CN100422077C - Composite graphite particle, its production method, Li ion secondary battery cathode material and Li ion secondary battery - Google Patents
Composite graphite particle, its production method, Li ion secondary battery cathode material and Li ion secondary battery Download PDFInfo
- Publication number
- CN100422077C CN100422077C CNB2003801065709A CN200380106570A CN100422077C CN 100422077 C CN100422077 C CN 100422077C CN B2003801065709 A CNB2003801065709 A CN B2003801065709A CN 200380106570 A CN200380106570 A CN 200380106570A CN 100422077 C CN100422077 C CN 100422077C
- Authority
- CN
- China
- Prior art keywords
- graphite particles
- composite graphite
- resin
- graphite
- granulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 224
- 239000010439 graphite Substances 0.000 title claims abstract description 223
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 41
- 239000010406 cathode material Substances 0.000 title abstract 2
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- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 13
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a lithium ion secondary battery capable of very successfully achieving both performances that have been conventionally incompatible and difficult to accomplish concurrently - a high initial charging/discharging efficiency and a large discharge capacity, and also being provided with both of excellent quick discharge characteristics and cyclic characteristics; and constituting materials thereof. Specifically, composite graphite particles comprising a carbon material, lower in crystallinity than graphite having an X-ray diffraction interplanar spacing d002 of less than 0.337 nm, on the at least surface portion of the graphite, wherein the aspect ratio of the composite graphite particles is up to 3, 0.5-20 mass% of the composite graphite particles consists of the carbon material, and a ratio (I1580/I1360) between a peak intensity (I1580 ) at 1580 cm<-1> at the Raman spectrum of the composite graphite particles and a peak intensity (I1360)at 1360 cm<-1> is at least 0.1 and less than 0.3, and a production method therefore; and a cathode material and a lithium secondary battery using the composite graphite particles.
Description
Technical field
The present invention relates to that loading capacity is big, initial charge is high, and then sudden discharge characteristic and also good lithium-ion secondary cell and the constituent material thereof of cycle characteristics.Particularly, relate to composite graphite particles and manufacture method thereof and negative material that uses this composite graphite and the lithium-ion secondary cell that forms by at least 2 kinds of different materials of rerum natura.
Background technology
In recent years, along with the miniaturization and the high performance of e-machine, the expectation of the high-energy-densityization of battery is constantly raise.Compare with other secondary cell, lithium-ion secondary cell can Towards Higher Voltage improving energy density, thereby be subjected to attracting attention of people.Lithium-ion secondary cell is with negative pole, and anodal and nonaqueous electrolyte is main integrant.The lithium ion that nonaqueous electrolyte produces moves between positive pole and negative pole in the charged process, forms secondary cell.
Usually, with the negative pole material of carbon material as above-mentioned lithium-ion secondary cell.As this carbon material, charge-discharge characteristic graphite good, that demonstrate big loading capacity and current potential flatness is considered to have prospect especially in (special public clear 62-23433 communique etc.).
In the graphite, the three-dimensional crystals regularity (being also referred to as crystallinity among the application sometimes) that is formed by the netted plane of condensation polycyclic hexagonal (being also referred to as the carbon wire side among the application sometimes) reaches all the more, the lamellar compound of then easy more formation stably and lithium.Thus, have report (electrochemistry and industrial physicochemistry, 61 (2), 1383 (1993) etc.) to claim that the crystallinity of graphite is high more, a large amount of lithiums inserts in the layer of carbon wire side, therefore can strengthen loading capacity.Also have report (J.Electrochem.Soc., Vol.140,9,2490 (1993) etc.) to claim, form various layer structures, its coexistence regional smooth and demonstrate noble potential near the lithium metal according to the lithium insertion amount in the carbon wire side layer is different.Therefore, when making lithium-ion secondary cell as negative material, can realize high-output power with graphite.Generally, final graphite and lithium are formed ideal graphite laminate compound L iC
6The time loading capacity be defined as with the theoretical capacity of graphite during as negative material, this limit loading capacity is 372mAh/g.
Yet for the lithium-ion secondary cell that uses graphite as negative material, the crystallinity of graphite is high more, and the side reactions such as decomposition of electrolytic solution take place easily at graphite surface when primary charging.The degradation production of this side reaction is constantly piled up, is grown at graphite surface, reaches the electronics that makes graphite up to it and can not directly move to thickness in solvent etc.Because side reaction during primary charging and cell reaction are irrelevant, so the electric weight that in first discharge process, can not take out, promptly so-called irreversible capacity significantly increases.That is to say to have the problem (J.Electrochem.Soc., Vol.117222 (1970) etc.) of first loading capacity with respect to ratio (the being also referred to as initial charge in this application sometimes) reduction of first charging capacity.Irreversible capacity is shown below.
Irreversible capacity=primary charging capacity-first loading capacity
In addition, also have report (J.Electrochem.Soc., Vol.137,2009 (1990)) claim, solvent molecule and lithium ion associating intercalation (co-intercalate), the graphite surface layer peels off, and the graphite surface that exposes again is by reducing initial charge with the electrolytic solution reaction.
The method that this by way of compensation initial charge reduces is known that the method for the positive electrode material that appends secondary cell.Yet the interpolation of excessive positive electrode material can bring again and make energy density reduce this new problem.
As mentioned above, the lithium-ion secondary cell for using graphite as negative material will help this two aspect of big loading capacity and high initial charge simultaneously, all depends on the crystallization degree of graphite, is the requirement of antinomy therefore.
As the method that addresses this problem, the high crystalline graphite that has proposed to help the loading capacity increase is as nuclear, with helping improving the low-crystalline graphite of initial charge or the method for the formation two-layer structure that carbon coats its surface.This be because, though the carbon loading capacity of low-crystalline is little, lower to the decomposition reaction of electrolytic solution.
The prior art of the carbon material of the two-layer structure that this employing crystallinity is different roughly is divided into following two kinds:
(1) use the low-crystalline carbon that generates from the thermolysis gas of organic compound such as propane, benzene to coat surface (for example the spy opens flat 4-368778 communique, the spy opens flat 5-275076 communique) as the high crystalline graphite of nuclear
(2) use the high crystalline graphite that pitch and hardening resin etc. coat or the dipping conduct is examined in liquid phase, sintering temperature about 1000 ℃ forms the carbon (for example spy open flat 4-368778 communique, spy open flat 5-94838 communique, spy and open flat 5-217604 communique, spy and open flat 6-84516 communique, spy and open flat 07-302595 communique, spy and open that flat 11-54123 communique, spy are opened flat 2000-229924 communique, the spy opens the 2000-3708 communique) of low-crystalline in its surface.
Yet from recent years concerning the desirability that loading capacity increases, above-mentioned any method all is inadequate.
From industrial angle, the method manufacturing process complexity of above-mentioned (1), cost is higher, has the problem of productivity aspect.In addition, because the low-crystalline carbon on surface is membranaceous covering as thin as a wafer, also have specific surface area to raise, the problem that initial charge reduces.
In addition, the problem of the method for above-mentioned (2) is: when the sintering temperature about 1000 ℃, the mutual welding of low-crystalline carbon on top layer, the low-crystalline carbon on top layer peeled off from the graphite that becomes nuclear when it was pulverized, and battery behaviors such as powder characteristics such as specific surface area and volume density, initial charge are reduced.
In addition, in the method for above-mentioned (1) and (2), low-crystalline carbon for the graphite nuclei surface that becomes nuclear, because its expansion when discharging and recharging, to shrink performance different, along with discharging and recharging rapidly and repeatedly discharging and recharging, because the low-crystalline carbon on top layer peels off, and also can cause above-mentioned same problem sometimes.
