CN100564253C - The greying thing of mesophasespherule, the negative material that uses it, negative pole and lithium-ion secondary cell - Google Patents
The greying thing of mesophasespherule, the negative material that uses it, negative pole and lithium-ion secondary cell Download PDFInfo
- Publication number
- CN100564253C CN100564253C CNB038003333A CN03800333A CN100564253C CN 100564253 C CN100564253 C CN 100564253C CN B038003333 A CNB038003333 A CN B038003333A CN 03800333 A CN03800333 A CN 03800333A CN 100564253 C CN100564253 C CN 100564253C
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- Prior art keywords
- thing
- greying
- mesophasespherule
- lithium
- negative pole
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Classifications
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- 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
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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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- 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
- H01M4/04—Processes of manufacture in general
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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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 is the processing that the spherular greying thing of intermediate phase is side by side applied force of compression and shearing force, makes the average lattice plane interval d of X-ray diffraction
002Less than 0.337nm, and in the raman spectrum of the argon laser that uses wavelength 514.5nm, be present in 1350cm
-1～1370cm
-1The peak strength I in field
DBe present in 1570cm relatively
-1～1630cm
-1The peak strength I in field
GRatio I
D/ I
GFor surpassing 0.4 invention to the method for the greying thing of the mesophasespherule below 2.It also is the invention of greying thing itself of mesophasespherule that has the prerequisite of relevant X-ray diffraction and raman spectrum concurrently.The greying thing of the mesophasespherule that obtains suitable negative pole and negative material as lithium-ion secondary cell, even under the situation of using the water cathode mixture paste, also can access and keep big loading capacity and high initial charge and lithium-ion secondary cell with the high charging efficiency rapidly that did not in the past reach.
Description
Technical field
The present invention relates to loading capacity, initial charge and the lithium-ion secondary cell and the constituent material thereof of 3 excellent propertys of charging efficiency rapidly.Use the negative pole of being made by the negative pole mixture paste of water class even particularly relate to, also can not making rapidly, charging efficiency reduces the lithium-ion secondary cell that also can keep loading capacity and initial charge.Further relate to negative pole and negative material that this lithium-ion secondary cell is used, and the greying thing and the manufacture method thereof that constitute the mesophasespherule of negative pole and negative material.
Background technology
In recent years, along with the miniaturization or the high performance of e-machine, the requirement of the high-energy-densityization of battery is increased gradually.Compare with other secondary cell, lithium-ion secondary cell improves energy density and noticeable because can Towards Higher Voltage.Lithium-ion secondary cell is with negative pole, and anodal and nonaqueous electrolyte is main integrant.In the charged process, the lithium ion that produces from nonaqueous electrolyte moves between positive pole and negative pole, becomes secondary cell.
Usually, use the negative pole material of carbon material as above-mentioned lithium-ion secondary cell.As such carbon material, at present main the use demonstrates high discharge capacity and current potential flatness, and has lit-par-lit structure, so that easy occlusion when charge/discharge/emit the graphite of lithium ion.
As graphite material, natural graphite, synthetic graphites such as the high temperature sintering body of coke, greying things such as pitch-based carbon fiber or mesocarbon fiber are by known.And then, open flat 5-290833 communique the spy and also put down in writing being that the mesophase pitch of raw material is heat-treated greying thing of the intermediate phase class that obtains etc. with tar or pitch.
Although the natural graphite in the above-mentioned graphite material has the high advantage of loading capacity, owing to have the scale shape, directed easily when forming negative pole, nonaqueous electrolyte is incomplete with contacting of graphite, and charge-discharge characteristic (being also referred to as rate characteristic) reduces rapidly.In addition, be accompanied by discharge and recharge graphite flexible and be same direction, can not keep the contact between graphite and produced the problem that cycle characteristics reduces.Relative with it, middle asphalt phase is heat-treated and the greying thing that obtains, the greying thing of the mesophasespherule that particularly in pitch, generates have spherical or with spherical close shape.Thus, when negative pole forms, be easy to stackedly randomly, in negative pole, can contain nonaqueous electrolyte equably.In addition, being accompanied by the flexible direction that discharges and recharges graphite is at random.Its result brings into play good charge-discharge characteristic rapidly and cycle characteristics.
Open flat 5-290833 communique according to the spy, obtain the pitch class is remained under 350～500 ℃ the heat fusing temperature and the carbonaceous mesophase phase microsphere that generates.Put down in writing make it carbonization after, under 2500～2900 ℃, carry out greying and the greying thing that obtains.In this communique, the median size of the greying thing of above-mentioned mesophasespherule is 25 μ m, and the average lattice plane of X-ray diffraction is d at interval
002Be 0.3365～0.3390nm, and the 1360cm in the argon laser raman spectrum
-1Peak strength with respect to 1580cm
-1The ratio of peak strength in 0.2～0.4 scope, this greying thing is as the negative material of lithium-ion secondary cell and be suggested.
, make negative pole at the greying thing with mesophasespherule, when constituting lithium-ion secondary cell with this negative pole, the use solvent types difference when making according to negative pole can not be given full play to the performance of this battery sometimes.
Usually, when making negative pole, at first carbon material and tackiness agent (adhesive resin) are mixed also pasteization in solvent (below, contain solvent and/or dispersion agent).After then the paste (being referred to as negative pole mixture paste) that obtains being coated on the current-collecting member such as Copper Foil, pressurizeing obtains negative pole.In this paste chemical industry preface, if with the non-water kind solvent of organic solvent etc. as solvent, it is big to access loading capacity, initial charge and all high good lithium-ion secondary cell of charging efficiency rapidly.
On the other hand, in recent years, from the viewpoint of environment aspect and secure context etc., it is the negative pole mixture paste of water class that people wish to make the water kind solvent., make under the situation of water kind solvent (medium that contains water) as this solvent, the battery behavior of charging efficiency etc. reduces rapidly sometimes.That is, with the greying thing of the mesophasespherule occasion as negative material, the performance of the lithium-ion secondary cell that obtains is limited by the solvent species of negative pole mixture paste.Be referred to as the solvent interdependence of lithium-ion secondary cell in this application.
The greying thing that the present application person open the known mesophasespherule that flat 5-290833 communique etc. put down in writing with above-mentioned spy makes the medium of water class or non-water class make negative pole as negative material, has studied the solvent interdependence of lithium-ion secondary cell.Its result has confirmed when making water class medium the situation that charge characteristic rapidly still reduces.
Summary of the invention
The present invention In view of the foregoing proposes, even purpose is that it is big also to obtain loading capacity under the situation of using the water cathode mixture paste, and initial charge and all high good lithium-ion secondary cell of charging efficiency rapidly.And then the purpose negative pole and the negative material that also are to provide the lithium-ion secondary cell of such 3 excellent propertys to use, and the greying thing and the manufacture method thereof that constitute the mesophasespherule of negative pole and negative material.
That is, the invention provides a kind of greying thing of mesophasespherule, wherein, the average lattice plane of X-ray diffraction is d at interval
002Less than 0.337nm, and in the raman spectrum of the argon laser that uses wavelength 514.5nm, be present in 1350cm
-1～1370cm
-1The peak strength I in field
DBe present in 1570cm relatively
-1～1630cm
-1The peak strength I in field
GRatio I
D/ I
GFor surpassing 0.4 to below 2, this greying thing is to be greying thing below 20% by the reduction rate that the mechanochemistry that side by side applies force of compression and shearing force is handled the median size that makes this mesophasespherule.
In addition, the median size that the volume of the greying thing of this mesophasespherule converts is preferably 3～50 μ m, and specific area is preferably 1～20m
2/ g.
The greying thing of any above-mentioned mesophasespherule is preferably buried the hardness height of greying thing of this mesophasespherule of hardness ratio and the median size little micropartical of median size than the greying thing of this mesophasespherule underground on the surface, more preferably for this micropartical is from silicon oxide, that selects in the cohort that aluminum oxide and titanium oxide constitute is at least a.
And then, in this application, also provide the invention of the negative material that the lithium-ion secondary cell of the greying thing of the above-mentioned mesophasespherule that contains any uses.
Moreover this negative material preferably also contains the greying thing graphite in addition of this mesophasespherule.Therein, more preferably for also to contain by the low graphite that carbon material coated of crystallinity of crystallinity than the greying thing of this mesophasespherule.
And then, in this application, also provide the invention of the negative pole of using by any lithium-ion secondary cell that constitutes of above-mentioned negative material.
In addition, in this application, also provide the invention of lithium-ion secondary cell with any above-mentioned negative pole.
And then, in this application, also provide invention to the manufacture method of the greying thing of above-mentioned mesophasespherule.In this manufacture method, it is side by side to apply force of compression and shearing force so that the reduction rate of the median size of this mesophasespherule is the processing below 20% that this mechanochemistry is handled.
Moreover, in this manufacture method, be preferably with the hardness height of the greying thing of this mesophasespherule of hardness ratio and median size than the little atomic coexistence of the median size of the greying thing of this mesophasespherule under, carry out aforementioned processing.Therein, preferred manufacture method is that aforementioned micro particles is from silicon oxide, and that selects in the cohort that aluminum oxide and titanium oxide constitute is at least a.
