CN100527484C - Anode active material hybridizing carbon nano fibers for lithium secondary battery - Google Patents
Anode active material hybridizing carbon nano fibers for lithium secondary battery Download PDFInfo
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- CN100527484C CN100527484C CNB2007101363290A CN200710136329A CN100527484C CN 100527484 C CN100527484 C CN 100527484C CN B2007101363290 A CNB2007101363290 A CN B2007101363290A CN 200710136329 A CN200710136329 A CN 200710136329A CN 100527484 C CN100527484 C CN 100527484C
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Abstract
The present invention is to provide anode active material hybridized with carbon nano fibers for lithium secondary battery prepared by following steps comprising, i) dispersing the nano size metal catalyst to the surface of anode material selected from graphite, amorphous silicon or the complex of graphite and amorphous silicon; and ii) growing the carbon nano fiber by chemical vapor deposition method, wherein carbon nano fibers are grown in a vine form and surround the surface of anode active material.
Description
Background of invention
Invention field
The manufacture method that the present invention relates to be used for the anode active material hybridizing carbon nano fibers of lithium secondary battery and be used to prepare the secondary lithium batteries anode.
Description of the Prior Art
In 21 century,, introduced the new model of the information technology that can carry out multimedia interaction communication, as notebook computer, mobile phone and DMB phone according to the semi-conductive development of giving the portable telecommunication apparatus miniaturization.According to the demand of multi-function electronic device, developed high power capacity with high-tension secondary cell and developed relevant electrode material.Since the nineties in 20th century early stage Sony developed its first based on the lithium rechargeable battery of graphite and since putting on market, the energy density of secondary cell and capacity increase rapidly.Yet, still develop than itself having the more secondary cell of high power capacity, higher charge/discharge capacity and more systemic circulation stability seeking.Because the capacity of battery depends on the charge/discharge performance of anode material, so the improvement of anode material has become the main bottleneck of development secondary cell.
In order to improve the chemical property of secondary cell medium-carbon graphite anode material, carried out the research of the surface reformation of various active material of positive electrode, as inorganic coating, crystal carbon coating, pyrocarbon coating, carbon nano-fiber dispersion or carbon nano-tube dispersion.These class methods are avoided going out the crystal structure that destroys anode material in the process in the embedding/embedding of the lithium ion of lithium secondary battery.On the other hand, in order to improve the charge-discharge performance of lithium secondary battery, developed the native graphite anode material that is coated with crystal carbon.
Disclose many technology and improved the charge-discharge performance that adopts the anode material of graphite in the lithium secondary battery.
People such as Iresha R.W Kottegoda disclose the native graphite anode material of reforming in oxidized zirconium surface (Electrochem.Solid-state lett.Vol.5, Issue 12 pp A273-A278 (2002)).Tasutomu Takamura also discloses the celion active material of positive electrode that is coated with conductive carbon so that improve chemical property, as high cyclical stability and high efficiency charge/discharge performance (Journal ofPower Source 90 pp 45-51 (2000)).Further, Korean Patent No.529069 " active material of positive electrode and its preparation method that are used for lithium secondary battery " discloses the crystal active material of positive electrode that is coated with amorphous carbon layer.Further, Korean Patent NO.477970 " active material of positive electrode and its preparation method that are used for lithium secondary battery " discloses a kind of method for preparing the active material of positive electrode compound, wherein the surface-coated of crystalline graphite particle has fine particle, then the heat treatment resulting granules.On the other hand, Korean Patent discloses NO.2005-99697 " active material of positive electrode and the lithium secondary battery that contains described anode that are used for lithium secondary battery " in early days and Korean Patent discloses NO.2005-100505 " active material of positive electrode and the lithium secondary battery that are used for lithium secondary battery " in early days, and the powder and the amorphous carbon particle that disclose the tabular graphite that ground are respectively assembled subsequently with the preparation active material of positive electrode.Yet being coated to the active material of positive electrode that tabular or fibrous active material prepares by amorphous carbon can not sell on market, because the irreversible capacity of battery correspondingly increases along with the increase of reversible capacity and surface area.
On the other hand, metal has been used as the material of reformation carbon anode material.Tasutomu Takamura etc. discloses and according to the METAL HEATING PROCESS precipitation method Ag, Cu, Bi, In or Zn metal laminate has been coated to the graphite anode material surface and improves charge/discharge performance (Journal of Power Source 81-82, pp368-372 (1999)).U.S. Patent No. 6797434 discloses and has comprised carbonaceous material and amorphous metal compound, as the active material of positive electrode of the mixture of tin oxide.In addition, disclose No.2004-100058 in early days in Korean Patent and " be used for active anode material of lithium secondary battery and preparation method thereof ", its nanocarbon/metal compound that discloses by adopting material with carbon element and metal precursor prepares active material of positive electrode.In addition, Korean Patent No.536247 " lithium secondary battery that is used for the active material of positive electrode of lithium secondary battery and contains described anode " discloses according to heat treatment method and formed inorganic oxide or hydroxide layer on the surface of graphitic carbon material, prepares active material of positive electrode as Al, Ag, B, Zn or Zr.