The loading capacity of battery depends on the loading capacity of graphite of the formation negative pole of every volume significantly.Therefore, in order to increase the loading capacity of battery, the bigger graphite of loading capacity (mAh/g) of filling unit weight to high-density is favourable.In addition, when filling graphite formation negative pole to high-density, in the method for above-mentioned (1) and (2), the closing force of the low-crystalline carbon on graphite and top layer is usually not enough.Thus, the adventitia of low-crystalline carbon peels off from graphite, exposes with the hyperergic graphite surface of electrolytic solution, and initial charge is reduced.
In addition, open in the 2000-3708 communique, also disclose in an embodiment with behind the pitch covering graphite the spy, at 2800 ℃ of following heat-treating methods, but the adventitia crystallinity low (the R value of Raman spectrum is 0.32, the measuring method aftermentioned of R value) that forms produces above-mentioned same problem.In addition, though use the flaky graphite on inclined-plane in core material, the aspect ratio of graphite is big, and the graphite orientation causes the reduction of sudden discharge characteristic and cycle characteristics when making negative pole.
Different with above-mentioned prior art, open the 2001-89118 communique for the particle shape crystallization spheric spy of composite graphite, it has certain effect aspect sudden discharge characteristic and the cycle characteristics.Yet, in this communique, do not mention outermost layer and inner crystalline difference.Only be with the coke and the pitch mixed sintering of many flats, be crushed to aspect ratio below 5, greying by this method for making, only can obtain the composite graphite particles of high crystalline then, and initial charge is still lower.
The present invention is intended to obtain a kind of with graphite during as the negative material of lithium-ion secondary cell, have the performance of following two kinds of antinomies concurrently, be big loading capacity and high initial charge, while sudden discharge characteristic and the also good lithium-ion secondary cell of cycle characteristics.Particularly, aim to provide a kind of composite graphite particles and manufacture method thereof that can satisfy the novelty of this performance, and the negative material and the lithium-ion secondary cell that use this composite graphite particles.
Summary of the invention
Promptly the present invention relates to following a kind of composite graphite particles, it is at the spacing d of X-ray diffraction
002On at least a portion surface less than the graphite of 0.337nm, have crystallinity and be lower than the carbon material of this graphite, the aspect ratio of this composite graphite particles is below 3, and 0.5～20 quality % of this composite graphite particles is this carbon material, in the Raman spectrum of this composite graphite particles, 1360cm
-1Peak strength (I
1360) with respect to 1580cm
-1Peak strength (I
1580) ratio (I
1360/ I
1580) more than 0.1 and less than 0.3.In addition, the preferred spacing d of the X-ray diffraction of this carbon material of this composite graphite particles
002Less than 0.343nm, and with respect to the spacing d of this graphite
002Ratio more than 1.001 and less than 1.02.
More preferably any composite graphite particles all is the graphite that granulation becomes flaky graphite.
In addition, the application also provides following a kind of composite graphite particles, wherein the globular graphite particle of flaky graphite granulation balling is reached 0.5～20 quality % to be scaled the carbon quality by mechanical external force, covered by following carbide lamella, this carbide lamella is by heating resin individually carbonization or resin and the carbonization of bituminous mixture heating up being formed.
And then; the application also provides following a kind of composite graphite particles; it is being on the globular granulation fossil China ink with the flaky graphite figuration by mechanical external force; following char-forming material by 0.5～20 quality % covers, but this char-forming material is to carry out carbonization by the char-forming material that mixing contains at least a kind of resin material in the mixture of the precursor that is selected from thermosetting resin, thermosetting resin and thermosetting resin raw material to get.In addition, this composite graphite particles preferably uses, but should char-forming material be the mixture of this resin material and tar class, and the composite graphite particles of the mass ratio of this resin material/tar class=5/95～100/0.
In addition, this resin material of aforesaid any composite graphite particles preferably is selected from the monomeric mixture of the precursor of phenol resins, phenol resins and phenol resins at least a kind.
And then the application also provides a kind of negative material that comprises the lithium-ion secondary cell of above-mentioned disclosed any composite graphite particles.In addition, also provide a kind of lithium-ion secondary cell that uses these any negative materials.
And then; the present invention also provides a kind of manufacture method that comprises the composite graphite particles of following operation; make flaky graphite become the globular granulating working procedure by mechanical external force; in the granulation fossil China ink that obtains; but the operation of mixing the char-forming material of at least a kind of resin material in the mixture contain the precursor that is selected from thermosetting resin, thermosetting resin and thermosetting resin raw material; so that the composite graphite particles that obtains in the follow-up carbonation process 80～99.5% for this granulation fossil China ink, and the operation of under 2000 ℃～3200 ℃, the mixture that obtains being carried out carbonization.In addition, in this manufacture method, but be somebody's turn to do the mixture that char-forming material is preferably this resin material and tar class, and this resin material/tar class=5/95～100/0 (mass ratio).
In addition, in each manufacture method, this resin material preferably is selected from least a kind in the monomeric mixture of the precursor of phenol resins, phenol resins and phenol resins.
And then, in above-mentioned each manufacture method, preferably before this carbonation process, further carry out operation at 200～300 ℃ of following these resin materials of thermofixation.
Description of drawings
Fig. 1 shows the model sectional view of the structure of the button cell be used to discharge and recharge test.
Embodiment
Below, explain the present invention.
The present invention relates to, at the spacing d of X-ray diffraction
002On at least a portion surface less than the graphite of 0.337nm, have crystallinity and be lower than the composite graphite particles of the carbon material of this graphite, the aspect ratio of this composite graphite particles is below 3,0.5～20 quality % of this composite graphite particles is this carbon material, in the Raman spectrum of this composite graphite particles, 1360cm
-1Peak strength (I
1360) with respect to 1580cm
-1Peak strength (I
1580) ratio (I
1360/ I
1580) more than 0.1 and less than 0.3 composite graphite particles.
Graphite
The graphite of core material that constitutes composite graphite material of the present invention is for demonstrating X-ray diffraction measured value d
002High crystalline graphite less than 0.337nm.As this graphite, can enumerate commercially available flakey natural graphite typically.The high graphite of crystallinity, crystallinity are growth regularly, generally all are flakey.In addition, because the shape reverse of the composite graphite particles that finally obtains mirrors the shape that hinders graphite, so the shape of graphite preferably uses aspect ratio (particulate major axis appearance is for the long ratio of minor axis) at the graphite below 3 near spherical.This graphite can be made by the method for example with flaky graphite as raw material.As flaky graphite, can use the graphite of commercially available prod or different shapes such as coarse-grained natural graphite or synthetic graphite.When using non-lepidiod graphite such as coarse-grained natural graphite or synthetic graphite, preferably, make it to become flakey at first with known shredding unit pulverizing.At this moment, the median size of crushed material preferably is adjusted into 5～60 μ m.As shredding unit, can use inverted draft pulverizer (ホ ソ カ ワ ミ Network ロ Application (strain) manufacturing), micronizer mill (day clear エ Application ジ ニ ア リ Application Network (strain)) etc.Wait the flaky graphite that obtains to have the part of acute angle in its surface by pulverizing, in the present invention, it is spherical preferably it being added the mechanical external force figuration, becomes the granulation fossil China ink of surface smoothing.In this granulating working procedure, use a large amount of flaky graphites of pulverizing to prepare usually, to form the granulation particle of aspect ratio below 3.But, in the present invention, do not get rid of yet and use the flaky graphite of pulverizing individually.Adding the mechanical external force figuration has no particular limits for the globular method, for example can enumerate, the method of under the coexistence of granulation aid such as what resin of tackiness agent, mixing a large amount of flaky graphites, in a large amount of flaky graphites, do not use tackiness agent and add the method for mechanical external force, perhaps be used in combination the two method.But more preferably do not use tackiness agent and add the mechanical external force granulation and be the globular method.As prilling granulator; can use GRANUREX (Off ロ イ Application ト industry (strain) manufacturing), ニ ユ-Network ラ マ シ Application (manufacturing of (strain) セ イ シ Application enterprise), multifunctional type powder treatment device tablets presss such as (ホ ソ カ ワ ミ Network ロ Application (strain) manufacturings), blend together system's ((strain) nara machinery make manufacturing), メ カ ノ マ イ Network ロ ス ((strain) nara machinery is made manufacturing), the compound makeup of mechanical type dry type particle and put (ホ ソ カ ワ ミ Network ロ Application (strain)) and wait device with shearing compression process ability.In addition, by using aforementioned shredding unit, the operation operating condition also can carry out granulation.