Description of drawings
Fig. 1 is the sectional view of evaluation battery that expression is used for the characteristic of evaluating graphite thing.
Fig. 2 is the diagrammatic illustration figure of device that is used to side by side to apply the processing of force of compression and shearing force.
Fig. 3 is the diagrammatic illustration figure of other device that is used to side by side to apply the processing of force of compression and shearing force.
Fig. 4 is the figure of water infiltration capacity (wetting ability) of the greying thing of the mesophasespherule that obtains of expression embodiment and comparative example.
Embodiment
Below, more specifically describe the present invention.
At first, the greying thing to mesophasespherule of the present invention describes.
The greying thing of＜mesophasespherule 〉
Mesophasespherule of the present invention is in general by be easy to promote graphited carbon material manufacturing by high-temperature heat treatment.Enumerate the tar class of petroleum-type or coal class, pitch class as such carbon material.For example, when coal tar was heated to 350～500 ℃, heavily polycondensation and gigantism took place in aromatic polycyclic molecule, produced to have optically anisotropic spherular mesophasespherule.Mesophasespherule can pass through benzene, toluene, and quinoline, oil in the tar, the organic solvent of tar heavy oil or washing wet goods separates from having optically isotropic bitumen base, carries out refining.The mesophasespherule that obtains is not limited to spherical, mostly be spherical or with spherical proximate shape.So, between the one's own profession dealer, be commonly referred to as " mesophasespherule " at ordinary times and come to be distinguished with other carbon material.
Under non-oxidizing atmosphere, separated mesophasespherule is once sintered with the temperature more than 300 ℃, when finally under surpassing 2000 ℃ situation, carrying out pyroprocessing, can access the greying thing of the mesophasespherule of raw material of the present invention.Because in fact the greying thing of mesophasespherule is keeping the shape before the greying, thus mostly be spherical or with spherical proximate shape.The greying thing of the mesophasespherule of asking in this also can carry out final pyroprocessing above under 2000 ℃ the situation after pulverizing mesophasespherule.Because mesophasespherule has optical anisotropy,, can bring into play good battery performance as negative material so, also do not have the problem of the such directed aspect of natural graphite even pulverizing under microsphere and the graphited situation., under overground situation, irreversible capacity increases, and this situation is unfavorable.Can suitably adopt known breaking method, working method to pulverize.Pulverizing preferably after once sintered with the condition more than 300 ℃, is carried out before the final pyroprocessing.In this application, the pulverizing product of mesophasespherule are carried out greying and the material that obtains is also referred to as the greying thing of mesophasespherule.
In addition, the final pyroprocessing under the non-oxidizing atmosphere is preferably being carried out more than 2500 ℃, more preferably carries out under the condition more than 2800 ℃., for fear of the distillation of greying thing or decomposition etc., even the ceiling temperature height of this final pyroprocessing is also about 3300 ℃ usually.
If mesophasespherule is being carried out final pyroprocessing and greying above under 2000 ℃ the temperature, can access the average lattice plane interval d of X-ray diffraction in the past
002Greying thing less than the mesophasespherule of 0.337nm., this greying thing is present in 1350cm in the raman spectrum of the argon laser that uses wavelength 514.5nm
-1～1370cm
-1The peak strength I in field
DBe present in 1570cm relatively
-1～1630cm
-1The peak strength I in field
GRatio I
D/ I
GBe below 0.35.
In the present invention, the greying thing of above-mentioned mesophasespherule in the past (below, also only be called " raw material greying thing " sometimes) is implemented surface modification treatment, make above-mentioned I
D/ I
GThan increasing.
That is, the present invention is the processing that the spherular greying thing of intermediate phase is applied simultaneously force of compression and shearing force, makes the average lattice plane interval d of X-ray diffraction
002Less than 0.337nm, and in the raman spectrum of the argon laser that uses wavelength 514.5nm, be present in 1350cm
-1～1370cm
-1The peak strength I in field
DBe present in 1570cm relatively
-1～1630cm
-1The peak strength I in field
GRatio I
D/ I
GFor surpassing 0.4 invention to the method for the greying thing of the mesophasespherule below 2.It also is the invention of greying thing itself of mesophasespherule that has the prerequisite of relevant X-ray diffraction and raman spectrum concurrently.
The axial average lattice plane of the C of the X-ray diffraction of the greying thing of the mesophasespherule of the present invention that obtains (below, be also referred to as " modified graphite thing ") is d at interval
002Less than 0.337nm, be preferably less than 0.3365nm.So average lattice plane is d at interval
002Short greying thing crystallinity height, in other words degree of graphitization is also high.So, when using, can access the high lithium-ion secondary cell of loading capacity as the negative material of lithium-ion secondary cell.
In addition, average lattice plane interval d
002Mean with CuK α line as the X line, by with the high purity silicon being the X-ray diffraction method (large space between muscles China fir youth, carbon fiber, p.733-742 (1986) editor in modern age society) of reference material and the value measured.
Modified graphite thing of the present invention presents specific raman spectrum.Specifically, in the raman spectrum of the argon laser that uses wavelength 514.5nm, make to be present in 1350cm
-1～1370cm
-1The peak strength in field be I
D, be present in 1570cm
-1～1630cm
-1The peak strength in field be I
GThe time the peak strength ratio I
D/ I
GBe in and surpass 0.4 to the scope below 2.
In addition, the said peak strength of the application means the intensity of peak height gained.
Use is satisfied this modified graphite thing of two prerequisites of above-mentioned X-ray diffraction and raman spectrum and is made negative pole, and when being used for lithium-ion secondary cell, the solvent interdependence of lithium-ion secondary cell disappears.That is, even make the negative pole mixture paste of water class, when also can play the loading capacity of keeping lithium-ion secondary cell and initial charge, the effect that also do not reduce of charge characteristic rapidly.In addition, in this case, at above-mentioned I
D/ I
GThan being 0.4 when following, charge characteristic can reduce rapidly sometimes.On the other hand, at I
D/ I
GRatio was greater than 2 o'clock, and loading capacity has the tendency of reduction.The above-mentioned I of modified graphite thing of the present invention
D/ I
GThan especially preferably in 0.45～1 scope.
Present inventors understand like this: make I because of the surface modification of the greying thing of the mesophasespherule of raw material
D/ I
GComparing this solvent interdependence exerts an influence.Though it is not necessarily clear and definite to obtain the principle of surface modification effect, think to have ground the reason on the surface of greying thing by applying force of compression and shearing force simultaneously.Therefore, think that more hydrophilic group appears in the surface of raw material greying thing, the wetting ability of greying thing itself improves.So the processing (below, also only be called [surface modification treatment]) that applies force of compression and shearing force in the present invention simultaneously also claims to can be described as and a kind ofly changes or a kind of mechanochemistry of giving the character of chemistry is handled by processing machinery or physics.Give hydrophilic method as confirming to the surface of raw material greying thing, can be by the greying thing after this surface modification treatment and the measurement of contact angle of water, or the seepage velocity by water, infiltration capacity mensuration waits to be estimated.
As long as the used device of surface modification treatment of the present invention can apply force of compression and shearing force to object being treated simultaneously, there is no particular limitation to device construction.
As such device, can use the mixing machine that for example pressurizes, the mixing roll of two roller mixing rolls etc., the screw grinding machine, blend together system's ((strain) nara machinery is made made), microcommand machinery ((strain) nara machinery is made made), mechanical fusion system (ホ ソ カ ワ ミ Network ロ Application (strain) system) etc.
In said apparatus, preferably adopt and utilize the speed of rotation difference to apply the device of shearing force and force of compression simultaneously.For example can be set forth in the mechanical fusion of ホ ソ カ ワ ミ Network ロ Application (strain) the system system of schematically illustrated its principle among Fig. 3 (a)～(b).This device has swing roller (rotor 31), the internal part different with this drum rotation speed (internals 32), the cycling mechanism of object being treated (for example circulation blade 33).Mark 35 is baffle plates, the 36th, and goods.Be fed into the centrifugal force due to the rotation that raw material greying thing 34 between rotor and the internals is subjected to rotor, and be subjected to force of compression and shearing force due to the velocity contrast of rotor and internals simultaneously.And raw material greying thing is subjected to the effect of this force of compression and shearing force repeatedly by cycling mechanism.
As other example, can be set forth in (strain) nara machinery that schematically shows among Fig. 2 and make the made system that blendes together.Mark 23 is blades, the 25th, and circulation path, the 26th, the outer cover of cooling or heating usefulness, the 27th, outlet valve, the 28th, relief outlet.Also be subjected to rotor 22 and the force of compression due to the velocity contrast between the resting barrel (stator 21) and the effect of shearing force of high speed rotating simultaneously repeatedly by the raw material greying thing of input port 24 supplies.