Yet in order to utilize the metal carbon anode surface of reforming according to said method, before coating, the surface-coated material should evenly disperse.In addition, in order to obtain the even metal oxide skin(coating), need a large amount of metal precursor.On the other hand, the tabular graphite of aspherical particle is difficult to evenly disperse, and they need extra heat treatment to have the layer of uniform thickness with preparation.
As for the active material of positive electrode of high power capacity, the metallic silicon anode material is known, and it is compared with the graphite anode material, has shown at least 10 times high-energy-density.Yet, in the process of charging and discharge, because the alloy of lithium and silicon, as Li
1.71-4.4The volumetric expansion that Si causes has caused bigger 4 times than the volume of silicon itself.Therefore, this expansion has caused the decomposition of silicon electrode structure, and it has caused discharge capacity to reduce rapidly, even less than 20% of initial discharge capacity.Finally, the silicon materials effect of active material of positive electrode that will not recur.In order to overcome above-mentioned defective, carried out the stability that big quantity research improves silicon electrode structure.Some research examples comprise that the silicon and the use of employing nano particle size particle contain transition metal, as the alloy of nickel and copper, the oxygen content that adopts carbon/silicon compound, change silicon and/or development electrode adhesive.Yet, because capacity attenuation that charge and discharge cycles repeatedly causes and the high power capacity problem of keeping the 1000mAh/g at least of silicon anode material are not still solved.
Carbon nanomaterial is developed as carbon electrode material as gas-phase growth of carbon fibre (VGCF), carbon nano-tube, carbon nano-fiber or fullerene.In addition, PCT patent brochure WO 03/67699A2 discloses by the spheroidal graphite materials with carbonaceous mesophase spherules; The carbon nano-fiber (VGCF) of 200nm diameter and 65-70nm nuclear internal diameter and ionic conductive polymer adhesive are mixed and are prepared the active material of positive electrode that is used for lithium battery.In addition, Japanese Patent Laid Open Publication No.2004-186067 discloses by the carbon nano-fiber of average grain diameter 10-500nm and the mixture of carbon bonding particle and has prepared the active material of positive electrode that is used for lithium battery.In addition, Japanese Patent Laid Open Publication No.2004-227988 discloses graphitic carbon nanofiber has been added in the graphite anode active material as conductive agent, and it is compared with traditional conductive agent, has shown good charge/discharge capacity.In addition, Japanese Patent Laid Open Publication No.2004-303613 discloses carbon nano-tube or the carbon nano-fiber active material of positive electrode as lithium secondary battery, and it suppresses the decomposition of PC electrode.
Because carbon nanomaterial has big surface area as carbon nano-tube or carbon nano-fiber, so can there be defective in this material because of envelope-bulk to weight ratio big in the electrode.Therefore, according to the increase of carbon nanomaterial amount, current-collector very difficult owing to nano material and in the electrode combines the machinability that reduces battery.In addition, carbon nanomaterial compare with graphite expensive be to be used for business-like another some restriction.
The problem that exists when using carbon nano-tube or carbon nano-fiber as active material of positive electrode in order to overcome, Korean Patent No.566028 " carbon nanomaterial and preparation method thereof that is used for the active material of positive electrode of lithium secondary battery " discloses carbon nano-fiber and metallic particles compound as active material of positive electrode, metal such as Ag, Sn, Mg, Pd or Zn.Yet the simple composite of carbon nanomaterial and anode material can be brought other problems, because carbon nano-fiber is with the large volume density of carbon nano-fiber in the growth of irregular direction and the electrode.Like this, carbon nano-fiber plays the main effect of active material of positive electrode, and it causes the low cycle performance of carbon nano-fiber itself.In order to overcome the low cycle performance of carbon nano-fiber, prepare active material of positive electrode by introducing heat treatment method at least 2000 ℃.Even improve conductivity between active material of positive electrode by adding conductive agent, but in charge and discharge cycles since the STRUCTURE DECOMPOSITION that main volumetric expansion causes still fail to avoid.
U.S. Patent No. 6440610 B1 " are used for active material of positive electrode of lithium secondary battery and preparation method thereof " and disclose a kind of method that is used in the surface of active material of positive electrode growth vapour deposition carbon nano-fiber or carbon nano-tube.Disclose by following step and prepared gas-phase growth of carbon fibre, comprised i) after mixing, the metal nitrate particle is adsorbed onto anode material and slaine is dissolved in the aqueous solution by spray drying process; Ii) at high temperature heat resulting material and be used for oxidation and reduction step, iii) by vapour deposition process growth carbon nano-fiber.Yet, there is following defective i in this preparation method) in the process of preparation catalyst, cause metal nitrate agglomeration of particles with strong hydrophobic performance, ii) because described gathering, carbon nano-fiber is grown brokenly, iii) at high temperature, and in continuous carbonization, oxidation and the reduction process, sintering metal catalyst granules, and the thermal conversion that iv) causes graphite granule.