Figuration is that globular granulation fossil China ink can become circle with single flaky graphite and obtain, also can be a plurality of flaky graphites are gathered together granulation and form any one.The shape that especially preferably to present a plurality of flaky graphite granulations be concentric circles.
As the graphite of the core material that becomes composite graphite particles of the present invention, can be listed below preferred example, median size is 5～60 μ m, and aspect ratio is below 3, and specific surface area is 0.5～10m
2/ g, in the X-ray diffraction the axial size of the C of crystallite (Lc) more than 40nm, d
002Less than 0.337nm and the 1360cm that measures by Raman spectroscopy with argon laser
-1Band strength (I
1360) and 1580cm
-1Band strength (I
1580) ratio I
1360/ I
1580(R value) is 0.06～0.25, and 1580cm
-1Half breadth be 10～60.
Carbon material
Composite graphite particles of the present invention is coated by carbon material at the surface portion at least of graphite.Carbon material can be the material of any proterties that can bring composite graphite particles described later.Usually, but this carbon material carries out carbonizing treatment preferably by behind coating on the above-mentioned granulation fossil China ink, dipping and/or mixing char-forming material by heating.But so-called char-forming material is meant by heating and can realizes carbonization and/or graphited material among the application.This heats generally more than 700 ℃, preferred 800～3200 ℃.Therefore, so-called carbonizing treatment also comprises graphitization processing among the present invention.Preferred especially 2000～3200 ℃.In addition, the surface portion at least of so-called graphite is meant entire exterior surface or its part of graphite among the present invention.As shown in the application's typical case, handle by granulation, when granulation fossil China ink is the second particle that is formed by a plurality of (flakey) graphite, be meant entire exterior surface or its part of this second particle.Under the situation of this second particle, but char-forming material invades the inside of second particle and carbonization sometimes.Certainly, also can form this carbon material in the monomeric inside of graphite sometimes.But the composite graphite particles of the present invention most preferably entire exterior surface of this graphite is coated by this carbon material.Preferred fraction of coverage is 50～100%.
In addition, among the application, but above-mentioned char-forming material is preferably the mixture of resin material and tar class, and the tar class is this resin material/tar class=5/95～100/0 with respect to the mass ratio of this resin material.More preferably 30/70～70/30.If the ratio of this resin material is more than 5%, then the greying of the carbide lamella of Xing Chenging (crystallization) is carried out fully, and the lifting effect of initial charge increases simultaneously.Use this resin material and tar class if mix, then the degree of graphitization (crystallinity) of carbon material can be adjusted into the effect that makes the present invention reach maximum, therefore preferred.
So-called tar class is meant among the application, and the tar that generates during wood distillation, the coal tar that is obtained by coal, the precursor of heavy wet goods carbon material that originates from oil also comprise it as raw material and the material that polycondensation obtains.Particularly, for example carbobitumen, bulk mesophase pitch, oil are that pitch classes such as pitch are also contained in the tar class of the present invention.When being heat-treated respectively individually, it produces graphite-structure about 3000 ℃.The optics aspect can be isotropy or anisotropy.
So-called resin material is meant in the mixture of synthesis material of the precursor that is selected from resin itself, resin and resin at least a kind among the application.This resin precursor also comprises reaction intermediate, oligopolymer and polymerization intermediate.The example of the mixture of the synthesis material of resin has, comprise monomer class and polymerization starter etc., can be by heating, stir and place the mixture that this mixture obtains resin.
In the present invention, as this resin material, preferred use is selected from least a kind in the mixture of thermosetting resin, thermosetting resin raw material and the precursor of thermosetting resin etc.
Heat of carbonization thermosetting resin time-like at high temperature, the carbide that obtains also comprises the graphite part with the high crystalline that on average is equivalent to graphite sometimes, owing to also contain the part with carbon turbostratic, is called carbon material among the present invention, to distinguish with core material graphite.
As thermosetting resin, preferably, can enumerate urea resin, maleic acid resin, coumarone resin, xylene resin and phenol resins etc. by the residual more resin of carbon amount of thermal treatment.
Among the present invention,, more preferably use at least a kind in the precursor of the mixture be selected from phenol resins, phenol resins raw material and phenol resins as this resin material.As example more specifically, can enumerate any in the mixture (monomer mixture) of the initial stage condenses (precursor of phenol resins) of phenol resins itself (can substituted phenols, with formaldehyde be the highly condensed thing of the aldehydes of representative), phenols and aldehydes and phenols and aldehydes.
The crystallinity that constitutes the carbon material of composite graphite particles of the present invention is lower than the crystallinity of core material graphite, the spacing d of preferred X-ray diffraction
002Less than 0.343nm.If the d of carbon material
002Less than 0.343nm, loading capacity further improves, and the adaptation of carbon material and graphite also improves.The difference of the crystallinity of graphite and carbon material more preferably, the d of carbon material
002D with respect to graphite
002Ratio more than 1.001 and in less than 1.02 scope.If more than 1.001, initial charge further improves, if less than 1.02, the adaptation of carbon material also further improves.
Composite graphite particles
Composite graphite particles of the present invention is a kind of, at the spacing d of X-ray diffraction
002On at least a portion surface less than the graphite of 0.337nm, have crystallinity and be lower than the composite graphite particles of the carbon material of this graphite, wherein the aspect ratio of this composite graphite particles is below 3,0.5～20 quality % of this composite graphite particles is this carbon material, in the Raman spectrum of this composite graphite particles, 1360cm
-1Peak strength (I
1360) with respect to 1580cm
-1Peak strength (I
1580) ratio (I
1360/ I
1580) more than 0.1 and, again illustrate this point here less than 0.3, describe in more detail below.
This composite graphite particles is characterised in that it is near the globular shape of aspect ratio below 3.With aforesaid graphite as core material, its at least surface portion exist crystallinity to be lower than the carbon material of this graphite.The crystallinity on the surface of this composite graphite particles can be stipulated by the R value of Raman spectroscopy, with the 1360cm of argon laser by Raman spectroscopy mensuration
-1Band strength (I
1360) and 1580cm
-1Band strength (I
1580) ratio I
1360/ I
1580(R value) must be more than 0.10 and less than 0.30.If the R value is lower than more than 0.1 or 0.3, then initial charge all can reduce under any situation.Preferred especially R value is 0.1～0.2.
In addition, the ratiometric conversion of this carbon material of the application is that the scale of carbon shows, will fix in the scope of 0.5～20 quality % by the proportional divider of shared carbon material in composite graphite particles.This ratio is occupied corresponding with 80～99.5% of composite graphite particles by this granulation fossil China ink.Behind the carbonation process, should char-forming material but mix, so that 80～99.5% being occupied of composite graphite particles by this granulation fossil China ink, but because according to the kind difference of selected char-forming material and therefore the residual rate difference of carbon can not be stipulated entirely.But,, but mix char-forming material about about 1～70 quality % usually with respect to granulation fossil China ink.Example is more specifically, but when char-forming material is phenol resins etc., mixes about 2～50 quality %, about preferred 20～35 quality %.If suitably test the ratio that can obtain suiting with reference to it.When the ratio of shared carbon material is lower than 0.5 quality % in the composite graphite particles, be difficult to cover fully the edge surface of active graphite, initial charge reduces.On the other hand, when surpassing 20 quality %, the ratio of the carbon material that loading capacity is relatively low is too much, and the loading capacity of composite graphite particles reduces.In addition, be used to form the increasing proportion of the raw material (thermosetting resin and tar-bitumen class) of carbon material, in covering process and heat treatment step thereafter, particle is welded together easily, the part generation of the carbon material layer of the composite graphite particles that finally obtains is broken and is peeled off, and initial charge is reduced.The ratio spy of this carbon material is preferably 3～15 quality % especially, more preferably 8～12 quality %.
