, can not negative pole be housed in the normalized cell container sometimes.The not special restriction of the coating process of cream, for example can enumerate coatings such as using scraper plate and excellent coating machine after, use roll squeezer etc. to carry out the method etc. of moulding.
As extrusion forming method, can enumerate the method for forming of roller pressurization, pressing machine pressurization etc.Preferred 1～3 ton/cm of pressure during extrusion forming
2About.The electrode density of electrode is high more, and the cell container of unit volume is big more usually.But if make electrode density too high, then cycle characteristics reduces usually.When using electrode of the present invention to use cream, even improve electrode density, the reduction of cycle characteristics is also little, therefore can obtain the electrode of high electrode density.Use the peak of the electrode density of the electrode that electrode of the present invention obtains with cream to be generally 1.7～1.9g/cm
3The negative pole that the electrode that obtains like this is suitable for battery is the negative pole of secondary cell particularly.
(battery, secondary cell)
Battery of the present invention or secondary cell are to contain the battery that above-mentioned electrode is used as integrant (preferred negative pole).
Then enumerate lithium secondary battery and battery of the present invention or secondary cell are described as concrete example.Lithium secondary battery is to present the battery that anodal and negative pole is immersed in the structure among electrolytic solution or the ionogen.Negative pole can use electrode of the present invention.
For the positive pole of lithium secondary battery; As positive active material; Usually can use the transition metal oxide that contains lithium; Preferably containing at least a kind the transition metal and the lithium that are selected among Ti, V, Cr, Mn, Fe, Co, Mo and the W is main oxide compound; The mol ratio that can use lithium and transition metal is 0.3～2.2 compound, is more preferably that to contain at least a kind the transition metal and the lithium that are selected among V, Cr, Mn, Fe, Co and the Ni be main oxide compound, and the mol ratio that can use lithium and transition metal is 0.3～2.2 compound.Moreover, also can contain Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B etc. with scope with respect to the transition metal of main existence less than 30 moles of %.Among above-mentioned positive active material, preferably use by general formula Li
xMO
2(M is Co, Ni, Fe, Mn at least a kind, x=0～1.2) or Li
yA
2O
4(A comprises Mn at least.Y=0～2) at least a kind of the material with spinel structure of expression.
And then positive active material especially preferably uses and contains Li
yM
aD
1-aO
2The material of (M is Co, Ni, Fe, Mn at least a kind, and D is at least a kind beyond the M among Co, Ni, Fe, Mn, Al, Zn, Cu, Mo, Ag, W, Ga, In, Sn, Pb, Sb, Sr, B, the P, y=0～1.2, a=0.5～1) or by Li
z(A
bE
1-b)
2O
4At least a kind of the material with spinel structure of (A is Mn, and E is at least a of Co, Ni, Fe, Mn, Al, Zn, Cu, Mo, Ag, W, Ga, In, Sn, Pb, Sb, Sr, B, P, b=1～0.2, Z=0～2) expression.
Can enumerate Li particularly
xCoO
2, Li
xNiO
2, Li
xMnO
2, Li
xCo
aNi
1-aO
2, Li
xCo
bV
1-bO
z, Li
xCo
bFe
1-bO
2, Li
xMn
2O
4, Li
xMn
cCo
2-cO
4, Li
xMn
cNi
2-cO
4, Li
xMn
cV
2-cO
4, Li
xMn
cFe
2-cO
4(wherein x=0.02～1.2, a=0.1～0.9, b=0.8～0.98, c=1.6～1.96, z=2.01～2.3).As the most preferred transition metal oxide that contains lithium, can enumerate Li
xCoO
2, Li
xNiO
2, Li
xMnO
2, Li
xCo
aNi
1-aO
2, Li
xMn
2O
4, Li
xCo
bV
1-bO
z(x=0.02～1.2, a=0.1～0.9, b=0.9～0.98, c=1.6～1.96, z=2.01～2.3).Moreover the x value increases and decreases according to discharging and recharging for discharging and recharging the preceding value of beginning.
The average particulate size of positive active material is not special to be limited, but preferred 0.1～50 μ m.The volume of the particle of preferred 0.5～30 μ m accounts for more than 95%.More preferably the shared volume of population below the particle diameter 3 μ m is below 18% of TV, and the shared volume of the population of 15 μ m～25 μ m is below 18% of TV.Specific surface area is not special to be limited, but is preferably 0.01～50m when adopting the BET method
2/ g is preferably 0.2m especially
2/ g～1m
2/ g.In addition, the pH of the supernatant when being dissolved in positive active material 5g among the zero(ppm) water 100ml is preferably 7～12.