On the other hand, if carbon nanomaterial from the Surface Vertical or the oblique growth of carbon anode active material, Sheng Chang carbon nano-fiber or carbon nano-tube will be twined so, this causes the increase of bulk density.Therefore, the density of active material of positive electrode diminishes with respect to the cumulative volume of electrode.In addition, the growth of carbon nanomaterial in graphite granule also comprises the gathering of graphite granule, and this causes being difficult to optimize the particle control of active material of positive electrode in the preparation electrode.
In addition, attempted the alloy of silicon and other rare metals so that improve the charge/discharge performance of silicon.Yet the silicon alloy with high charge/discharge performance does not also make.
When known crystal structure when the metal active material becomes unbodied form, in the volumetric expansion process that the embedding/embedding according to lithium ion goes out, can keep the structural stability of metal active material.Recently, reported to comprise and at high temperature melt the crystalline metal and the rapid melt spinning method of the step of crystals cooled metal at short notice that it is amorphous so that crystalline silicon is changed into as a kind of useful method.Yet the industrial applicability of the method also has some restrictions.
On the other hand, the active material of positive electrode of being made up of graphite or metal in the lithium secondary battery goes out to tend in the process expand or shrink in the embedding/embedding of lithium ion, and this stems from the decomposition of crystal structure.Finally, because the decay of circulation volume can not re-use this anode material.
Summary of the invention
The purpose of this invention is to provide a kind of lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization of being used for by the preparation of following step, step comprises i) metallic catalyst of nano particle size is dispersed in the surface of the anode material of the compound that is selected from graphite, amorphous silicon and/or graphite and amorphous silicon; And ii) by chemical vapour deposition technique growth carbon nano-fiber, wherein carbon nano-fiber with the form growth of rattan and be centered around the active material of positive electrode surface around.
In addition, prepare described amorphous silicon by under inert atmosphere, utilizing mechanical friction can carry out preliminary treatment.And, be the compound that the amorphous silicon of the graphite of 1-50wt% and 50-99wt% prepares graphite and amorphous silicon by weight ratio.
In addition, the structure of carbon nano-fiber is plate object structure or the herringbone structure with anode active material hybridizing.
On the other hand, the increment of carbon nano-fiber is 1-200 weight portions with respect to the active material of positive electrode of 100 weight portions, and the diameter of carbon nano-fiber is 5-300nm, and draw ratio is 10-10000, and the thickness of the carbon nano-fiber on the active material of positive electrode is 5-1000nm.The preferred growth amount of carbon nano-fiber is 5-100 weight portions with respect to the active material of positive electrode of 100 weight portions, the preferred diameter of carbon nano-fiber is 5-100nm, preferred draw ratio is 10-1000, and the preferred thickness of the carbon nano-fiber on the active material of positive electrode is 10-500nm.The further preferred increment of carbon nano-fiber is 10-80 weight portions with respect to the active material of positive electrode of 100 weight portions, the further preferred diameter of carbon nano-fiber is 5-50nm, further preferred draw ratio is 10-100, and the further preferred thickness of the carbon nano-fiber on the active material of positive electrode is 15-200nm.
On the other hand, in the presence of catalyst, utilize the carbon source that is selected from carbon monoxide, methane, acetylene or ethene to prepare described carbon nano-fiber by chemical vapour deposition technique.In addition, described metallic catalyst comprises and is selected from least a of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In, it is the form of alkoxide, oxide, chloride, nitrate or carbonate, and the catalyst that adopts sol-gal process, the precipitation method, hydrothermal method, spraying heating, spray drying process or Prepared by Ball Milling carried catalyst form.
More particularly, described carbon nano-fiber prepares by following step, comprise i) under 300-650 ℃, utilize mixed gas flow (3-5L/min:1L/min) heating of helium and hydrogen to be selected from the active material of positive electrode particle of the compound of graphite, amorphous silicon and/or graphite and amorphous silicon; Ii) under 400-800 ℃,, in the presence of the carbon monoxide-olefin polymeric that makes by nickel nitrate and carbonic hydroammonium, utilize the carbon source that is selected from carbon monoxide, methane, acetylene or ethene, by vapour deposition process growth carbon nano-fiber with the mixed gas flow of helium and hydrogen.
Other purposes of the present invention provide the lithium secondary battery that is made by active material of positive electrode of the present invention.