Further, enumerate the preferred physics value of composite graphite particles of the present invention, median size is 5～60 μ m, and aspect ratio is below 3, and specific surface area is 0.5～10m
2/ g, in the X-ray diffraction the axial size of the C of crystallite (Lc) more than 40nm, d
002Below 0.337nm.If median size and aspect ratio are in the prescribed value scope, loading capacity and initial charge improve, and other battery behavior such as charge-discharge characteristic and cycle characteristics also further improves rapidly.If the not enough 10m of specific surface area
2/ g, the viscosity adjustment of the negative pole mixing paste (mixture of negative material and tackiness agent dispersion liquid) when forming negative pole is easy, and the engaging force of tackiness agent also improves.If the Lc and the d of X-ray diffraction
002In prescribed value, can obtain sufficient loading capacity.
In addition, preferred this carbon material coats the outside surface of this graphite among the application, so the part of this carbon material of this composite graphite particles also shows as carbide lamella sometimes.
The manufacture method of composite graphite particles
The application also provides a kind of manufacture method that comprises the composite graphite particles of following operation; make flaky graphite become the globular granulating working procedure by mechanical external force; in the granulation fossil China ink that obtains; but the operation of mixing the char-forming material of at least a kind of resin material in the mixture contain the precursor that is selected from thermosetting resin, thermosetting resin and thermosetting resin raw material; so that the composite graphite particles that obtains in the follow-up carbonation process 80～99.5% for this granulation fossil China ink, and the operation of under 2000 ℃～3200 ℃, the mixture that obtains being carried out carbonization.
Below the manufacture method of composite graphite particles of the present invention is given an example.As previously mentioned, preferably use with flaky graphite by granulation operation etc. in advance figuration be globular graphite.When coating this granulation fossil China ink with type thermosetting resin or with the mixture of type thermosetting resin and tar class individually; for example can adopt, coating material and granulation fossil China ink be dropped in mixing machine, the temperature range more than the softening temperature of coating material in addition strong shearing force carry out mixing method.Perhaps with the solution of coating material or dispersion liquid with after granulation fossil China ink mixes, dry except that desolvating or the method for dispersion solvent etc.Preferred especially type thermosetting resin is low molecular weight substance (precursor of resin) or monomer mixture, and polymer quantizes by heating when coating granulation fossil China ink.Similarly, contain the tar time-like in coating material, the polycondensation of carrying out the tar class when coating also is effective.
As the necessary thermosetting resin of coating material among the present invention, preferred phenol resins when coating this granulation fossil China ink with phenol resins, preferably uses the precursor of phenol resins or contains the monomeric material of phenol resins.The precursor of phenol resins or the monomeric material that contains phenol resins also can coat granulation fossil China ink equably except by easy fusion of heating or the solubilisate.In addition, the phenol resins layer that forms by heating when coating also has and the granulation fossil China ink feature of driving fit securely.
Coating material can evenly or under the dispersive state coat at multiple constituent.Coating material also can change it to be formed, and carries out coating repeatedly.For example can be; on this granulation fossil China ink, coat the phenol resins form by phenol and formaldehyde as the 1st layer after; the xylenol resin that coating is formed by xylenol (xylenol) and formaldehyde is as the 2nd layer; on this granulation fossil China ink, coat pitch as the 1st layer after, coat phenol resins as the 2nd layer.
The covering amount of coating material can be set at, make final in composite graphite particles the ratio of shared carbide lamella be 0.5～20 quality %.
Preferably after coating coating material on this granulation fossil China ink, perhaps when coating processing, in 200～300 ℃ scope, make thermosetting resin cured.Owing in this curing process, can cause the volatilization of light volatiles contained in thermosetting resin and tar class, therefore preferably heat up usually with the competent time more than 4 hours.So keep the heating-up time, can make coating fully, successfully be cured, so the adaptation of coating material and granulation fossil China ink increases.
Behind hardening process, preferably carry out the granularity adjustment in case of necessity by pulverize and sieve processing etc., carry out sintering.Sintering is preferably carrying out more than 2000 ℃.More preferably 2500～3200 ℃, more preferably 2800～3200 ℃.Sintering processes can be used with the common graphitizing furnace of acheson furnace as representative.Preferably under non-oxidizable atmosphere, carry out.
The application also provides the negative material that contains any above-mentioned composite graphite particles.
Composite graphite particles of the present invention also can apply to the purposes beyond the negative pole neatly according to its feature, and for example the electro-conductive material used of fuel cell separator plate and refractory body are particularly preferred for the negative material of above-mentioned lithium-ion secondary cell with graphite etc.
That is, the key element of negative material of the present invention is to contain above-mentioned composite graphite particles at least.Therefore, composite graphite particles of the present invention itself also is a negative material of the present invention.In addition, in the purposes of lithium-ion secondary cell, mix the negative pole mixture of composite graphite particles of the present invention and tackiness agent and add negative pole mixing paste that solvent obtains, the current-collecting member that applied them in addition is also in the scope of negative material of the present invention.
Negative material and lithium-ion secondary cell to the lithium-ion secondary cell that uses composite graphite particles of the present invention describes below.
The negative material that lithium-ion secondary cell is used
The negative material that the application also provides the lithium-ion secondary cell that contains any above-mentioned composite graphite particles to use.
Negative pole of the present invention is by being cured above-mentioned negative material of the present invention and/or figuration obtains.The formation of this negative pole can be carried out according to common manufacturing process, so long as can give full play to the performance of this composite graphite particles, and makes the plastic property height with respect to powder, and the method that obtains the negative pole of chemistry, electrochemical stability gets final product, without any restriction.
When making negative pole, can use the negative pole mixture that in composite graphite particles, adds tackiness agent.As tackiness agent, preferably adopt relative ionogen and electrolyte solvent to have the material of chemical stability, electrochemical stability.For example can use the fluorine-type resin of poly(vinylidene fluoride), tetrafluoroethylene etc., polyethylene, polyvinyl alcohol, styrene-butadiene rubber(SBR), carboxymethyl cellulose etc.Also can be used in combination.
The usually preferred consumption of tackiness agent is, accounts for the amount about 1～20 quality % of negative pole mixture total amount.
Negative pole mixture layer can followingly form particularly, for example, will adjust to the composite graphite particles and the tackiness agent mixed preparing negative pole mixture of suitable particle diameter by classification etc., usually this negative pole mixture is coated on the single face of current collector or the two sides to form.At this moment can use common solvent, the negative pole mixture evenly and is securely engaged with current collector, obtain negative pole.Paste can stir by various mixing tanks and prepare.
For example, with fluorinated toners such as composite graphite particles of the present invention and tetrafluoroethylene in the Virahol equal solvent, mix, mixing after, coating forms the negative pole mixture.In addition, also water-soluble binders such as fluorinated resin such as composite graphite particles of the present invention and poly(vinylidene fluoride) or carboxymethyl cellulose can be mixed with N-Methyl pyrrolidone, dimethyl formamide or water, ethanol equal solvent be called pulpous state after, coating forms the negative pole mixture.