In the method for the invention, the stirring than general is big usually with shearing force to be applied to force of compression on the raw material greying thing simultaneously., these mechanical stress preferably are applied on the surface of raw material greying thing, and wish that stress intensity is a degree of not destroying the particle structure of greying thing.When the particle structure of greying thing is destroyed, the tendency of the irreversible capacity increase that causes lithium-ion secondary cell is arranged.If represent with concrete example, this surface modification treatment is preferably carried out in the mode that the reduction rate of the median size of raw material greying thing is suppressed to below 20%.
For example when use has the device of swing roller and internal part, be that 5～50m/ second, between the two distance are 1～100mm, treatment time to be to carry out under 3 minutes～90 minutes the condition preferably in the roll surface speed difference of swing roller and internal part.
When this external use has the device of resting barrel/high speed rotating rotor, be 10～100m/ second, treatment time to be to carry out under 30 seconds～10 minutes the condition preferably in the roll surface speed difference of resting barrel and rotor.
By the above manufacture method of the present invention that exemplifies, can access modified graphite thing of the present invention, promptly satisfy the greying thing of mesophasespherule of two prerequisites of aforesaid X-ray diffraction and raman spectrum.
The shape of modified graphite thing of the present invention preferably still be spherical or with spherical proximate shape.Because also be after having carried out applying the processing of force of compression and shearing force simultaneously, so also can be granular or pulverize due to the indefinite particle of shape.
The median size of the volume conversion gained of modified graphite thing of the present invention is preferably 3～50 μ m.If median size is more than 3 μ m, when the negative material as lithium-ion secondary cell uses, can not cause the reduction of the security of the increase of irreversible capacity or battery.In addition, if below 50 μ m, then can access the good lithium-ion secondary cell of tackiness of negative pole.
Above-mentioned median size particularly preferably is 5～30 μ m.In addition, the pure proportion of modified graphite thing is preferably more than 2.2.
In addition, in the specific area of nitrogen adsorption BET method, the specific area of modified graphite thing of the present invention is preferably 1～20m
2/ g.If 20m
2Below/the g, can not increase the irreversible capacity of battery, security is good.More preferably be 5m
2Below/the g.In addition, if 1m
2More than/the g, under the situation of the negative pole mixture paste that makes the water class, the good battery behavior that is easy to obtain.
Modified graphite thing of the present invention preferably is embedded with the hardness height and the median size micropartical littler than the median size of this modified graphite thing of this modified graphite thing of hardness ratio itself on the surface.
If with the condition of this micropartical coexistence under carry out this surface modification treatment of raw material greying thing, can access such modified graphite thing of the present invention.As this micropartical, so long as have, then can use any material and be not particularly limited than little median size of the median size of this modified graphite thing and harder material.At this micropartical is under the situation of condensation product, so long as the little material of particle diameter of the particle diameter ratio modified graphite thing of primary particle gets final product.Though this atomic form and median size are not stipulated,, then can be accessed the surface modification effect of raw material greying thing if more than 1nm.Hope is the upper limit with 100nm, so that do not hinder the modified graphite thing of the present invention contact each other that obtains, and can not produce bad influence to charge-discharge characteristic.
This micropartical can be the material that helps electroconductibility or discharge and recharge, and also this is not had the material of help.Specifically, can exemplify metal, metal oxide, metal nitride, metal boride, metallic carbide etc.
In these materials, wish to adopt hard particles of possess hydrophilic property.Be preferably silicon oxide therein, the micropartical of aluminum oxide or various metal oxides.Particularly preferably use from silicon oxide at least a micropartical of selecting in the cohort that aluminum oxide and titanium oxide constitute.Silicon oxide, aluminum oxide and titanium oxide are preferably made by vapor phase process.Silicon oxide is preferably anhydrous silicon oxide.
Under the condition of hard particles that has these possess hydrophilic properties, when modification was carried out on the surface of raw material greying thing, the modified graphite thing that obtains had further improved wetting ability.
When such surface modification treatment, usually relative raw material greying thing can use this micropartical about 0.01～10 quality %.In addition, this micropartical can with in advance with the material of raw material greying thing dry mixed in this surface modification treatment, also can in this of raw material greying thing handled, add.
In addition, the relative goods greying of this micropartical thing that is used is preferably and buries underground about 0.01～5 quality %, more preferably is the quantity about 0.01～0.5 quality %, and hope and greying thing are integrated.
In this surface modification treatment that makes this above-mentioned micropartical coexistence, can access except wetting ability, the surface is also imperceptibly by the modified graphite thing of rugosityization.When the grinding effect on greying thing surface increases, think that the near surface that this micropartical is embedded in raw material greying thing has also increased effect of the present invention.
In the present invention, in the scope of not damaging effect of the present invention, can add known conductive material, ionic conductivity material, tensio-active agent, the various interpolation materials of macromolecular compound etc.Before can being this surface modification treatment the period of this interpolation, in the processing, the arbitrary period after the processing.
The negative material that＜lithium-ion secondary cell is used 〉
In this application, the negative material that also provides the lithium-ion secondary cell that contains above-mentioned modified graphite thing of the present invention to use.
Usually, when the negative pole that the making lithium-ion secondary cell is used, at first carbon material and tackiness agent are mixed in solvent (containing solvent and/or dispersion agent) and pasteization.After then being coated on the paste (being referred to as negative pole mixture paste) that obtains on the current-collecting member, removing and to desolvate, obtain negative pole thus by curing such as pressurization and/or shaping.The negative material of the present application means all material up to this curing and/or forming process.That is be prerequisite, in this negative material, to contain above-mentioned modified graphite thing at least.So modified graphite thing of the present invention itself also is the negative material that lithium-ion secondary cell of the present invention is used.In addition, mixed the negative pole mixture of modified graphite thing of the present invention and tackiness agent, and then added solvent and the negative pole mixture paste that obtains, and then this paste has been coated on the material that obtains on the current-collecting member etc. also in the scope of negative material of the present invention.
In the present invention, if any of modified graphite thing that uses the invention described above be as negative material, even then adopt the negative pole mixture paste method of water class, the charging efficiency rapidly of lithium secondary battery can not reduce yet.
Because raw material greying thing is by its surperficial hydrophilization, and then rugosityization etc. and obtain surface modification, so can bring into play good charge characteristic rapidly.
Therefore, though the modified graphite thing in the water kind solvent, also adhere securely with tackiness agent, even repeated charge also can contact between the three of modified graphite thing, aqueous adhesive and current collector securely.And then think that tackiness agent is filming and between the modified graphite thing equably, suppressed to hinder the principal element of electroconductibility, ionic conductivity, electrolyte permeability etc.
Below negative material that lithium-ion secondary cell of the present invention is used be described in further detail.
Negative material of the present invention also can add in addition graphite of modified graphite thing of the present invention (the greying thing of the mesophasespherule after the surface modification treatment) (below, be also referred to as " other graphite " sometimes) and use.
And the situation of graphite with other under, when the graphite of other different of combined shaped and/or median size, because charging efficiency raising rapidly is more satisfactory with modified graphite thing of the present invention.
If represent, globular modified graphite thing of the present invention and flakey and/or fibrous other the combination of graphite are arranged with concrete example; Lepidiod modified graphite thing of the present invention and spherical and/or fibrous other the combination etc. of graphite.This is external all to be under the globular situation each other, and modified graphite thing of the present invention about median size 30 μ m and combination of other graphite about median size 10 μ m etc. are for example arranged.
There is no particular limitation for this other graphite, can enumerate the greying thing (raw material greying thing) of the mesophasespherule in the past of the processing of not carrying out applying simultaneously force of compression and shearing force specifically.And then, also can exemplify to the tar that adds the hot coal class, pitch and the intermediate phase sintered carbon (loose density intermediate phase) that obtains coke class (green coke charcoal, the oil-containing coke, pitch coke, needle coke, petroleum coke etc.) finally heat-treating more than 2500 ℃ and greying and the material that obtains.Perhaps can enumerate petroleum-type tar, pitch are heat-treated and greying and the material that obtains.In addition, as other graphite, also can exemplify synthetic graphite, natural graphite etc.The material that the also above-mentioned graphite material that exemplifies of other graphite combines.
In above-mentioned other graphite, preferably use the graphite that coats by the crystallinity carbon material lower than the crystallinity of modified graphite thing of the present invention (the greying thing of the mesophasespherule after this surface modification treatment).
The said here graphite with coating of low-crystalline is meant the graphite that core material is higher relatively than coating material crystallinity.The carbon material of coating material (below, be also referred to as coating material) be that graphite (below, be also referred to as core material) crystallinity than core material is low and than the low carbonaceous of modified graphite thing (the greying thing of the mesophasespherule after this surface modification treatment) crystallinity or the carbon material of graphite matter.It is inner and/or surperficial that coating material can be present in the particle of core material, is preferably the surfaces that are present in core material more than half of coating material.
In the X-ray diffraction of this graphite after coating, can not judge the crystallinity of core material and the crystallinity of coating material separately.So the average lattice plane of the X-ray diffraction of the crystallinity of coating material by independent thermal treatment and when obtaining this coating material is d at interval
002Limit.That is the preferred average lattice plane interval d that, represents this coating material
002More than 0.337nm, more preferably be more than the 0.340nm.This strength ratio (I that Raman analyzes
D/ I
G) be shown generically more than 0.15.