The accompanying drawing summary
Fig. 1 has shown the variation of active material of positive electrode structure, and carbon nanofibers grow and with graphite active board hydridization.
Fig. 2 A has shown the method flow that is used for preparation carbon nano-fiber on active material of positive electrode in an embodiment of the present invention.Fig. 2 B has shown the method flow that is used for preparation carbon nano-fiber on active material of positive electrode in comparing embodiment 1 of the present invention and 2.Fig. 2 C has shown the method that is used for preparing carbon nano-fiber in comparing embodiment 4 of the present invention (U.S. Patent No. 6440610 B1) on active material of positive electrode.
Fig. 3 is the image of the field emission scanning electron microscope (FE-SEM) of the graphite surface among the preparation embodiment 1, and wherein carbon nano-fiber is by hydridization.Fig. 3 A is image (x1000 doubly), and Fig. 3 B is image (x5000 doubly), and Fig. 3 C is image (x100000 doubly).
Fig. 4 is the high-definition picture of the transmission electron microscope (TEM) of the graphite surface of preparation among the embodiment 1, wherein carbon nano-fiber with the form of rattan by hydridization.Fig. 4 A and Fig. 4 B have shown the herringbone structure that carbon nano-fiber on the graphite surface and Fig. 4 C have shown carbon nano-fiber.
Fig. 5 is the image of the field emission scanning electron microscope (FE-SEM) of the silicon face among the preparation embodiment 4, and wherein carbon nano-fiber is by hydridization.Fig. 5 A is image (x1000 doubly), and Fig. 5 B is image (x10000 doubly), and Fig. 5 C is image (x50000 doubly).
Fig. 6 is the image of the field emission scanning electron microscope (FE-SEM) of the silicon face among the comparative preparation embodiment 2, and wherein carbon nano-fiber is not by hydridization.Fig. 6 A is that image (x2000 doubly) and Fig. 6 B are image (x50000 doubly).
Fig. 7 is according to time of planetary milled processed progress, is indicated in the peak of the x-ray fluorescence diffraction (XRD) of the Si powder that is used for preparing embodiment 3 and 4.It has shown the degree of crystallinity that has reduced silicon according to planetary milled processed.
Fig. 8 is according to time of planetary milled processed progress, is indicated in the peak of x-ray fluorescence diffraction (XRD) of the compound of the silicon that is used for preparing embodiment 5-9 and powdered graphite.It has shown the degree of crystallinity that has reduced silicon according to planetary milled processed.The density on the plane of silicon and graphite composite (III) reduces.
Fig. 9 A is after planetary milled processed, is used for preparing the diffraction pattern of transmission electron microscope (TEM) of the Si powder of embodiment 4.Fig. 9 B is the high resolution graphics of the transmission electron microscope (TEM) of described Si powder, and the surface of described Si powder is that part is unbodied.
Figure 10 is after planetary milled processed, is used for preparing the diffraction pattern of transmission electron microscope (TEM) of the Si powder of embodiment 9, and it has shown that crystalline silicon becomes amorphous silicon.
Detailed Description Of The Invention
The present invention relates to be selected from the active material of positive electrode of the compound of graphite, amorphous silicon and graphite and amorphous silicon, carbon nano-fiber is in this material growth and hydridization, with and preparation method thereof, wherein carbon nano-fiber with the growth of the form of rattan and be centered around the active material of positive electrode surface around.
The invention provides a kind of for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, wherein carbon nano-fiber with the form growth of rattan and be centered around the compound that is selected from graphite, amorphous silicon and/or graphite and amorphous silicon anode material the surface around. In the present invention, the metallic catalyst for the growth carbon nano-fiber makes by the coprecipitation at the aqueous solution. And for the form growth carbon nano-fiber with rattan, described metallic catalyst has been evenly dispersed in the surface of active material of positive electrode, then the mixture of drying and heating of metal catalyst and active material of positive electrode.
By chemical vapour deposition technique, make the carbon nano-fiber with following structure. The diameter of the carbon nano-fiber that obtains is 5-300nm, and draw ratio is 10-10000, and the form of carbon nano-fiber is plate object or herringbone structure, and the thickness of the carbon nano-fiber on covering active material of positive electrode surface is 5-1000nm. Because the carbon nano-fiber of growth centers on active material of positive electrode with the form of rattan, so can go out in the embedding/embedding of lithium ion the volumetric expansion that prevents active material of positive electrode in the process. The preferred 5-50nm of the diameter of the carbon nano-fiber that obtains, preferred draw ratio is 10-100, and the thickness 15-200nm preferably that covers the carbon nano-fiber on active material of positive electrode surface.
On the other hand, if carbon nano tube growth on the surface of active material of positive electrode, so with according to the circulation that repeats, use the situation of carbon nano-fiber and compare, can improve electrical conductivity, reduce the charge/discharge performance. Considered that the volumetric expansion of active material of positive electrode can not be grown in the CNT control on active material of positive electrode surface.