Lithium secondary battery is provided with barrier film sometimes between positive pole and negative pole.As barrier film, for example can enumerate with polyolefine such as Vilaterm, Vestolen PP 7052 is the non-woven fabrics, fabric (cloth), microporous membrane of principal constituent or barrier film that they are combined etc.
Electrolytic solution and ionogen as constituting lithium secondary battery of the present invention can use known organic electrolyte, inorganic solid electrolyte, polymer solid electrolyte.From the viewpoint of electroconductibility, preferred organic electrolyte.
As organic electrolyte, the ether of preferred diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diglyme, ethylene glycol phenyl ether etc.; Methane amide, N-NMF, N; Dinethylformamide, N-ethyl-formamide, N, N-DEF, N-methylacetamide, DMAC N,N, N-ethyl acetamide, N; N-diethyl acetamide, N, the acid amides of N-dimethyl propylene acid amides, hexamethylphosphoramide etc.; The sulfocompound of DMSO 99.8MIN., tetramethylene sulfone etc.; The dialkyl ketone of methylethylketone, mibk etc.; Oxyethane, propylene oxide, THF, 2-methoxyl group THF, 1,2-glycol dimethyl ether, 1, the carbonic ether of the cyclic ether of 3-dioxa penta ring etc., ethylene carbonate, Texacar PC etc.; Gamma-butyrolactone; N-Methyl pyrrolidone; The solution of the organic solvent of acetonitrile, Nitromethane 99Min. etc.Wherein, Preferably enumerate out ethers, DMSO 99.8MIN., acetonitrile, THF of the ester class, dioxa penta ring, diethyl ether, methylene diethyl ether etc. of ethylene carbonate, butylene carbonate, diethyl carbonate, methylcarbonate, Texacar PC, carbonic acid vinylidene ester, gamma-butyrolactone etc. etc., the carbonic ether of particularly preferably enumerating out ethylene carbonate, Texacar PC etc. is a non-aqueous solvent.These solvents can use separately or two or more mixing are used.
The solute of these solvents (ionogen) can use lithium salts.The general lithium salts of being known has LiClO
4, LiBF
4, LiPF
6, LiAlCl
4, LiSbF
6, LiSCN, LiCl, LiCF
3SO
3, LiCF
3CO
2, LiN (CF
3SO
2)
2Deng.
As polymer solid electrolyte, can enumerate polyethylene oxide derivant and contain polymkeric substance, the poly propylene oxide derivative of this verivate and contain polymkeric substance, phosphate ester polymer, the polycarbonate derivatives of this verivate and contain polymkeric substance of this verivate etc.
Moreover, constitute the selection of going up necessary member for the battery beyond above-mentioned and do not receive any restriction.
Battery of the present invention or secondary cell; Excellent charge; And the high current load characteristic is also excellent, therefore applicable to main field of using plumbous secondary cell, NI-G secondary cell, nickel-hydrogen secondary cell in the past, and the for example power tool of electric drill etc. and hybrid vehicle etc.
Embodiment
Representational example below is shown to be come the present invention is more specifically described.Moreover these examples are the simple example that are used to explain, the present invention is not at all by these example restrictions.
The rerum naturas of in following example, using etc. are measured through following method.
(specific surface area)
Use specific area measuring device NOVA-1200 (ユ ア サ ア イ オ ニ Network ス (strain) system), adopt and measure as the BET method of general specific area measuring method.
(cell evaluation method)
(1) cream preparation:
The KF polymkeric substance L1320 (N-Methyl pyrrolidone (NMP) the solution goods that contain the PVDF (PVDF) of 12 quality %) that in the graphite material of 1 mass parts, adds the Wu Yu chemistry corporate system of 0.1 mass parts; It is mixing to use planetary stirring machine to carry out, and forms host stoste.
(2) electrode is made
In host stoste, add NMP, regulate viscosity after, it is thick to use scraper plate on the high purity Copper Foil, to be coated with into 250 μ m.Then with it 120 ℃ of following vacuum-dryings 1 hour, stamping-out becomes Φ 18mm.The electrode that the pressing plate clamping stamping-out of the supersteel system of use goes out, counter electrode is suppressed and is made that pressing pressure is about 1 * 10
2～3 * 10
2N/mm
2(1 * 10
3～3 * 10
3Kg/cm
2).Use vacuum drier to descend dry 12 hours then, be made for to estimate and use electrode at 120 ℃.
(3) cell preparation:
Be described below and make three utmost point batteries.Moreover the following dew point that operates in is implemented down for the dry argon gas atmosphere below-80 ℃.