As the manufacture method of aforementioned coating graphite, can the organifying compound adhere to and/or be immersed on the core material, it is being carried out final high-temperature heat treatment in less than 2800 ℃ temperature range more than 900 ℃ and is obtaining aforementioned graphite.Particularly preferably for obtaining aforementioned graphite carrying out final high-temperature heat treatment in less than 2300 ℃ temperature range more than 1150 ℃.Final high-temperature heat treatment temperature be less than the situation more than 900 ℃ or 2800 ℃ under, can not obtain good charging efficiency rapidly.
Core material can be selected from various natural graphites, synthetic graphite, is preferably flaky graphite, blocky graphite, globular graphite etc.Core material preferably has the space of appropriateness.The particle diameter of core material is preferably in the scope of 1～30 μ m.Though the specific area of core material is not mentioned especially, is preferably 0.5m
2More than/the g.The crystallinity of core material is by the average lattice plane interval d of X-ray diffraction
002Represent less than 0.337nm.
As the raw material of coating material, select by thermal treatment the residual organic compound of carbon part.Preferably contain hardly to hinder and discharge and recharge reaction or promote the heavy metal of the decomposition of electrolytic solution, the organic compound of light metal element.Particularly, be preferably thermosetting resin, thermoplastic resin, the mink cell focus of coal class or petroleum-type, tar, pitch etc.Particularly, the organic compound that preferably contains carbonaceous micropartical (micro mist of coal, a QI (QI is the quinoline non-soluble part), carbon block, the micropartical of carbon or graphite etc.).Mix with the graphite of core material after the raw material of these coating materials can being kept its original state or dissolving or being dispersed in the solvent, then, heat-treat.
The total amount of coating material after with respect to the final relatively pyroprocessing of the blending ratio of core material is preferably coating material 0.5～30 quality %, more preferably is 3～20 quality %.When coating material was superfluous, loading capacity reduced.When coating material was very few, initial charge reduced.
The addition of this other graphite is different and different according to the shape of other graphite and modified graphite thing of the present invention or median size etc., the total amount of other graphite and modified graphite thing of the present invention relatively, with about 0.5～90 quality % for well.When making the interpolation upper limit be preferably the 70 quality % left and right sides, can access the more good material of charging efficiency rapidly.
For example, when the median size of modified graphite thing of the present invention is 20～30 μ m,, use the flakey (size of planar portions: 3～15 μ m) natural graphite and/or synthetic graphite of 5～40 quality % as other graphite.
Perhaps, when the median size of modified graphite thing of the present invention is 5～15 μ m,, use the coating graphite (the graphite of coating material) of 20～70 quality % with low-crystalline of median size 15～30 μ m as other graphite.
Though there is no particular limitation to other the blending means of graphite of this modified graphite thing and this, general directly powder is kept dry state and use various mixing machines.
And then if in the scope of not damaging purpose of the present invention, also with other carbon material (containing noncrystal hard graphite etc.), organism, the mixture of metallic compound, coating, sandwich, granulation thing.In addition, also can implement the processing, thermal treatment, oxide treatment etc. of the various chemistry of liquid phase, gas phase, solid phase.
In addition, in the present invention,, wish to adopt relative ionogen to have the stability of chemistry, the organic binder bond of electrochemical stability as the tackiness agent that is used for negative pole mixture paste.For example use the fluorine-type resin of poly-ethylene fluoride, tetrafluoroethylene etc., polyethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubbers etc.Also these can be used with.
In above-mentioned substance, in order to reach purpose of the present invention, bring into play effect to greatest extent, particularly preferably use polyvinyl alcohol (water-soluble), carboxymethyl cellulose (water-soluble), styrene butadiene rubbers tackiness agents such as (water dispersibles).
Tackiness agent preferably uses the amount about whole 0.5～20 quality % that measure of negative pole mixture usually.
Then, also mention the making method of negative pole, come the anticathode material to be further detailed.For example, modified graphite thing of the present invention is adjusted to suitable particle diameter by classification etc., modulate the negative pole mixture by mixing with tackiness agent.This negative pole mixture is dispersed in the solvent, and is after the paste-like, be coated on usually on the single face or two sides of current collector.Then, if make its drying, then negative pole mixture layer evenly and securely is bonded on the current collector, can form negative pole mixture layer.
More particularly, will be for example carboxymethyl cellulose, styrene butadiene rubbers etc. are used as tackiness agent, at any and water with modified graphite thing of the present invention, the solvent of alcohols etc. also becomes after the slurry, can be coated with.Perhaps with tetrafluoroethylene, the fluorine-type resin powder and the Virahol of poly-ethylene fluoride etc., N-Methyl pyrrolidone, the solvent of dimethyl formamide etc. also becomes after the slurry, can be coated with.
Therein, consider that the drying of solvent removes safety, the influence of environment aspect, wishing to adopt with water or aqueous alcohols etc. is solvent, make carboxymethyl cellulose, dissolving such as the tackiness agent of styrene butadiene rubbers etc. and/or disperse and the negative pole mixture paste of the water class that obtains.
Paste can be modulated by using stirrings such as known stirrer, mixing machine, mixing roll, kneader.
Coating thickness when in the present invention, being coated on negative pole mixture paste on the current collector is that 10～200 μ m are more suitable.
In addition, modified graphite thing of the present invention also can mix with the toner dry type of polyethylene, polyvinyl alcohol etc., and in metal die the hot-forming negative pole that forms.In this case, the solvent interdependence of lithium-ion secondary cell disappears certainly.The loading capacity of lithium-ion secondary cell or rapidly efficiency for charge-discharge under the too much situation of tackiness agent, reduce sometimes.In dry type is mixed, need a large amount of tackiness agents in order to obtain sufficient negative pole intensity, so preferably adopt aforesaid wet type (making tackiness agent be dispersed in method in the solvent) method.
After forming negative pole mixture layer, when carrying out the crimping of exert pressure etc., can further increase the bonding strength of negative pole mixture layer and current collector.
There is no particular limitation as the shape of the current collector that is used for negative pole.Can use the paper tinsel shape, or netted etc. the netted current collector of mesh, porous metal etc.As current-collecting member, can enumerate copper, stainless steel, nickel etc.Under the situation of paper tinsel shape, the thickness of current collector is advisable about with 5～20 μ m.
The negative pole that＜lithium-ion secondary cell is used 〉
The invention of the negative pole that the lithium-ion secondary cell that also provides negative material of the present invention to constitute is in this application used.
Negative pole of the present invention obtains by above-mentioned negative material of the present invention is solidified and/or is shaped.Though 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 greying thing and the plasticity height of relative powder, the method that obtains the negative pole of chemistry, electrochemical stability are got final product, without any restriction.
Though modified graphite thing of the present invention is specially adapted to as the negative pole of above-mentioned lithium-ion secondary cell with material and negative pole, also can bring into play its characteristics and purposes beyond the negative material of migrating.In the present invention, and then the lithium-ion secondary cell that uses this negative pole can be provided.
＜lithium-ion secondary cell 〉
Lithium-ion secondary cell is usually with negative pole, and the ionogen of anodal and non-water class is main battery integrant.Anodal and negative pole becomes the carrier of lithium ion respectively.This battery principle is that lithium ion embeds in the negative pole when charging, and lithium ion takes off embedding from negative pole during discharge.
There is no particular limitation except the negative pole that the negative material of use contains modified graphite thing of the present invention constitutes for lithium-ion secondary cell of the present invention.Integrant for other is a standard with the key element of general lithium-ion secondary cell.
As anodal material (positive active material), preferably select to embed/take off the lithium that embedding fully measures and the material that obtains.As such positive electrode active material, can exemplify the compound chalkogenide of lithium and transition metal, the composite oxides of lithium and transition metal are wherein arranged.
The composite oxides of lithium and transition metal (being also referred to as the transition metal oxide that contains lithium) can be the materials that obtains after lithium and the transition metal solid solution more than 2 kinds.Specifically, can be by LiM (1)
1-XM (2)
XO
2(X is the numerical value of the scope of 0≤X≤1 in the formula, M (1), M (2) is made of at least a transition metal) or LiM (1)
2-YM (2)
YO
4(Y is the numerical value of the scope of 0≤Y≤1 in the formula, M (1), M (2) is made of at least a transition metal) expression.
In above-mentioned oxide compound, as the represented transition metal of M, can enumerate Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn etc.
In particular, can enumerate by LiCoO
2Or Li
XNi
YM
1-YO
2(M is the above-mentioned transition metal except Ni, is preferably from Co, and Mn, Cr, Ti, V, Fe, that selects among the Al is at least a, 0.05≤X≤1.10,0.5≤Y≤1.0) represented with composite oxides lithium.
For example, can be initial feed with the oxide compound or the salt of Li, transition metal, these initial feed according to form mixing, and are existed under the atmosphere at oxygen that sintering obtains the above-mentioned transition metal oxide that contains lithium like this in 600 ℃～1000 ℃ temperature range.Initial feed is not limited to oxide compound or salt in addition, also can be synthetic by water oxide compound etc.