Recently, graphite has been substituted the active material of positive electrode that pure lithium metal is used as lithium secondary battery. Various material with carbon elements, as carbon nano-fiber, coke, mesocarbon, Delanium and/native graphite has been used as active material of positive electrode. And, because crystalline graphite has the wider voltage of scope than coke or amorphous carbon, and commercially as active material of positive electrode.
Because the degree of crystallinity that graphite is higher is convenient to the embedding/embedding of lithium ion and is gone out and shown good cycle performance, so have Delanium greater than 90% degree of crystallinity by being produced as active material of positive electrode in heat treatment more than 2000 ℃. On the other hand, owing to there is restriction in its native graphite that is easy to obtain at the high deposition of occurring in nature because it has than Delanium when high irreversible capacity and low cycle performance are applied to battery. Therefore, native graphite needs further to process to be used for commercial batteries, such as the surface reforming of native graphite, by process of lapping, mixing and compound thin crystal material with carbon element, add various additives and adopt acid solution to come oxidation processes part graphite surface. , in the situation on the surface of native graphite, make battery repeat charge/discharge and increased electrical conductivity, and reduced cycle performance at carbon nano tube growth. We think that this CNT that is grown in the active material of positive electrode surface can not prevent the volumetric expansion of active material of positive electrode.
Catalyst for the preparation of carbon nano-fiber is known. For example, adopted transition metal, such as Fe, Co and Ni (Catal.Rev.-Sci.Eng., 42 (4) pp481-510 (2000)). In the present invention, used at least a metallic catalyst that is selected among Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and/or the In. The form of catalyst can be alkoxide, oxide, chloride, nitrate or carbonate.
For metal catalyst particles being supported on the surface of active material of positive electrode, can adopt gel-sol method, the precipitation method, hydrothermal method, spraying heating, spray drying process and/or ball-milling method.And the active material of positive electrode that contains metallic particles can be produced by introducing further oxidation or reduction process.Yet the preferred precipitation method also do not require further oxidation or reduction process.
Superficial growth carbon nano-fiber at active material of positive electrode can adopt carbon source, is used for gas-phase reaction under the high temperature as carbon monoxide, methane, acetylene and/or ethene.Preferred carbon source can be carbon monoxide or the ethene in the 400-800 ℃ of scope.The increment of carbon nano-fiber can be the 5-200wt% with respect to the active material of positive electrode amount.The preferred growth amount of carbon nano-fiber can be the 5-100wt% with respect to the active material of positive electrode amount.
Fig. 1 has set forth according to the present invention and the structure of the graphite of carbon nano-fiber hydridization.Be used as the active material of positive electrode of lithium secondary battery with native graphite that piles up and carbon nano-fiber hydridization.As shown in Figure 1, carbon nano-fiber of the present invention centers on the native graphite that piles up with the form of rattan.Therefore, the surface of native graphite and carbon nano-fiber hydridization, wherein native graphite plays the effect of the backing material of carbon nano-fiber.Disclosure of the present invention is different from U.S. Patent No. 6440610 B1 " negative active core-shell material and the manufacture method thereof that are used for lithium secondary battery ", and wherein carbon nanomaterial is from the Surface Vertical or the oblique growth of graphite anode active material.In addition, can distinguish from following The fact has been fully proved ground: be presented at the method figure that being used for Fig. 2 (A) prepare carbon nano-fiber of the present invention and be different from the U.S. Patent No. 6440610 B1 disclosed methods that are presented at Fig. 2 (C).
On the other hand, in compressing grains, the carbon nano-fiber that is grown in surface of crystalline silicon can easily separate, because the bonding force step-down between crystal silicon particle and the carbon nano-fiber.As shown in Figure 6, when influenced by external force, carbon nano-fiber tends to be easy to the surface isolation from crystalline silicon.Therefore, carbon nano-fiber can not be effectively around the surface of crystalline silicon, this can not prevent the volumetric expansion of silicon in repeatedly the charge process.
Inventor's recent findings the amorphous organosilyl new method of a kind of preparation, it is by applying shear stress to crystalline silicon in inert atmosphere, this has caused the decomposition of silicon crystalline structure.In addition, if apply shear stress, can obtain the amorphous silicon of high level so by graphite granule is mixed with silicon.Use the amorphous silicon of high level, can on the silicon active material of positive electrode, carry out the growth of carbon nano-fiber with the form of hydridization.Finally, the adjustment of crystal block section in the silicon structure and pars amorpha can be controlled the hydridization of carbon nano-fiber and silicon active material of positive electrode.
In the present invention, utilize the growth control technology, realized form on active material of positive electrode the evenly growth of carbon nano-fiber, and need not to use the body phase of carbon nanomaterial with hydridization.Therefore, finish the present invention by form hybrid material between carbon nano-fiber and active material of positive electrode, this has kept the charge/discharge performance and the cycle performance of the high power capacity of graphite and/or silicon materials.