In the box that has spiral lid (the about 18mm of internal diameter) of Vestolen PP 7052 system, (microporous membrane of Vestolen PP 7052 system (セ Le ガ one De 2400) is range upon range of across coming by barrier film for the carbon dioxide process carbon electrode that has Copper Foil that will in above-mentioned (2), make and metallic lithium foil.Likewise range upon range of again metallic lithium with reference to usefulness.To wherein adding electrolytic solution, process testing battery.
(4) electrolytic solution:
The electrolytical LiPF of conduct of dissolving 1 mol in the mixed solution of EC (ethylene carbonate) 8 mass parts and DEC (diethyl carbonate) 12 mass parts
6Form.
(5) charge and discharge cycles test:
At current density 0.2mA/cm
2Carry out constant current constant voltage under (being equivalent to 0.1C) and discharge and recharge test.Charging (inserting lithium to carbon) is with 0.2mA/cm from rest potential
2Carry out CC (Constantcurrent: constant current) be charged to 0.002V.Then, switch under 0.002V, carry out CV (Constantvolt: constant voltage) charging, the moment that is reduced to 25.4 μ A at current value stops.
Discharge (emitting from carbon) is with 0.2mA/cm
2(being equivalent to 0.1C) carried out CC discharge, cuts off (cut off) during for 1.5V at voltage.
(graphite material 1)
Embodiment 1
The oil that the small-sized grinding machine (bantam mill) that uses ホ ソ カ ワ ミ Network ロ Application to make is pulverized by to measure resulting weight loss on heating composition at 300 ℃～1200 ℃ TG be 11.8 quality % is green coke charcoal (a non-needle coke).Use day turbine classifier of clear エ Application ジ ニ ア リ Application グ corporate system to carry out air classification, obtaining D50 is the carbon raw material of 14.2 μ m.This chippy carbon raw material is filled in the plumbago crucible that has screw cap, uses acheson furnace under 3000 ℃, to carry out graphitization processing, obtain LR laser raman R value and be 0.03, CTE is 4.2 * 10
-6/ ℃ graphite material.The specific surface area of the graphite material that obtains is little, can obtain loading capacity, initial stage efficient, battery that cycle characteristics is all good.The result is shown in table 1.
Embodiment 2
Except after pulverizing, before the graphitization processing, having implemented 1200 ℃ thermal treatment (easy fired), carried out the test same with embodiment 1.The result is shown in table 1.
Comparative example 1
Except before pulverizing the green coke charcoal, carrying out 1200 ℃ thermal treatment (calcining), carry out the test same with embodiment 1.The result is shown in table 1.Specific surface area is big, and tap density is also low.
Comparative example 2
Do not pulverize the green coke charcoal and under 3000 ℃, carry out graphitization processing, then likewise pulverize, carry out air classification with embodiment 1 with regard to former state ground.Implement analysis, the cell evaluation same with embodiment 1.The result is shown in table 1.Specific surface area is very big, and initial stage efficient also reduces.
Result by table 1 knows, is passing through calcining, graphited heating, and weight loss on heating becomes the graphite material of pulverizing less than after the 5 quality % (comparative example), and loading capacity is low, initial stage efficient is poor.
Know on the other hand; Through will being that the carbon raw material powder of 5 quality %～20 quality % is broken at the weight loss on heating composition when 300 ℃ are heated to 1000 ℃ under the inert atmosphere; Then chippy carbon raw material is carried out graphitization processing, can obtain by raman spectroscopy spectrometric thus at 1360cm
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2 and is 4.0 * 10 at 30 ℃～100 ℃ thermal expansivity (CTE)
-6/ ℃～5.0 * 10
-6/ ℃ graphite material (embodiment).Know that in addition when the graphite material of embodiment was used as the electrode active material of battery, loading capacity uprised, initial stage efficient is also good.
(graphite material 2)
Embodiment 3
The oil that uses the small-sized grinding machine of ホ ソ カ ワ ミ Network ロ Application system to pulverize by to measure resulting weight loss on heating composition at 300 ℃～1200 ℃ TG be 11.8 quality % is the green coke charcoal.Use day turbine classifier of clear エ Application ヅ ニ ア リ Application グ corporate system to carry out air classification, obtaining D50 is the carbon raw material of 14.2 μ m.This chippy carbon raw material is filled in the plumbago crucible that has screw cap, uses acheson furnace under 3000 ℃, to carry out graphitization processing, obtained LR laser raman R value and be 0.03, CTE is 4.2 * 10
-6/ ℃ graphite material.The specific surface area of the graphite material that obtains is little, can obtain loading capacity, initial stage efficient, battery that cycle characteristics is all good.The result is shown in table 2.
Embodiment 4
Except after pulverizing, before the graphitization processing, having implemented 1200 ℃ thermal treatment (easy fired), carry out the test same with embodiment 3.The result is shown in table 2.