In the present invention, positive active material can use above-claimed cpd separately, also can use the above-claimed cpd more than 2 kinds with.For example in positive pole, also can add the carbonate of Quilonum Retard etc.
Form positive pole by such positive electrode material.For example be coated on the two sides of current collector and form the cathode mixture layer by the formed cathode mixture of conductive agent that will be used for giving positive electrode material and tackiness agent and electrode conductivuty.As tackiness agent, can use any of the material that in negative pole, exemplifies.As conductive agent, for example can use the greying thing.
There is no particular limitation for the shape of current collector.Can use netted etc. netted current collector of paper tinsel shape or mesh, porous metal etc.As the material of current collector, can enumerate aluminium, stainless steel, nickel etc.Be advisable with 10～40 μ m as its thickness.
In addition, under the anodal situation, also similarly can be by cathode mixture being dispersed in be in the solvent paste-like with negative pole, be coated on the current collector and drying forms the cathode mixture layer by cathode mixture with this paste-like.Can be after forming the cathode mixture layer, further carry out the crimping of exert pressure etc.Thus, the cathode mixture layer evenly also is bonded on the current collector securely.
Such when anodal more than forming, can suitably use the various additives of known in the past conductive agent or tackiness agent etc.
As being used for ionogen of the present invention, can use the organic class ionogen of solvent and electrolytic salt formation or the polymer ionogen of polymer and electrolytic salt formation etc.As electrolytic salt, can use LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5), LiCl, LiBr, LiCF
3SO
3, LiCH
3SO
3, LiN (CF
3SO
2)
2, LiC (CF
3SO
2)
3, LiN (CF
3CH
2OSO
2)
2, LiN (CF
3CF
2OSO
2)
2, LiN (HCF
2CF
2CH
2OSO
2)
2, LiN ((CF
3)
2CHOSO
2)
2, LiB[C
6H
3(CF
3)
2]
4, LiAlCl
4, LiSiF
6Deng.Particularly, from the viewpoint of oxidative stability, preferably use LiPF
6, LiBF
4
Electrolytic salinity in organic class ionogen is preferably 0.1～5 mol, more preferably is 0.5～3.0 mol.
As organic electrolytelike solvent, can use NSC 11801, propylene carbonate, diethyl carbonate, dimethyl carbonate, 1,1 or 1, the 2-glycol dimethyl ether, 1,2-diethoxyethane, tetrahydrofuran (THF), 2-methyltetrahydrofuran, γ-furanidine ketone, 1,3-two oxa-s penta ring, the 4-methyl isophthalic acid, 3-two oxa-s penta ring, methoxybenzoyl, diethyl etherate, tetramethylene sulfone, methyl sulfolane, acetonitrile, chlorine nitrile, propionitrile, trimethyl borate, methyl orthosilicate, Nitromethane 99Min., dimethyl formamide, N-Methyl pyrrolidone, acetic acid ethyl, former trimethylammonium, oil of mirbane, benzoyl chloride, benzoyl bromide, tetrahydro-thiophene, methyl-sulphoxide, 3-methyl-2-oxazolidone, ethylene glycol, the non-proton organic solvent of methyl-sulfate etc.
Making nonaqueous electrolyte is under the electrolytical situation of polymer, though contain the matrix polymer of gelation by softening agent (nonaqueous electrolytic solution), as this matrix polymer, can be separately or use the fluorine family macromolecule etc. of ether family macromolecule, polymethacrylate, polyacrylic ester, polyvinylidene difluoride (PVDF) or the vinylidene-hexafluoropropylene copolymer etc. of polyoxyethylene or its crosslinked body etc. with.
From the viewpoint of oxidation-reduction stability etc., in these materials, wish to use the fluorine family macromolecule of polyvinylidene difluoride (PVDF) or vinylidene-hexafluoropropylene copolymer etc.
As the electrolytic salt or the solvent that constitute the softening agent that the polymer ionogen contains, can use any of aforementioned substances.Electrolytic salinity in the softening agent electrolytic solution is preferably 0.1～5 mol, more preferably is 0.5～2.0 mol.
There is no particular limitation as the electrolytical making method of such polymer, for example, can enumerate forming macromolecular compound, lithium salts and the solvent of matrix, heating and fused method.And then, can enumerate macromolecular compound, lithium salts and solvent are dissolved in the organic solvent of suitable mixing usefulness after, make the method for the organic solvent evaporation that mixes usefulness.Can enumerate monomer, lithium salts and solvent in addition, and it is shone with ultraviolet ray, electron rays or molecular ray form polymeric method.
In addition, the adding proportion of the solvent in the polymer ionogen is preferably 10～90 quality %, more preferably is 30～80 quality %.When ratio was above-mentioned 10～90 quality %, specific conductivity increased, and the intensity of machinery increases, and was easy to filming.
In lithium-ion secondary cell of the present invention, also can use spacer.
There is no particular limitation as spacer.For example, can enumerate and spin cloth, non-woven fabrics, synthetic resins microporous film etc.Especially to use the synthetic resins microporous film to be advisable.From the aspect of thickness, film toughness, membrane resistance, the polyolefins micro-porous film is more suitable therein.Polyethylene and polypropylene microporous film specifically, or with its compound micro-porous film etc.
In lithium-ion secondary cell of the present invention, because the initial charge height, so also can use the polymer ionogen.
Use the electrolytical lithium-ion secondary cell of polymer to be commonly referred to as integrated battery.Can constitute by the negative pole that contains modified graphite thing of the present invention, positive pole and polymer ionogen.For example by with negative pole, polymer ionogen, anodal sequential cascade, and be housed in and constitute this battery in the battery exterior component.In addition, in addition can also be at negative pole and anodal outside configuration polymer ionogen.Integrated battery modified graphite thing of the present invention being used for negative material can make the polymer ionogen contain propylene carbonate ester.Though in general the relative graphite electrolytic reaction of propylene carbonate ester is strong, modified graphite thing of the present invention relatively decomposition reaction is low.
And then the structure of lithium-ion secondary cell of the present invention is arbitrarily, and there is no particular limitation for its shape, mode.Can from round tube type, square, Coin shape, button-type etc., at random select.In order to obtain more highland hermetic type battery with nonaqueous electrolyte of security, wish to have when overcharging the abnormal conditions that wait to press in can induced cell and rise and the mechanism of cut-out electric current.Under the situation of using the electrolytical integrated battery of polymer, also can make the structure that is configured to be sealing in the laminated film.
Embodiment
Then more specifically describe the present invention by embodiment.The present invention is not limited to these embodiment.In addition, in following embodiment and comparative example, utilize the greying thing to make the button-type secondary cell of the evaluation usefulness of formation shown in Figure 1, estimate thus., actual battery can be that standard is made with the known method based on purport of the present invention.In this evaluation electricity pool, to act on very negative pole, polarity is anodal.
In addition, in following embodiment and comparative example, the physical properties of particle is measured by following mode.
Median size is measured by laser diffraction formula size-grade distribution meter.
Average lattice plane is tried to achieve by X-ray diffraction at interval.
Specific area is the BET specific area of nitrogen adsorption gained.
Hardness is measured by following method.In cylindrical container (internal diameter 20mm), fill 5g greying thing, knock 200 times., from test portion fill iron and steel rounding bar that face top push internal diameter with cylindrical container, carry out compression experiment, represent to detect the load of the flex point (, detecting the point that load reduces) of load with relative value based on the destruction of particle with constant speed thereafter.That is, making the flex point load of the used greying thing of aftermentioned embodiment 1 is 1, and the relative value of the flex point load of each greying thing and hard particles is shown.
The Raman of greying thing analyzes by the Japanese beam split system NR-1800 of society, uses the argon laser of wavelength 514.5nm to carry out.
(1) modulation of negative material
Under 3000 ℃ condition, make the thermal treatment coal-tar pitch and the mesophasespherule that obtains (Kawasaki Steel (strain) system, median size 25 μ m) greying, obtain the greying thing (raw material greying thing) of mesophasespherule.This greying thing is spherical, and average lattice plane is d at interval
002Be 0.3362nm, pure proportion is 2.228 (density 2.228g/cm
3).In addition, specific area is 0.45m
2/ g.The relative value of hardness is 1.
Then, use the treatment unit ((strain) nara machinery is made made: blend together system) of general structure shown in Figure 2, under following condition, this greying thing is applied simultaneously the processing of force of compression and shearing force.
That is, be 40m/ second and treatment time to be to handle under 6 minutes the condition by roll surface speed at rotor, disperse drop into greying thing this device on one side, side by side apply force of compression and shearing force on one side repeatedly.
The greying thing that applies simultaneously after the processing of above-mentioned force of compression and shearing force is spherical, and median size is 24 μ m.Raman analyzes this strength ratio (I of gained
D/ I
G) be 0.47.This average lattice plane is d at interval
002Constant, maintain 0.3362nm.
(2) modulation of negative pole mixture paste
Apply the greying thing after the processing of force of compression and shearing force when using above-mentioned obtaining, modulate the negative pole mixture paste of water kind solvent and organic kind solvent respectively.