When the negative pole mixture that is formed by the mixture of composite graphite particles of the present invention and tackiness agent was coated on the current collector, its suitable applied thickness was 10～300 μ m.
After forming negative pole mixture layer, carry out crimping, can further improve the bond strength of negative pole mixture layer and current collector by exert pressure etc.
In lithium-ion secondary cell of the present invention, there is no particular limitation to be used for the shape of current collector of negative pole, can use the netted current collector of paper tinsel shape, mesh, expanded metal etc. etc.As current-collecting member, can enumerate copper, stainless steel, nickel etc.Under the situation of paper tinsel shape, about preferred 5～20 μ m of the thickness of current collector.
The lithium-ion secondary cell that uses above-mentioned negative material also is provided among the present invention.
Lithium-ion secondary cell
Lithium-ion secondary cell is main battery integrant with negative material, positive electrode material and non-water system ionogen usually.Positive electrode material and negative material become the carrier of lithium ion respectively.Battery principle is that in the lithium ion embedding negative pole, lithium is from taking off embedding from negative pole during discharge during charging.
There is no particular limitation except use contains the negative material of composite graphite particles of the present invention for lithium-ion secondary cell of the present invention.Integrant for other is a benchmark with the key element of common lithium-ion secondary cell.
(positive electrode material)
As the positive electrode material that uses in the lithium-ion secondary cell of the present invention (positive active material), preferably select the material that can embed/take off the lithium that embedding fully measures for use.For example lithium-containing compound, formula M such as lithium-containing transition metal oxide, transition metal chalkogenide, barium oxide and Li compound thereof
xMo
6S
8-yXue Fulie phase (Chevrel phase) compound shown in (X is the numerical value of the scope of 0≤X≤4 in the formula, and Y is the numerical value of the scope of 0≤Y≤1, and M is metals such as transition metal), gac, activated carbon fiber etc.Barium oxide such as V
2O
5, V
6O
13, V
2O
4, V
3O
8Deng shown in.
Lithium-containing transition metal oxide is the composite oxides of lithium and transition metal, also can be the material that lithium and the transition metal solid solution more than 2 kinds obtain.Composite oxides can use separately, also can make up more than 2 kinds and use.Lithium-containing transition metal oxide is particularly as LiM (1)
1- xM (2)
xO
2(x is the numerical value of the scope of 0≤x≤4 in the formula, and M (1), M (2) are made up of at least a transition metal.) or LiM (1)
1-yM (2)
yO
4Shown in (x is the numerical value of the scope of 0≤Y≤4 in the formula, and M (1), M (2) are made up of at least a transition metal).
In the formula, the transition metal shown in M (1), the M (2) is Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn etc., preferred Co, Ni, Fe, Mn, Ti, Cr, V, Al etc.
In addition, lithium-containing transition metal oxide can for example pass through, oxide compound or salt with Li, transition metal are initial feed, the composition of these initial feed according to the metal oxide of expectation mixed, and under the atmosphere that oxygen exists in 600 ℃～1000 ℃ temperature range sintering and obtaining.Initial feed is not limited to oxide compound or salt in addition, also can be oxyhydroxide etc.
For the lithium-ion secondary cell among the present invention, positive active material can use above-mentioned lithium compound separately, also can make up more than 2 kinds and uses.In addition, in positive electrode material, also can add the carbonic acid an alkali metal salt of Quilonum Retard etc.
For example can pass through, will be by above-mentioned lithium compound, tackiness agent and the formed cathode mixture of conductive agent that is used to pay electrode conductivuty be coated in the single face or the two sides of current collector, form the cathode mixture layer, to form positive electrode material.As tackiness agent, can use in the material that in negative pole, exemplifies any.As conductive agent, can use for example carbon material such as graphite and carbon black.
Positive pole also with negative pole similarly, can make it be paste-like in the solvent by cathode mixture is dispersed in, be coated on the current collector and drying by cathode mixture with this paste-like, to form the cathode mixture layer, after forming the cathode mixture layer, further carry out the crimping of exert pressure etc.Thus, the cathode mixture layer evenly and securely glues by on current collector.
There is no particular limitation for the shape of current collector.Can use the netted current collector of paper tinsel shape, mesh, expanded metal etc. etc.As current collector, can enumerate aluminium foil, stainless steel foil, nickel foil etc.Preferred 10～40 μ m of its thickness.
(nonaqueous electrolyte)
As the nonaqueous electrolyte that is used for lithium-ion secondary cell of the present invention, be the electrolytic salt that in common electrolytic solution, uses.Can enumerate LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5)
4, 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
4Deng lithium salts.From the angle of oxidative stability, especially preferably use LiPF
6, LiBF
4
Electrolytic salinity in the electrolytic solution is preferably 0.1～5 mol, more preferably 0.5～3.0 mol.
Nonaqueous electrolyte can be liquid nonaqueous electrolyte, polymer ionogen such as solid electrolyte or gel electrolyte.Under the former situation, nonaqueous electrolyte battery is made of so-called lithium ion battery, and in the latter case, nonaqueous electrolyte battery is made of polymer electrolytic cells such as so-called polymer solid electrolyte, polymer gel electrolyte batteries.
When forming liquid nonaqueous electrolyte liquid, as solvent, can use for example NSC 11801, propylene carbonate, methylcarbonate, diethyl carbonate, 1,1-or 1, the 2-glycol dimethyl ether, 1, carbonates such as 2-diethoxyethane, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, butyrolactam, 1,3-dioxy furans, the 4-methyl isophthalic acid, 3-dioxy furans, phenylmethylether, ethers such as ether, tetramethylene sulfone, thioethers such as methyl sulfolane, acetonitrile, the chlorine nitrile, nitriles such as propionitrile, trimethyl borate, quanmethyl silicate, Nitromethane 99Min., dimethyl formamide, N-Methyl pyrrolidone, vinyl acetic monomer, trimethyl orthoformate, oil of mirbane, Benzoyl chloride, benzoyl bromide, the tetrahydro-thiophene, methyl-sulphoxide, 3-methyl-2-oxazolidone, ethylene glycol, sulfite, non-proton organic solvents such as dimethyl sulfite.
When making nonaqueous electrolyte become polymer ionogen such as polymer solid electrolyte, polymer gel electrolyte, use polymer by softening agent (nonaqueous electrolytic solution) gelation as matrix.As the polymer that constitutes this matrix, the fluorine family macromolecule compound of acrylic ester macromolecular compounds such as ethers polymer, polymethacrylate macromolecular compound, polyacrylic ester, poly(vinylidene fluoride) (PVDF) or vinylidene fluoride-hexafluoropropylene copolymer etc. such as preferred especially polyoxyethylene or its crosslinked body etc.
In aforementioned polymer solid electrolyte or polymer gel electrolyte, plastification material can be added,, aforesaid electrolytic salt and non-aqueous solvent can be used as plastification material.When being polymer gel electrolyte, the electrolytic salinity of softening agent in nonaqueous electrolytic solution is preferably 0.1～5 mol, more preferably 0.5～2.0 mol.
There is no particular limitation for the making method of solid electrolyte, can enumerate, mix the macromolecular compound, lithium salts and the solvent that form matrix, the method of heating and melting macromolecular compound, after making macromolecular compound, lithium salts and non-aqueous solvent (softening agent) be dissolved in organic solvent, make the method for mixing with organic solvent evaporation, and will mix as polymerization single polymerization monomer, lithium salts and the non-aqueous solvent (softening agent) of the raw material of polymer electrolyte, and to this mixture irradiation ultraviolet radiation, electron rays or molecular ray etc. to form the method for polymkeric substance.
In addition, the adding proportion of the non-aqueous solvent in the aforementioned solid electrolyte (softening agent) is preferably 10～90 quality %, more preferably 30～80 quality %.If be lower than 10 quality %, then specific conductivity reduces, if be higher than 90 quality %, then the physical strength step-down is difficult to filming.