Because the anode material of the hydridization that is formed by carbon nano-fiber and graphite does not mainly influence the variation of active material of positive electrode initial particle, wherein carbon nano-fiber is centered around graphite surface with the form of rattan, need not the active material of positive electrode that further process of lapping is used as lithium secondary battery so can use this hybrid material.Can adopt known method to prepare secondary cell.Specifically, utilize following step to prepare electrode, comprise i) with binding agent (PVDF) and nmp solvent dissolving; Ii) preparation contains the slurry of binding agent and active material of positive electrode, and wherein their weight ratio is respectively 15: 85; And iii) the slurry that is obtained to be coated to thickness be on 15 microns the copper coin.For the electrode thoroughly removing organic solvent, make will be in 120-180 ℃ vacuum furnace dry 12 hours.After the electrode that drying obtained, utilize the surface of the roller piezoelectricity utmost point so that electrode is bonded on the copper coin securely and for keeping the density constant of electrode.The shape of electrode is the coin of diameter 12mm.And, adopt the lithium metal to prepare comparative electrode, and electrolyte is by 1M LiPF
6(EC:DEC=1:1v/v) make.By adopting FE-SEM to observe, confirmed that carbon nanofibers grow is on the active material of positive electrode of carbon nano-fiber/graphite hydridization.The equipment that is used to observe is that the FE-SEM type JSM-6700F of JEOL production and the standard multiple of SEM are adjusted to x100000 when beginning.In addition, the observed result of SEM draws simultaneously to explain this structure under the condition of 200kV.
Can understand the present invention more accurately by following preparation embodiment, comparative preparation embodiment, embodiment and comparing embodiment.Yet scope of the present invention also is not limited by the following examples.
Embodiment
(preparation embodiment 1) preparation contains the negative pole with the native graphite anode material of carbon nano-fiber hydridization
9g native graphite, 5.09g nickel nitrate (Ni (NO
3)
26H
2O), 0.5g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 550 ℃ with resulting material from 100 ℃.This material was placed 2 hours down at 550 ℃.By the ethene that flows: hydrogen: helium (80ml/min:40ml/min:80ml/min) mist carries out gas carburization reaction 5min.The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 23wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-50nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Fig. 3 and Fig. 4 have shown the structure of the carbon nano-fiber that obtains among this embodiment.Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 2) preparation contains the negative pole with the native graphite anode material of carbon nano-fiber hydridization
10g native graphite, 0.79g nickel nitrate (Ni (NO
3)
26H
2O), 0.29g ferric nitrate (Fe (NO
3)
29H
2O), 1.0g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 580 ℃ with resulting material from 100 ℃.This material was placed 2 hours down at 580 ℃.By the carbon monoxide that flows: hydrogen (160ml/min:40ml/min) mist carries out gas carburization reaction 30min.The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 16wt%, and draw ratio is greater than 50, and the diameter of fiber is 20-60nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is the plate object structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 3) preparation contains the negative pole with the amorphous silicon anode material of carbon nano-fiber hydridization
The Metal Ball of 50g crystalline silicon and 500g diameter 10mm is placed in the metal bowl in the argon atmospher.Adopt planetary ball mill, with the rotating speed grinding crystalline silicon of 200rpm.Milling time is 3 hours (Fig. 7).The unbodied Si powder of the part that 10g ground, 0.99g cobalt nitrate (Co (NO
3)
39H
2O), 2.2g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending; Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 550 ℃ with resulting material from 100 ℃.This material was placed 2 hours down at 550 ℃.By the ethene that flows: hydrogen: helium (80ml/min:40ml/min:80ml/min) mist carries out gas carburization reaction 10min.The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 15wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 4) preparation contains the negative pole with the amorphous silicon anode material of carbon nano-fiber hydridization
Except the milling time that adopts planetary ball mill became 6 hours by 3 hours, active material of positive electrode and carbon nano-fiber prepare (Fig. 7 and Fig. 9) according to the mode identical with preparation embodiment 3.
The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 31wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Fig. 5 has shown the structure of the carbon nano-fiber that obtains among this embodiment.Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 5) preparation contains the negative pole with the compound anode material of the native graphite of carbon nano-fiber hydridization and amorphous silicon
43.5g the Metal Ball of crystalline silicon, 6.5g native graphite and 500g diameter 10mm is placed in the metal bowl in the argon atmospher.Adopt planetary ball mill, with the rotating speed grinding crystalline silicon of 200rpm.Milling time is 1 hour (Fig. 8).The amorphous silicon that 10g ground/graphite composite powder, 0.99g cobalt nitrate (Co (NO
3)
39H
2O), 2.2g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 550 ℃ with resulting material from 300 ℃.This material was placed 2 hours down at 550 ℃.By the ethene that flows: hydrogen: helium (80ml/min:40ml/min:80ml/min) mist carries out gas carburization reaction 10min.The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 12wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 6) preparation contains the negative pole with the compound anode material of the native graphite of carbon nano-fiber hydridization and amorphous silicon
Except the milling time that adopts planetary ball mill became 8 hours by 1 hour, active material of positive electrode and carbon nano-fiber prepare (Fig. 8) according to the mode identical with preparation embodiment 5.