The modulation of the negative pole mixture paste of＜water class 〉
With water is solvent, with modified graphite thing 97 quality %, as the carboxymethyl cellulose 1 quality % and the styrene butadiene rubbers 2 quality % mixing of tackiness agent, stirs 5 minutes with 500r pm with homogenizer, modulates the negative pole mixture paste of water class.
The modulation of the negative pole mixture paste of＜organic class 〉
With the N-Methyl pyrrolidone is solvent, with modified graphite thing 90 quality %, as the poly-ethylene fluoride 10 quality % mixing of tackiness agent, stirs 5 minutes with 500rpm with homogenizer, modulates the negative pole mixture paste of organic class.
(3) making 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, by roller press the negative pole mixture that this is coated on the Copper Foil is pressurizeed.By its stamping-out become the circle of diameter 15.5mm, make the negative pole 2 that by negative pole mixture layer constitute with current collector 7b adhesion thereafter.
(4) anodal is made
Lithium metal foil is pressed on the nickel sheet, makes it the circle that integrated and stamping-out becomes diameter 15.5mm, make the positive pole 4 that constitutes by lithium metal foil with the current collector 7a adhesion of nickel sheet.
(5) ionogen
In solvent, make LiPF with the mixed of NSC 11801 33mol%, Methyl ethyl carbonate 67mol%
6Dissolving is so that reach 1mol/dm
3Concentration, modulate nonaqueous electrolytic solution.Making makes nonaqueous electrolytic solution be immersed in spacer 5 in the polypropylene porous plastid.
(6) making of evaluation battery
As estimating battery, make the button-type secondary cell of structure with Fig. 1.
At first, the negative pole on adhering to current collector 7b 2 and adhere to clamping between the positive pole 4 on the current collector 7a and be immersed in spacer 5 in the electrolyte solution and stacked.Thereafter, will adorn cap 1 outward and lump together with outer tinning 3, so that negative electrode collector 7b side is housed in the outer dress cap 1, positive electrode collector 7a side is housed in the outer tinning 3.At this moment, the circumference of adorning cap 1 and outer tinning 3 outside installs insulating washer 6 additional, riveted joint and airtight two circumferences.
For the evaluation battery of making as mentioned above, under 25 ℃ temperature, carry out the following test that discharges and recharges.
(7) discharge and recharge test
＜initial stage discharging efficiency 〉
The constant current charge of carrying out 0.9mA is till loop voltage reaches 0mV.Then, switch to constant-potential charge, continue 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 1.5V.At this moment, try to achieve charging capacity and loading capacity, calculate initial charge by following formula from the 1st round-robin energising amount.
Initial charge (%)=(loading capacity/charging capacity) * 100
In this test, the process that lithium ion embeds in the greying thing is charging in addition, and the process of taking off embedding from the greying thing is discharge.
＜charging efficiency rapidly 〉
Continue above-mentioned test, carry out the high speed charging in the 2nd circulation.
Making current value is 5 times 4.5mA, carries out constant current charge till loop voltage reaches 0mV.Utilize following formula, calculate charging efficiency rapidly from the charging capacity that obtains.
(8) the wetting ability evaluation of negative material
As described below the wetting ability of the negative material that obtains is estimated.Modified graphite thing 15g of the present invention is filled in the cylindrical vessel that the bottom is made of wire cloth and filter paper, knocks 160 times.Thereafter, the bottom of this container is contacted with the water surface, the timeliness of measuring the infiltration capacity of water changes.
The loading capacity (mAh/g) of every 1g modified graphite thing that table 1 expression is measured by aforesaid way and initial charge (%), the value of charging efficiency (%) rapidly.In addition, Fig. 4 represents hydrophilic evaluation result.
With the condition of following such dry oxidation silicon coexistence under carry out (1) operation of embodiment 1, modulate negative material.Condition in addition is identical with embodiment 1.
Promptly, in embodiment 1 (1) operation, except dry oxidation silicon (Japanese ア エ ロ ジ Le (strain) system AEROSIL300 with raw material greying thing 100 mass parts and 0.2 mass parts, median size 7nm, hardness relative value 4.2) in mixing and the input treatment unit, and to make the treatment time be beyond 2 minutes, applies the processing of force of compression and shearing force similarly to Example 1 simultaneously.
Greying thing after this surface modification treatment is spherical, and median size is 23 μ m.Raman analyzes this strength ratio (I of gained
D/ I
G) be 0.57.The average lattice plane of this of X-ray diffraction is d at interval
002Be 0.3362nm.
To this negative material, carry out evaluation similarly to Example 1.Table 1 expression battery behavior, Fig. 4 represents the wetting ability of negative material.
Will be in embodiment (1), when (1) modulation negative material, the device that applies the processing of force of compression and shearing force is simultaneously changed into the treatment unit (the mechanical fusion of ホ ソ カ ワ ミ Network ロ Application (strain) system system) of the general structure shown in Fig. 3 (a)～(b), and under following condition, carry out surface modification treatment, in addition, all the other and embodiment 1 carry out in the same manner.
That is be under the condition in roll surface speed 20m/ second of 5mm, swing roller and 60 minutes treatment times, side by side to apply the processing of force of compression and shearing force repeatedly in the distance of swing roller and internal part, with the greying thing.Greying thing after this surface modification treatment is spherical, and median size is 25 μ m.
Raman analyzes this strength ratio (I of gained
D/ I
G) be 0.45.The average lattice plane of this of X-ray diffraction is d at interval
002Be 0.3362nm.
Then, make negative pole mixture paste, negative pole, lithium-ion secondary cell.
To this negative material, estimate similarly to Example 1.Table 1 expression battery behavior, Fig. 4 represents the wetting ability of negative material.
Make titanium oxide (Japanese ア エ ロ ジ Le (strain) the system P25 of raw material greying thing 100 mass parts and 0.5 mass parts identical with embodiment 3, median size 21nm, hardness relative value 4.6) coexistence and be under 10 minutes the condition, to carry out surface modification treatment similarly to Example 3 in the treatment time.Greying thing after this surface modification treatment is spherical, and median size is 24 μ m.
Raman analyzes this strength ratio (I of gained
D/ I
G) be 0.63.The average lattice plane of this of X-ray diffraction is d at interval
002Be 0.3362nm.
Then, make negative pole mixture paste, negative pole, lithium-ion secondary cell.
To this negative material, carry out evaluation similarly to Example 1.Table 1 expression battery behavior, Fig. 4 represents the wetting ability of negative material.
Shown in the embodiment 1～4 of table 1, confirmed negative material of the present invention is used as the lithium-ion secondary cell of negative pole not only under the situation of the negative pole mixture paste that uses organic class, even under the situation of the negative pole mixture paste that makes the water class, also can keep big loading capacity and high initial charge, and have high charging efficiency rapidly.
Shown in Fig. 4 (embodiment 1～4), negative material of the present invention has increased the infiltration capacity of water by applying the processing of force of compression and shearing force simultaneously in addition.And then, this processing by with the atomic coexistence of hard under carry out, further increased the infiltration capacity of water.In addition, for relatively, pulverize raw material greying thing, and make the material identical with the specific area of modified graphite thing of the present invention.It is carried out same suction test, can not confirm the increase of the infiltration capacity of water.From this thing, investigate the negative material of the present invention hydrophilization to heavens that becomes.
Comparative example 1
Raw material greying thing (Raman's analytical value I with embodiment 1
D/ I
GThan=0.20) do not carry out this surface modification treatment ground and replace the modified graphite thing of embodiment 1 and use.In addition, modulate the negative pole mixture similarly to Example 1, make negative pole and lithium-ion secondary cell.Fig. 4 represents the wetting ability of this raw material greying thing.The result of table 1 expression battery behavior.
As shown in Figure 4, negative material shows wetting ability hardly.
In addition as shown in Figure 1, in the greying thing (raw material greying thing) with the mesophasespherule of the processing that side by side do not apply force of compression and shearing force is used as lithium-ion secondary cell that negative material uses, under the situation of using organic class negative pole mixture paste, though demonstrate and the loading capacity of the equal size of embodiment 1, high initial charge and high charging efficiency rapidly, but under the situation of using the water cathode mixture paste, charging efficiency reduces rapidly.
Comparative example 2
Use ヘ Application シ エ Le stirrer (Mitsui mine (strain) system), at the raw material greying thing and the dry oxidation silicon that stir mix embodiment 2 under the condition that rotation speed is 700rpm and 30 minutes.Modulate negative material similarly to Example 2 with the mixture that obtains.In addition, in this combination treatment, can not apply force of compression and shearing force simultaneously.
After mixing, the Raman of this mixture analyzes this strength ratio (I of gained
D/ I
G) be 0.21.The average lattice plane of this of X-ray diffraction is d at interval
002Be 0.3362nm.In addition, silicon oxide is separated with the greying thing, measure this strength ratio (I that the monomeric Raman of greying thing analyzes gained by air classifier
D/ I
G) with X-ray diffraction should be average lattice plane interval d
002The result be identical analytical value with the mixture that contains dry oxidation silicon.