(dividing plate)
In giving secondary cell, can use dividing plate at lithium of the present invention.There is no particular limitation for the material of dividing plate, for example can enumerate, and spins cloth, non-woven fabrics, synthetic resins microporous film etc.Preferred especially synthetic resins microporous film.From thickness, film toughness, membrane resistance equal angles, wherein special preferred polyolefm class micro-porous film.Polyethylene and polypropylene microporous film specifically, or its compound micro-porous film etc.
In addition, can not use dividing plate yet and use gel electrolyte.
Use the secondary cell of gel electrolyte to pass through, negative material, positive electrode material and the gel electrolyte that will contain aforementioned composite graphite particles are according to for example sequential cascade of negative material, gel electrolyte, positive electrode material, and be housed in the battery exterior component, constitute this battery.And then, also gel electrolyte can be arranged on the outside of negative material and positive electrode material.
Further, the structure of lithium-ion secondary cell of the present invention without any restriction, there is no particular limitation to its shape, mode.According to purposes, installing machine, desired charge/discharge capacity etc., can select any shape or mode in round tube type, square, Coin shape, the button type etc.In order to obtain the higher hermetic type battery with nonaqueous electrolyte of security, preferably be provided with when the abnormal conditions of overcharging etc. and can press the mechanism that rises and cut off electric current in the induced cell.Under the situation of using polymer solid electrolyte battery and high-molecular gel battery, also can form the structure that makes it to be sealing in the laminated film.
Embodiment
Then be described more specifically the present invention by embodiment, the present invention is not limited to these embodiment.
In addition, in following embodiment and comparative example, make the evaluation of structure button type secondary cell as shown in Figure 1, evaluating combined thus graphite granule.But,, can make actual battery according to known method based on notion of the present invention.In this evaluation electricity pool, to act on very negative pole, polarity is anodal.
The preparation of＜negative pole mixture paste 〉
With respect to the composite graphite particles of 98 quality %, Xiang Shuizhong adds as the styrene-butadiene rubber(SBR) of 1 quality % of tackiness agent and the carboxymethyl cellulose of 1 quality %, makes it to become pulpous state with preparation negative pole mixture paste.
The manufacturing of＜negative pole 〉
Above-mentioned negative pole mixture paste is coated on the Copper Foil (current-collecting member) with homogeneous thickness, and then makes solvent evaporates and dry with 90 ℃ in a vacuum.Then, the negative pole mixture that this is coated on the Copper Foil is pressurizeed, then, it is die-cut into the circle of diameter 15.5mm with Copper Foil, make the negative pole 2 that constitutes by negative pole mixture layer of the current collector 7b driving fit that forms with Copper Foil with roller press.
＜anodal is made 〉
Lithium metal foil is pressed on the nickel screen, is die-cut into the cylindric of diameter 15.5mm, the current collector 7a driving fit that nickel screen forms is made the positive pole 4 that lithium metal foil constitutes on this current collector.
＜ionogen 〉
In the mixed solvent of the ratio of 33vol% NSC 11801 and 67vol% Methyl ethyl carbonate, make LiPFe
6Dissolving reaches 1mol/dm
3Concentration, the preparation nonaqueous electrolytic solution.The nonaqueous electrolytic solution that obtains is immersed in the polypropylene porous plastid, makes the dividing plate 5 that has soaked into electrolytic solution.
The making of＜evaluation electricity pool 〉
As estimating battery, make the button type secondary cell of structure with Fig. 1.
At first, driving fit at (the effect utmost point) 2 of the negative pole on the current collector 7b and driving fit clamping between (polarity) 4 of the positive pole on the current collector 7a soaked into the dividing plate 5 and the lamination of electrolyte solution.Thereafter, will adorn cap 1 outward and lump together with outer tinning 3, so that negative electrode collector 7b side is contained in the outer dress cap 1, positive electrode collector 7a side is contained in the outer tinning 3.At this moment, adorn outside in the peripheral position of cap 1 and outer tinning 3 and insert insulating washer 6, riveted joint is airtight two peripheries also.
The evaluation battery of as above making carries out the following test that discharges and recharges under 25 ℃ temperature.
As above the evaluation battery of Zhi Zaoing carries out the following test that discharges and recharges under 25 ℃ temperature.
＜discharge and recharge test 〉
Current value with 0.9mA carries out constant current charge till loop voltage reaches 0mV.Then, the moment that reaches 0mV in loop voltage switches to constant-potential charge, continues charging till current value becomes 20 μ A.Stop 120 minute thereafter.
Then, the current value with 0.9mA carries out the constant current discharge till loop voltage reaches 2.5V.At this moment, try to achieve charging capacity and loading capacity, calculate initial charge by following formula from the 1st round-robin energising amount.
In this test, the process that lithium ion embeds in the composite graphite particles is charging in addition, and the process of taking off embedding from composite graphite particles is discharge.
The loading capacity (mAh/g) of every 1g composite graphite particles of measuring is as shown in table 2 with the battery behaviors such as value of initial charge (%).
As shown in table 2, use the lithium-ion secondary cell of composite graphite particles of the present invention to demonstrate big loading capacity at negative pole, and had higher initial charge.
Then,, after similarly charging with the 1st circulation, carry out the constant current discharge, reach 2.5V up to loop voltage with the current value of 20mA as the 2nd circulation.At this moment according to the 1st round-robin loading capacity and the 2nd round-robin loading capacity, estimate sudden discharge efficient by following formula.
In addition, except that these evaluation tests, carry out constant current charge, reach 0mV up to loop voltage with the current value of 6mA.Then, the moment that reaches 0mV in loop voltage switches to constant-potential charge, continues charging till current value becomes 20 μ A.Stop 120 minute thereafter.
Then, carry out the constant current discharge with the current value of 6mA, till loop voltage reaches 2.5V.Repeat this and discharge and recharge 20 circulations, try to achieve the 1st circulation and the 20th round-robin loading capacity, by following formula computation cycles characteristic.
＜graphite 〉
As the graphite of the core that constitutes composite graphite particles of the present invention, in following embodiment and comparative example, use granulation fossil China ink with rerum natura as shown in table 1.
This granulation fossil China ink is the inverted draft pulverizer 200AFG that makes by with ホ ソ カ ワ ミ Network ロ Application (strain), with the flakey natural graphite of median size 30 μ m under air pressure 300kPa, the machine internal recycle after 1 hour granulation and.In the granulation fossil China ink that obtains, remove the granulation inadequate fine powder of particle diameter below 5 μ m.Removing meal again reaches below the 75 μ m sieve it.
Table 1
Embodiment 1
In the mixture of 500g ethylene glycol and 2.5g vulkacit H, add 25g phenol resins (residue carbon elements 40%) dissolving and form solution, in this solution, add 90g granulation fossil China ink (median size 20 μ m, aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer then and desolvate, obtain granulation fossil China ink with resin-coated.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours the cured resin coating material at 270 ℃ down with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the present invention of 10% covering amount.
In addition,, in the coating material of embodiment 1, do not add granulation fossil China ink, make its thermal process through similarly to Example 1, the carbide of preparation coating material for the crystallinity of the carbide of estimating embodiment 1.X-ray diffraction is measured d
002Be 0.3366nm, Lc38nm is with the d of the granulation fossil China ink that is used as core
002, Lc (table 1) compares and shows that crystallinity is low slightly.
In the solution that formalin and the 4g vulkacit H of 39g phenol, 66g 37% are formed, add 110g granulation fossil China ink (median size 20 μ m, aspect ratio is 2), under dispersion state, stir.Be heated to 90 ℃ and make monomer polymerization, coat granulation fossil China ink, filter and take out resin-coated granulation fossil China ink particle with phenol resins.This coating graphite particle has the coating layer that resinous principle is 20% (being scaled residue carbon elements is 10%).In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours down, solidify coating layer at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the present invention of 10% covering amount.