The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 21wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 7) preparation contains the negative pole with the compound anode material of the native graphite of carbon nano-fiber hydridization and amorphous silicon
Except the milling time that adopts planetary ball mill became 13 hours by 1 hour, active material of positive electrode and carbon nano-fiber prepare (Fig. 8) according to the mode identical with preparation embodiment 5.
The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 35wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 8) preparation contains the negative pole with the compound anode material of the native graphite of carbon nano-fiber hydridization and amorphous silicon
Except the milling time that adopts planetary ball mill became 18 hours by 1 hour, active material of positive electrode and carbon nano-fiber prepare (Fig. 8) according to the mode identical with preparation embodiment 5.
The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 39wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(preparation embodiment 9) preparation contains the negative pole with the compound anode material of the native graphite of carbon nano-fiber hydridization and amorphous silicon
Except the milling time that adopts planetary ball mill became 25 hours by 1 hour, active material of positive electrode and carbon nano-fiber prepare (Fig. 8 and Figure 10) according to the mode identical with preparation embodiment 5.
The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 50wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-20nm.And by the observation of TEM, the structure of seeing carbon nano-fiber is a herringbone structure.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(comparative preparation embodiment 1) preparation contains the negative pole with the crystalline silicon/graphite anode material of carbon nano-fiber hydridization
The 43.5g crystalline silicon powder and the 6.5g native graphite powder that sieved through 320 mesh sieves are placed on the plastic bowl of 500ml, mix 1 hour with the dry type ball-milling method then.
10g silicon/graphite mixed-powder, 0.99g cobalt nitrate (Co (NO
3)
39H
2O), 2.2g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min: 40ml/min) resulting material is heated to 550 ℃ from 300 ℃.This material was placed 2 hours down at 550 ℃.By the ethene that flows: hydrogen: helium (80ml/min:40ml/min:80ml/min) mist carries out gas carburization reaction 10min (Fig. 2 B).The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 12wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-80nm.The growth of carbon nano-fiber mainly occurs in the surface of graphite active material, and has only observed the growth of small amount of carbon nanofiber on the surface of silicon.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(comparative preparation embodiment 2) preparation contains the negative pole with the crystalline silicon anode material of carbon nano-fiber hydridization
The crystalline silicon powder that 10g sieved through 320 mesh sieves, 0.99g cobalt nitrate (Co (NO
3)
39H
2O), 2.2g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 550 ℃ with resulting material from 300 ℃.This material was placed 2 hours down at 550 ℃.By the ethene that flows: hydrogen: helium (80ml/min:40ml/min:80ml/min) mist carries out gas carburization reaction 10min (Fig. 2 B).The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 28wt%, and draw ratio is greater than 50, and the diameter of fiber is 10-30nm.The growth of carbon nano-fiber mainly only occurs in the corner portions located of Si powder, but not on the planar section of Si powder (Fig. 6 A).In addition, Si powder is easy to separate with carbon nano-fiber and does not have hydridization (Fig. 6 B).
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
(comparative preparation embodiment 3) preparation only contains the negative pole of native graphite
Only utilize native graphite as active material of positive electrode, make negative pole on the copper coin by slurry (native graphite: adhesive=85:15, weight ratio) is applied to.
(comparative preparation embodiment 4) preparation contains the negative pole of native graphite anode material and carbon nanomaterial
Prepared carbon nano-fiber according to U.S. Patent No. 6440610 B1 disclosed methods.Then, slurry (by the active material of positive electrode that U.S. Patent No. 6440610 B1 disclosed methods make, native graphite: adhesive=85:15, weight ratio) is applied to makes negative pole on the copper coin.
Below description be the method that is used for preparing the carbon nano-fiber of U.S. Patent No. 6440610 B1." after in 20g nickel nitrate dissolving water inlet, this solution mixes with the 200g native graphite.Obtain graphite material on the superficial layer by spray-drying mixt, wherein the particle of nickel nitrate is formed on this surface.Obtain to form on it resulting graphite material of nickel oxide by the resulting graphite granule of carbonization under 800 ℃ temperature, then in air, this carbide of oxidation is about 4 hours under 400 ℃ temperature, pass through to obtain resulting graphite material via reducing process, wherein under 500 ℃ temperature, used hydrogen about 20 hours.Obtain the native graphite powder on the superficial layer of formation Ni particle.With vapour deposition process by will be resulting under about 600 ℃ temperature powder advance in the pottery and and inject the fiber that vessel come growth vapor phase growth on the Ni catalyst acetylene.After about 30 minutes of reaction, substitute acetylene gas with argon, the vapor phase growth fiber is cooled to normal temperature at leisure " (Fig. 2 C).