Except the mixture that uses greying thing that aforesaid way obtains and dry oxidation silicon, all the other modulate negative pole mixture paste similarly to Example 1, and then making negative pole and lithium-ion secondary cell.Table 1 expression battery behavior.
As shown in table 1, even under the condition of coexistence dry oxidation silicon, mix, the lithium-ion secondary cell that uses as negative material with the greying thing of the processing that side by side do not apply force of compression and shearing force is under the situation of using the water cathode mixture paste, and charging efficiency reduces rapidly.
Replace the raw material greying thing of embodiment 4 and use and pulverize behind the mesophasespherule in advance and the greying thing (median size 17 μ m) of the mesophasespherule crushed material that greying obtains under 3000 ℃ condition.Condition in addition, all the other apply the processing of force of compression and shearing force similarly to Example 4 simultaneously.
The greying thing of the mesophasespherule crushed material before this surface modification treatment is that spherical and indefinite shape is mixed the shape that exists.Average lattice plane is d at interval
002Be 0.3362nm, pure proportion is 2.228, and specific area is 0.95m
2/ g.The relative value of hardness is 0.9.
Greying thing after this surface modification treatment also is that spherical and indefinite shape is mixed the shape that exists, and median size does not become 17 μ m., specific area is 3.45m
2/ g, this strength ratio (I that Raman analyzes
D/ I
G) be 0.75.The average lattice plane of this of X-ray diffraction is d at interval
002Be 0.3362nm.
Modulate negative pole mixture paste similarly to Example 4, and then make negative pole and lithium-ion secondary cell.The battery behavior that table 1 expression is estimated similarly to Example 4.
Comparative example 3
In embodiment 5, except not applying simultaneously the processing of force of compression and shearing force, modulate negative material similarly to Example 5, and then make negative pole and lithium-ion secondary cell.The battery behavior that table 1 expression is estimated similarly to Example 5.
As shown in table 1, at this strength ratio (I that analyzes with Raman
D/ I
G) in the lithium-ion secondary cell that uses as negative pole of the greying thing of low comparative example 3, under the situation of using the water cathode mixture paste, charging efficiency reduces rapidly.Relative with it, increasing this strength ratio (I that Raman analyzes by the processing that applies force of compression and shearing force simultaneously
D/ I
G) embodiment 5 in, even under the situation of using the water cathode mixture paste, charging efficiency also significantly improves rapidly.In addition, initial charge also improves.In addition, confirmed in the effect of using charging efficiency rapidly under the situation of organic class negative pole mixture paste and initial charge further to improve.
The modified graphite thing that any method of embodiment 1～4 is made and the mixture of this other greying thing shown in the table 2 are used as the negative pole of lithium-ion secondary cell.Modulate negative pole mixture paste similarly to Example 1, and then make negative pole and lithium-ion secondary cell.Carry out evaluation similarly to Example 1, the result is represented by table 2.
Comparative example 4
With the mixture of the raw material greying thing of embodiment 1 and natural graphite (the エ ス イ-シ-system SNO-10 of society) negative material as lithium-ion secondary cell.Modulate negative pole mixture paste similarly to Example 1, and then make negative pole and lithium-ion secondary cell.Carry out evaluation similarly to Example 1, the result is represented by table 2.
Below, exemplify particularly and contain by crystallinity than the low graphite that carbon material coated of the crystallinity of modified graphite thing of the present invention and the negative material of this modified graphite thing.
Embodiment 12
(1) by the modulation of crystallinity the graphite that carbon material coated lower than the crystallinity of modified graphite thing of the present invention
In autoclave, put into natural graphite (Yueshi China ink (strain) system BF10A, median size 10 μ m, the average lattice plane interval d of 100 mass parts
002Be 0.3356nm, this strength ratio (I that Raman analyzes
D/ I
G) be 0.09) as core material, so the raw material of the carbon material of conduct coating core material, put into the solution that the coal-tar pitch that makes 20 mass parts is dissolved in the tar oil of 100 mass parts, under agitation be heated to 140 ℃.After continuing heating, remove oil in the tar, obtain the graphite that pitch adheres to and/or be immersed in surface and/or inside by underpressure distillation.Then, put it in the crucible of stainless steel the rare gas element that in sintering oven, circulates, sintering under 500 ℃ condition.With pulverizer it pulverized thereafter.And then, under 1300 ℃,, obtain by the crystallinity graphite that carbon material coated lower (below, be also referred to as " coating graphite ") than the crystallinity of modified graphite thing of the present invention to its sintering.
The carbon material that is coating graphite is the material that pitch is carried out final thermal treatment and obtain at 1300 ℃, and crystallinity is lower than the crystallinity of modified graphite thing of the present invention.In order to confirm this point, only coal-tar pitch is put into stainless steel crucibles, the rare gas element that in sintering oven, circulates, sintering under 500 ℃ condition individually.With pulverizer it pulverized thereafter.And then, 1300 ℃ to its sintering, obtain carbon material.The result that the crystallinity of this carbon material is analyzed is this average lattice plane interval d of X-ray diffraction
002Be 0.343nm.The monomeric crystallinity of carbon material of learning such coating graphite is lower than the crystallinity of modified graphite thing of the present invention.In addition, the clad ratio of this carbon material is equivalent to 8 whole quality %.This strength ratio (I that the Raman of this coating graphite analyzes
D/ I
G) be 0.28, median size 13 μ m.
(2) modulation of negative material and negative pole mixture paste
Coating graphite that aforesaid way is obtained and the modified graphite thing made by the method for embodiment 1 are with this modified graphite thing: the mass ratio of this coating graphite=60: 40 and mixing, modulate the negative pole mixture paste of water kind solvent and organic kind solvent similarly to Example 1 respectively.
Use this negative material, make negative pole and lithium-ion secondary cell similarly to Example 1.The characteristic of the lithium-ion secondary cell that obtains is also carried out similarly to Example 1 evaluation.In addition, also redeterminate following charging efficiency rapidly, the result concludes expression by table 3.
＜sudden discharge efficient 〉
The continuation initial stage discharges and recharges, and carries out high rate discharge in the 2nd circulation.After charging similarly for the first time, making current value is 20 times 18mA, carries out the constant current discharge till loop voltage reaches 1.5mV.Utilize following formula, calculate sudden discharge efficient from the loading capacity that obtains.
Embodiment 13
Use the mesophasespherule (Kawasaki Steel (strain) system) of the median size 25 μ m that pulverizer uses embodiment 1 to be crushed to after the median size 14 μ m, under 3000 ℃ condition, its greying is obtained raw material greying thing.Under the condition identical,, obtain the modified graphite thing to its processing that applies force of compression and shearing force simultaneously with embodiment 1.The modified graphite thing median size that obtains is 13 μ m, and Raman analyzes this strength ratio (I of gained
D/ I
G) be 0.83.The modified graphite thing that this modified graphite thing is replaced the negative material that is used as embodiment 12 uses.Under other condition situation similarly to Example 12, make negative material, negative pole mixture paste, negative pole and lithium-ion secondary cell.The characteristic of the lithium-ion secondary cell that obtains is carried out similarly to Example 12 evaluation.The result is represented by table 3.
Comparative example 5
The raw material greying thing that embodiment 1 is used replaces as the modified graphite thing of the negative material of embodiment 12 and uses.Under other condition situation similarly to Example 12, make negative material, negative pole mixture paste, negative pole and lithium-ion secondary cell.The characteristic of the lithium-ion secondary cell that obtains is carried out similarly to Example 12 evaluation.The result is represented by table 3.
Shown in the comparative example 5 of table 3, replace negative material of the present invention (modified graphite thing) and use the good characteristic that is had under the negative pole mixture paste situation of lithium-ion secondary cell with respect to the organic class of use of unmodified raw material graphite and coating graphite, when making the negative pole mixture paste of water class, loading capacity, charging efficiency and the reduction of sudden discharge efficient rapidly.
Comparative example 6
In embodiment 12, do not use this modified graphite thing and use this coating graphite separately.Under other condition situation similarly to Example 12, make negative material, negative pole mixture paste, negative pole and lithium-ion secondary cell.The characteristic of the lithium-ion secondary cell that obtains is carried out similarly to Example 12 evaluation.The result is represented by table 3.
Shown in the comparative example 6 of table 3, the lithium-ion secondary cell that does not use negative material of the present invention (modified graphite thing) and use coating graphite separately is when making the negative pole mixture paste of water class, although have high loading capacity and high initial charge, charging efficiency and sudden discharge efficient reduce rapidly.Its reason is: because this coating material has used lepidiod natural graphite as core material, and this coating graphite orientation in the negative pole, nonaqueous electrolyte becomes incomplete with contacting of coating graphite.