In the mixture of 500g tar lightweight oil and 1.5g vulkacit H, add 6.7g carbobitumen (105 ℃ of softening temperatures; residue carbon elements 60%) and 15g phenol resins (residue carbon elements 40%) form solution; in this solution, add 90g granulation fossil China ink (median size 20 μ m; aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer the tar lightweight oil that desolvates then, obtain the graphite that pitch/mixed with resin coats.In air, this coating graphite particle is warming up to 270 ℃, and then kept 2 hours down, solidify this coating material at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the present invention of 10% covering amount.
Embodiment 4
Formalin, 2g vulkacit H and 7.5g coal measures mesophase pitch fine powder (median size 4 μ m with 20g phenol, 33g 37%; 350 ℃ of softening temperatures; residue carbon elements 80%) mixes formation solution; in this solution, add 110g granulation fossil China ink (median size 20 μ m; aspect ratio is 2), under dispersion state, stir.Under 90 ℃, make the mentioned component polymerization, to coat granulation fossil China ink.Then, filter taking-up coating graphite particle.This granulation fossil China ink is coated (pitch compound resin composition is 18%, and being scaled residue carbon elements is 10%) by the pitch compound resin.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours down, solidify coating material at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the present invention of 10% covering amount.
Comparative example 1
In the mixture of 500g ethylene glycol and 0.1g vulkacit H, add 1g phenol resins (residue carbon elements 40%) and form solution, in this solution, add 100g granulation fossil China ink (median size 20 μ m, aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer then and desolvate, obtain the resin-coated graphite granule.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours the cured resin coating layer at 270 ℃ down with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the comparative example of 0.4% covering amount.
Comparative example 2
In the mixture solution of 60g phenol resins (residue carbon elements 40%), 500g tar lightweight oil and 6g vulkacit H, add 76g granulation fossil China ink (median size 20 μ m, aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer then and desolvate, obtain the graphite granule of resin-coated.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours down, solidify coating layer at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the comparative example of 24% covering amount.
Comparative example 3
With 0.6g phenol resins (residue carbon elements 40%), 0.4g carbobitumen (105 ℃ of softening temperatures; residue carbon elements 60%), 500g tar lightweight oil, 0.1g vulkacit H mix formation solution; in this solution, add 100g granulation fossil China ink (median size 20 μ m; aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer the tar lightweight oil that desolvates then, obtain the coating graphite particle.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours down, solidify coating material at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the comparative example of 0.48% covering amount.
Comparative example 4
With 30g phenol resins (residue carbon elements 40%), 20g carbobitumen (105 ℃ of softening temperatures; residue carbon elements 60%), 500g tar lightweight oil, 6g vulkacit H mix formation solution; in this solution, add 76g granulation fossil China ink (median size 20 μ m; aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer the tar lightweight oil that desolvates then, obtain the resin-coated graphite granule.In air, this resin-coated graphite granule is warming up to 270 ℃, and then kept 2 hours down, solidify coating material at 270 ℃ with 5 hours.Pulverizing this hardening thing reaches below the 75 μ m sieve it.In nitrogen atmosphere, under 1000 ℃, carry out preceding carbonizing treatment then, and then by under 3000 ℃, carrying out carbonization, obtain having the composite graphite particles of the comparative example of 24% covering amount.
Comparative example 5
According to embodiment 1, not carry out any coating and handle, all the other are according to obtaining the granulation fossil China ink of comparative example with embodiment 1 same method.
Comparative example 6
16.7g carbobitumen (105 ℃ of softening temperatures, residue carbon elements 60%) is dissolved in the 500g tar lightweight oil, in this solution, adds 90g granulation fossil China ink (median size 20 μ m, aspect ratio is 2), under dispersion state, stir.Under reduced pressure under 150 ℃, heat up in a steamer the tar lightweight oil that desolvates then, obtain graphite covered by asphalt.In nitrogen atmosphere, under 1000 ℃, this coating graphite particle is carried out preceding carbonizing treatment, be crushed to below the 75 μ m sieve.And then, obtain having 10% the composite graphite particles that is equivalent to prior art by under 3000 ℃, carrying out carbonization.
Comparative example 7
According to comparative example 6, except not carrying out 3000 ℃ carbonization, all the other obtain being equivalent to the granulation fossil China ink of prior art according to the method same with comparative example 6.
Comparative example 8
According to embodiment 1; as graphite granule; use is to lepidiod natural graphite mechanical external force in addition; but there is not balling; and keep lepidiod chamfering process graphite (median size 15 μ m; aspect ratio is 3.5), all the other obtain being equivalent to the granulation fossil China ink of prior art according to the method same with embodiment 1 in addition.
The powder characteristics and the battery behavior that have shown the composite graphite particles of embodiment and comparative example among table 2-1 and the table 2-2.
In embodiments of the invention 1～4, on granulation fossil China ink, coat the char-forming material of having set suitable R value.Compare and can see with the comparative example 5 that does not have char-forming material, though loading capacity reduces slightly, kept high discharge capacity, efficiency for charge-discharge, sudden discharge efficient, cycle characteristics aspect are also good in the early stage.Particularly as type thermosetting resin, the monomer of use phenol resins contains the embodiment 2,4 of thing in raw material, has outstanding sudden discharge efficient and cycle characteristics.
On the other hand, for comparative example 5 that does not have char-forming material and char-forming material the granulation particulate is coated inadequate comparative example 1,3, its initial charge, sudden discharge efficient, cycle characteristics aspect significantly reduce.On the contrary, be higher than the comparative example 2,4 of preferable range for char-forming material, the carbon material of welding lacks initial charge etc. and improves effect owing to the pulverizing of composite graphite particles is peeled off during coating.In addition, loading capacity significantly reduces.Increase by specific surface area also can be confirmed peeling off of char-forming material.
In char-forming material under the situation of the comparative example that is equivalent to prior art 6 of obsolete thermosetting resin, the crystallinity of char-forming material is too high and the R value reduces, and initial charge is reduced.And then, reduce to from 3000 ℃ in carbonization temperature under 1000 ℃ the situation of comparative example 7 of low temperatureization, electrical capacity is significantly reduced, sudden discharge efficient and cycle characteristics also reduce in addition.In addition, be positioned in the aspect ratio of graphite granule under the situation of the comparative example that is equivalent to prior art 8 outside the scope of the present invention's regulation, because the shape of composite graphite particles makes sudden discharge efficient and cycle characteristics reduce.
Table 2-2
| Sample | Loading capacity (mAh/g) | Initial charge (%) | Sudden discharge efficient (%) | Cycle characteristics (%) |
| Embodiment 1 | 363 | 95 | 91 | 92 |
| |
365 | 95 | 93 | 94 |
| |
360 | 94 | 94 | 95 |
| Embodiment 4 | 362 | 94 | 95 | 95 |
| Comparative example 1 | 371 | 90 | 74 | 84 |
| Comparative example 2 | 344 | 91 | 81 | 88 |
| Comparative example 3 | 371 | 90 | 75 | 85 |
| Comparative example 4 | 342 | 91 | 85 | 89 |
| Comparative example 5 | 370 | 87 | 71 | 82 |
| Comparative example 6 | 366 | 88 | 90 | 91 |
| Comparative example 7 | 347 | 92 | 87 | 88 |
| Comparative example 8 | 363 | 91 | 69 | 78 |
Industrial applicibility
By the present invention, can productivity well and at low cost provide the negative material composite graphite particles that is applicable to lithium rechargeable battery. This composite graphite particles is as the lithium rechargeable battery of negative material, not only can realize to heavens in the past because the high initial charge/discharge efficiency that antinomy was difficult to realize and large these two kinds of performances of discharge capacity, but also have good sudden discharge characteristic and cycle characteristics concurrently. Therefore, composite graphite particles of the present invention can satisfy in recent years the requirement to energy content of battery densification. And then, install the machine of negative material of the present invention and lithium secondary battery and can realize miniaturization and high performance, have widely industrial applicibility.