Comparative example 3
Except before pulverizing the green coke charcoal, carrying out 1200 ℃ thermal treatment (calcining), carry out the test same with embodiment 3.The result is shown in table 2.Specific surface area is big, and tap density also reduces.
Comparative example 4
Do not pulverize the green coke charcoal and under 3000 ℃, carry out graphitization processing, then likewise pulverize, carry out air classification with embodiment 3 with regard to former state ground.Analysis, the cell evaluation same have been implemented with embodiment 3.The result is shown in table 2.Specific surface area is very big, and initial stage efficient also reduces.
(graphite material 3)
Embodiment 5
The oil that uses the small-sized grinding machine of ホ ソ カ ワ ミ Network ロ Application system to pulverize by to measure resulting weight loss on heating composition at 300 ℃～1200 ℃ TG be 11.8 quality % is the green coke charcoal.Use day turbine classifier of clear エ Application ジ ニ ア リ Application グ corporate system to carry out air classification, obtaining D50 is the carbon raw material of 4.8 μ m.This chippy carbon raw material is filled in the plumbago crucible that has screw cap, uses acheson furnace under 3000 ℃, to carry out graphitization processing, obtained LR laser raman R value and be 0.03, CTE is 4.2 * 10
-6/ ℃ graphite material.The specific surface area of the graphite material that obtains is little, can obtain loading capacity, initial stage efficient, battery that cycle characteristics is all good.The result is shown in table 3.
Embodiment 6
Except after pulverizing, before the graphitization processing, having implemented 1200 ℃ thermal treatment (easy fired), carry out the test same with embodiment 5.The result is shown in table 3.
Comparative example 5
Except before pulverizing the green coke charcoal, carrying out 1200 ℃ thermal treatment (calcining), carry out the test same with embodiment 5.The result is shown in table 3.Specific surface area is big, and tap density also reduces.
Among the present invention the expression numerical range " more than " and " following " include given figure.
Claims (10)
1. the method for making of a graphite material comprises: will be under inert atmosphere weight loss on heating composition when 300 ℃ are heated to 1200 ℃ be that the non-needle-like green coke powdered carbon of 5 quality %～20 quality % is broken, then chippy non-needle-like green coke charcoal is carried out graphitization processing.
2. the method for making of graphite material as claimed in claim 1, said non-needle-like green coke charcoal is that oil is pitch coke or carbobitumen coke.
3. according to claim 1 or claim 2 the method for making of graphite material, the graphitization processing temperature is 3000 ℃～3300 ℃.
4. according to claim 1 or claim 2 the method for making of graphite material uses acheson furnace to carry out graphitization processing.
5. a graphite material adopts claim 1 or 2 described method for makings to obtain, and said graphite material is spectrometric at 1360cm by raman spectroscopy
-1Near peak intensity (I
D) and at 1580cm
-1Near peak intensity (I
G) strength ratio I
D/ I
G(R value) is 0.01～0.2, and, be 4.0 * 10 at 30 ℃～100 ℃ thermal expansivity (CTE)
-6/ ℃～5.0 * 10
-6/ ℃.
6. graphite material as claimed in claim 5, in the size distribution of the volume reference of measuring through laser diffractometry, D50% is 10～25 μ m.
7. graphite material as claimed in claim 5, bulk volume density are 0.70g/cm
3More than, and the powder density when having carried out rapping for 400 times is 1.0g/cm
3～1.35g/cm
3
8. graphite material as claimed in claim 5, specific surface area are 0.8～1.8m
2/ g.
9. graphite material as claimed in claim 5, the centre plane spacing d of (002) face of measuring by X-ray diffraction method
002Be 0.3362nm～0.3370nm.
10. graphite material as claimed in claim 5, the aspect ratio of the particle of being calculated by optical microscope image is 1～5.
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| JP2005350138A JP5033325B2 (en) | 2005-12-05 | 2005-12-05 | Graphite material, carbon material for battery electrode, and battery |
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| JP2005365878A JP5162092B2 (en) | 2005-12-20 | 2005-12-20 | Graphite material, carbon material for battery electrode, and battery |
| JP365878/2005 | 2005-12-20 | ||
| JP368727/2005 | 2005-12-21 | ||
| JP2005368727A JP5162093B2 (en) | 2005-12-21 | 2005-12-21 | Graphite material, carbon material for battery electrode, and battery |
| PCT/JP2006/324293 WO2007066673A1 (en) | 2005-12-05 | 2006-12-05 | Graphite material, carbon material for battery electrode and battery |
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| CN101321695A (en) | 2008-12-10 |
| JP2007153661A (en) | 2007-06-21 |
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