Shown in the embodiment 12～13 of table 3, confirmed to use the lithium-ion secondary cell of negative material of the present invention (mixture of modified graphite thing and coating graphite) not only under the situation of the negative pole mixture paste that uses organic class, even under the situation of the negative pole mixture paste that makes the water class, also can when keeping big loading capacity and high initial charge, also have high charging efficiency rapidly.Particularly, when mixing the coating graphite that the carbon material by low-crystalline coats, when can confirm to have the loading capacity of further raising, keep high charging efficiency rapidly, sudden discharge efficient, initial charge.As negative material, the modified graphite thing of the application of the invention and the mixture of coating graphite have solved the low charging efficiency rapidly under this coating graphite situation of independent use (comparative example 6) and the problem of low sudden discharge efficient.
Table 2
Table 3
The possibility of industrial application
The new modified graphite compound that obtains by surface modification treatment of the present invention is high crystallization Property has been improved the surface characteristic that outmost surface has turbulent flow, wetability etc. This modified graphite compound Suitable negative pole and negative material as lithium rechargeable battery. Particularly, even replace organic Class intermixture paste and when making negative pole with the water cathode mixture paste, also accessing Keep big discharge capacity and high initial charge/discharge efficiency and have in the past do not reach high The lithium rechargeable battery of charge efficiency rapidly. Thus, except environment aspect, secure context Outside the requirement, can also satisfy the requirement to the high-energy-density of battery in recent years. Advance one Step extends, and can also miniaturization and the high performance that carry machine be contributed.
Claims (9)
1. the greying thing of a mesophasespherule is characterized in that: the average lattice plane interval d of X-ray diffraction
002Less than 0.337nm, and in the raman spectrum of the argon laser that uses wavelength 514.5nm, be present in 1350cm
-1～1370cm
-1The peak strength I in field
DBe present in 1570cm relatively
-1～1630cm
-1The peak strength I in field
GRatio I
D/ I
GFor surpassing 0.4 to below 2, be embedded with median size little and hardness higher hard particles of median size than this greying thing on the surface of described greying thing, make it integrated, this hard particles is select from the cohort that metal, metal oxide, metal nitride, metal boride and metallic carbide constitute at least a.
2. the greying thing of mesophasespherule as claimed in claim 1 is characterized in that: the median size that volume converts is 3～50 μ m, and specific area is 1～20m
2/ g.
3. the greying thing of mesophasespherule as claimed in claim 1 is characterized in that: described micropartical is select from the cohort that silicon oxide, aluminum oxide and titanium oxide constitute at least a.
4. negative material that lithium-ion secondary cell is used contains the greying thing of the described mesophasespherule of claim 1.
5. negative material as claimed in claim 4 is characterized in that: the greying thing graphite in addition that also contains the described mesophasespherule of claim 1.
6. the negative pole that lithium-ion secondary cell is used is characterized in that: be made of the described negative material of claim 5.
7. a lithium-ion secondary cell is characterized in that: have the described negative pole of claim 6.
8. the manufacture method of the greying thing of the described mesophasespherule of claim 1, it is characterized in that: with the hardness height of the greying thing of this mesophasespherule of hardness ratio and median size than the little atomic concurrent conditions of the median size of the greying thing of this mesophasespherule under, the mechanochemistry that the greying thing of this mesophasespherule is side by side applied force of compression and shearing force is handled so that the reduction rate of the median size of this mesophasespherule is below 20%.
9. manufacture method as claimed in claim 8 is characterized in that: described micropartical is select from the cohort that silicon oxide, aluminum oxide and titanium oxide constitute at least a.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP88798/2002 | 2002-03-27 | ||
| JP2002088798A JP4672955B2 (en) | 2001-08-10 | 2002-03-27 | Negative electrode material for lithium ion secondary battery and method for producing the same |
| JP2002297734A JP4672958B2 (en) | 2002-10-10 | 2002-10-10 | Graphite particles, lithium ion secondary battery, negative electrode material therefor and negative electrode |
| JP297734/2002 | 2002-10-10 |
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| Publication Number | Publication Date |
|---|---|
| CN1514805A CN1514805A (en) | 2004-07-21 |
| CN100564253C true CN100564253C (en) | 2009-12-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038003333A Expired - Lifetime CN100564253C (en) | 2002-03-27 | 2003-02-07 | The greying thing of mesophasespherule, the negative material that uses it, negative pole and lithium-ion secondary cell |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100575971B1 (en) |
| CN (1) | CN100564253C (en) |
| TW (1) | TWI223465B (en) |
| WO (1) | WO2003080508A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477476A (en) * | 2011-03-29 | 2013-12-25 | 三菱化学株式会社 | Negative electrode carbon material for non-aqueous secondary battery, negative electrode, and non-aqueous secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100805104B1 (en) * | 2005-08-31 | 2008-02-21 | 삼성에스디아이 주식회사 | Carbonaceous material having high surface area and conductivity and method of preparing same |
| KR100719716B1 (en) * | 2005-09-27 | 2007-05-17 | 삼성에스디아이 주식회사 | Negative electrode for lithium rechargeable battery and lithium rechargeable battery comprising the same |
| JP5042854B2 (en) * | 2005-12-14 | 2012-10-03 | 日本コークス工業株式会社 | Graphite particles, carbon-graphite composite particles, and methods for producing them |
| EP2081243B1 (en) * | 2006-11-10 | 2012-08-08 | Tokai Carbon Co., Ltd. | Negative electrode material for lithium ion secondary battery and method for producing the same |
| JP5196149B2 (en) * | 2008-02-07 | 2013-05-15 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing the same, lithium ion secondary battery and electrochemical capacitor |
| JP5207006B2 (en) * | 2011-10-04 | 2013-06-12 | 戸田工業株式会社 | Spherical carbon material and method for producing spherical carbon material |
| JP5917361B2 (en) * | 2011-12-16 | 2016-05-11 | Ｊｆｅケミカル株式会社 | Method for producing amorphous carbon particles, amorphous carbon particles, negative electrode material for lithium ion secondary battery, and lithium ion secondary battery |
| CN103855397B (en) * | 2012-12-05 | 2018-07-20 | 宁波杉杉新材料科技有限公司 | The preprocess method and products obtained therefrom of a kind of natural graphite material and application |
| CN103482606B (en) * | 2013-09-23 | 2015-06-17 | 大连宏光锂业股份有限公司 | Production method for intermediate phase carbon anode material |
| JP5838245B2 (en) * | 2014-07-22 | 2016-01-06 | 日本ケミコン株式会社 | Method for producing carbon having metal compound nanoparticles dispersed and supported |
| KR102461344B1 (en) | 2015-11-10 | 2022-10-28 | 삼성에스디아이 주식회사 | Negative electrode for a rechargeable lithium battery and rechargeable lithium battery comprising same |
| CN114883558A (en) * | 2016-11-14 | 2022-08-09 | 昭和电工材料株式会社 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN107482203B (en) * | 2017-08-21 | 2020-12-18 | 北方奥钛纳米技术有限公司 | Coating modification method of graphite negative electrode material, graphite negative electrode material and application |
| KR102527750B1 (en) * | 2019-09-17 | 2023-04-28 | 제이에프이 케미칼 가부시키가이샤 | Manufacturing method of graphite material |
| CN113066977B (en) * | 2021-03-18 | 2022-09-23 | 宁德新能源科技有限公司 | Anode material, and electrochemical device and electronic device including same |
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| JP3082557B2 (en) * | 1994-02-10 | 2000-08-28 | 松下電器産業株式会社 | Manufacturing method of non-aqueous electrolyte secondary battery |
| JP3593140B2 (en) * | 1994-03-31 | 2004-11-24 | Ｊｆｅケミカル株式会社 | Method for producing carbon material for secondary battery negative electrode |
| JPH10255800A (en) * | 1997-03-07 | 1998-09-25 | Mitsui Kozan Kasei Kk | Negative electrode material for lithium secondary battery |
| JP2000012034A (en) * | 1998-06-17 | 2000-01-14 | Petoca Ltd | Graphite material for lithium secondary battery and its manufacture |
| EP1134827A3 (en) * | 2000-03-16 | 2007-06-13 | Sony Corporation | Non-aqueous electrolyte secondary battery and method of preparing carbon-based material for negative electrode |
| JP4421750B2 (en) * | 2000-08-16 | 2010-02-24 | Ｊｆｅケミカル株式会社 | Carbon material manufacturing method and lithium ion secondary battery |
-
2003
- 2003-02-07 WO PCT/JP2003/001297 patent/WO2003080508A1/en active Application Filing
- 2003-02-07 CN CNB038003333A patent/CN100564253C/en not_active Expired - Lifetime
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477476A (en) * | 2011-03-29 | 2013-12-25 | 三菱化学株式会社 | Negative electrode carbon material for non-aqueous secondary battery, negative electrode, and non-aqueous secondary battery |
| CN103477476B (en) * | 2011-03-29 | 2017-09-08 | 三菱化学株式会社 | Negative electrode for nonaqueous secondary battery carbon material, negative pole and non-aqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040007548A (en) | 2004-01-24 |
| TW200403879A (en) | 2004-03-01 |
| TWI223465B (en) | 2004-11-01 |
| KR100575971B1 (en) | 2006-05-02 |
| CN1514805A (en) | 2004-07-21 |
| WO2003080508A1 (en) | 2003-10-02 |
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