Claims (10)
1. composite graphite particles, it is at the spacing d of X-ray diffraction
002Less than 0.337nm and use at least a portion surface of granulation fossil China ink of a large amount of flaky graphites; have crystallinity and be lower than the carbon material of this graphite; the aspect ratio of this composite graphite particles is below 3; 0.5～20 quality % of this composite graphite particles is this carbon material; in the Raman spectrum of this composite graphite particles, 1360cm
-1Peak strength I
1360With respect to 1580cm
-1Peak strength I
1580Ratio I
1360/ I
1580More than 0.1 and less than 0.3.
2. the composite graphite particles of claim 1 record, wherein the spacing d of the X-ray diffraction of this carbon material
002Less than 0.343nm, and with respect to the spacing d of this graphite
002Ratio more than 1.001 and less than 1.02.
3. the composite graphite particles of claim 1 record, wherein by mechanical external force with the globular graphite particle of a large amount of flaky graphite granulation ballings to be scaled the carbon quality, reach 0.5～20 quality %, covered by following carbide lamella, this carbide lamella is by heating resin individually carbonization or resin and the carbonization of bituminous mixture heating up being formed.
4. the composite graphite particles of claim 1 record; it is being on the globular granulation fossil China ink with a large amount of flaky graphite figurations by mechanical external force; following char-forming material by 0.5～20 quality % covers, but this char-forming material is to carry out carbonization by the char-forming material that mixing contains at least a kind of resin material in the mixture of the precursor that is selected from thermosetting resin, thermosetting resin and thermosetting resin raw material to get.
5. the composite graphite particles of claim 4 record be the mixture of this resin material and tar class but wherein be somebody's turn to do char-forming material, and the mass ratio of this resin material and tar class is 5/95～100/0.
6. the composite graphite particles of claim 4 record, wherein this resin material is at least a kind that is selected from the monomeric mixture of the precursor of phenol resins, phenol resins and phenol resins.
7. the manufacture method of the composite graphite particles of claim 1 record comprises following operation:
Make a large amount of flaky graphites become the globular granulating working procedure by mechanical external force;
In the granulation fossil China ink that obtains, but the char-forming material that mixes at least a kind of resin material in the mixture contain the precursor that is selected from thermosetting resin, thermosetting resin and thermosetting resin raw material is so that 80～99.5 quality % of the composite graphite particles that obtains in the follow-up carbonation process are the operation of this granulation fossil China ink; And
The operation of under 2000 ℃～3200 ℃, the mixture that obtains being carried out carbonization.
8. the manufacture method of the composite graphite particles of claim 7 record be the mixture of this resin material and tar class but wherein be somebody's turn to do char-forming material, and the mass ratio of this resin material and tar class is 5/95～100/0.
9. the manufacture method of the composite graphite particles of claim 7 record, wherein this resin material is at least a kind that is selected from the monomeric mixture of the precursor of phenol resins, phenol resins and phenol resins.
10. the manufacture method of the composite graphite particles of each record in the claim 7～9 wherein before this carbonation process, is further carried out the operation at 200～300 ℃ of following these resin materials of thermofixation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002368514 | 2002-12-19 | ||
| JP368514/2002 | 2002-12-19 |
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| CN200810146127.9A Division CN101350407B (en) | 2002-12-19 | 2003-12-18 | Composite graphite particles and production method therefor, and cathode material of lithium ion secondary battery and lithium ion secondary battery using this |
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| CN200810146127.9A Expired - Lifetime CN101350407B (en) | 2002-12-19 | 2003-12-18 | Composite graphite particles and production method therefor, and cathode material of lithium ion secondary battery and lithium ion secondary battery using this |
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Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100704096B1 (en) |
| CN (2) | CN100422077C (en) |
| TW (1) | TWI243498B (en) |
| WO (1) | WO2004056703A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596881A (en) * | 2011-04-08 | 2014-02-19 | 中央电气工业株式会社 | Modified natural graphite particles |
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| EP2403802A4 (en) * | 2009-03-02 | 2015-07-01 | Showa Denko Kk | Composite graphite particles and lithium secondary battery using the same |
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| CN102255076B (en) * | 2010-05-19 | 2016-02-10 | 深圳市比克电池有限公司 | The graphite material of coated with carbon bed, preparation method and application |
| JP5150010B1 (en) * | 2010-07-02 | 2013-02-20 | シェンヅェン ビーティーアール ニュー エナジー マテリアルズ インコーポレイテッド | Method for producing lithium ion battery negative electrode material |
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| CN103035919A (en) * | 2012-12-14 | 2013-04-10 | 深圳市斯诺实业发展有限公司永丰县分公司 | Method for preparing modified graphite negative electrode material of lithium ion power battery |
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| CN107207258B (en) | 2015-02-24 | 2019-09-27 | 昭和电工株式会社 | Carbon material, its manufacturing method and application thereof |
| JP6412520B2 (en) * | 2015-06-01 | 2018-10-24 | Ｊｆｅケミカル株式会社 | Carbonaceous coated graphite particles for lithium ion secondary battery anode material, lithium ion secondary battery anode and lithium ion secondary battery |
| KR102492760B1 (en) * | 2019-01-14 | 2023-01-27 | 주식회사 엘지에너지솔루션 | Method for preparing negative electrode active material |
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| CN116914135A (en) * | 2020-04-24 | 2023-10-20 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical device using same, and electronic device |
| KR20210132927A (en) * | 2020-04-28 | 2021-11-05 | 재단법인 포항산업과학연구원 | Negative electrode material for rechargeable lithium battery, method for manufacturing the same and rechargeable lithium battery including the same |
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| WO2022099457A1 (en) * | 2020-11-10 | 2022-05-19 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical apparatus using same, and electronic device |
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| KR102480217B1 (en) * | 2021-07-29 | 2022-12-22 | 주식회사 엘피엔 | The new spherical carbonaceous material, battery including the same as an anode active material, and method of preparing the spherical carbonaceous material |
| CN114824226B (en) * | 2022-05-13 | 2023-07-14 | 欣旺达电动汽车电池有限公司 | Negative electrode plate, preparation method thereof, lithium ion battery and electric equipment |
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- 2003-12-18 WO PCT/JP2003/016241 patent/WO2004056703A1/en active Application Filing
- 2003-12-18 KR KR1020057011367A patent/KR100704096B1/en active IP Right Grant
- 2003-12-18 CN CNB2003801065709A patent/CN100422077C/en not_active Expired - Lifetime
- 2003-12-18 CN CN200810146127.9A patent/CN101350407B/en not_active Expired - Lifetime
- 2003-12-19 TW TW092136136A patent/TWI243498B/en not_active IP Right Cessation
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| JPH07302595A (en) * | 1994-05-09 | 1995-11-14 | Asahi Organic Chem Ind Co Ltd | Manufacture of carbon particle and negative electrode containing this carbon particle |
| EP0917228A1 (en) * | 1997-05-30 | 1999-05-19 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100704096B1 (en) | 2007-04-06 |
| TW200414579A (en) | 2004-08-01 |
| KR20050084413A (en) | 2005-08-26 |
| TWI243498B (en) | 2005-11-11 |
| CN101350407B (en) | 2014-07-30 |
| CN1726168A (en) | 2006-01-25 |
| WO2004056703A1 (en) | 2004-07-08 |
| CN101350407A (en) | 2009-01-21 |
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