According to said method, we test.Yet, can not obtain to have the carbon nano-fiber of the expectation of following condition, the thickness (5-1000nm) of this condition such as diameter (5-300nm), draw ratio (10-10000), carbon nano-fiber.We are getable to be fibrous type carbon polymer material.Yet we utilize analytical equipment to record the productive rate of carbon nano-tube.At any time, the amount of the carbon nano-tube in the carbon polymer material is less than the 5wt% of total carbon polymer material.
Utilize resulting carbon nanomaterial among this embodiment, make negative pole on the copper coin by slurry (resulting carbon nanomaterial: adhesive=85:15, weight ratio) is applied to.
(comparative preparation embodiment 5) preparation contains the negative pole with the native graphite anode material of carbon nano-tube hybridization
10g native graphite, 3.65g ferric nitrate (Fe (NO
3)
29H
2O), 7.3g carbonic hydroammonium (NH
4HCO
3) and 300ml water mix 1 hour with supending.Utilize the funnel filter to filter resulting suspension and remove water constituent.Then, utilize vacuum furnace with resulting solid constituent 100 ℃ dry 24 hours down, 1g is dry, and the graphite solid composition of crossing is coated on the quartz plate.Adopt horizontal quartz ampoule, with the firing rate of 10 ℃/min with the helium that flows: hydrogen mixed gas (160ml/min:40ml/min) is heated to 680 ℃ with resulting material from 300 ℃.This material was placed 2 hours down at 550 ℃.By the carbon monoxide that flows: hydrogen (160ml/min:40ml/min) mist carries out gas carburization reaction 30min.The amount that has been demonstrated synthetic carbon nano-fiber by the observed result of FE-SEM is 5wt%, and draw ratio is greater than 50, and the diameter of fiber is 20-40nm.And by the observation of TEM, the structure of seeing carbon nanomaterial is a carbon nano-tube.
Utilize resulting active material of positive electrode, make negative pole on the copper coin by slurry (active material of positive electrode: adhesive=85:15, weight ratio) is applied to.
Table 1 has shown the amount of the carbon nano-fiber of the component of the active material of positive electrode among preparation embodiment and the comparative preparation embodiment and growth.
Table 1
| Sample | Quantity of graphite (weight portion) | Silicon amount (weight portion) | Grinding time (hr) | Amorphous degree (%) | The amount (%) of the carbon nano-fiber of growth |
| Preparation embodiment 1 | 100 | 0 | 0 | - | 23 |
| |
100 | 0 | 0 | - | 16 |
| Preparation embodiment 3 | 0 | 100 | 3 | 15 | 15 |
| Preparation embodiment 4 | 0 | 100 | 6 | 59 | 31 |
| |
13 | 87 | 1 | 2 | 12 |
| Preparation embodiment 6 | 13 | 87 | 8 | 71 | 21 |
| Preparation embodiment 7 | 13 | 87 | 13 | 86 | 35 |
| Preparation embodiment 8 | 13 | 87 | 18 | 89 | 39 |
| Preparation embodiment 9 | 13 | 87 | 25 | 89 | 50 |
| Comparative preparation embodiment 1 | 13 | 87 | 0 | 0 | 12 |
| |
0 | 100 | 0 | 0 | 28 |
| Comparative preparation embodiment 3 | 100 | 0 | 0 | - | 0 |
| Comparative preparation embodiment 4 | 100 | 0 | 0 | - | <5 |
| |
100 | 0 | 0 | - | 5 |
In this table, " amorphous degree " compares crystalline silicon d by XRD
(III)Main peak intensity in the plate is measured.Calculate by following formula:
(the crystalline silicon d before grinding
(III)The main peak intensity of silicon d (III) plate of the main peak intensity in the plate-be used to prepare)/crystalline silicon d before grinding
(III)Main peak intensity * 100 (%) in the plate
" amount of the carbon nano-fiber of growth " calculated by following formula:
Weight * 100 (%) of the active material of positive electrode before (weight of the active material of positive electrode before the weight-reaction of the active material of positive electrode of hydridization)/reaction
The charge/discharge test of the anode in (embodiment 1-9) secondary cell
Adopt the anode among the preparation embodiment 1-9 to measure charge/discharge capacity
Adopt the half-cell of assembling, carry out 30 charge (12min circulation, circulation in 1 hour, circulation in 10 hours).In circulation each time, measure the degree of keeping of charge/discharge capacity.Table 2 has shown the degree of keeping of charge/discharge capacity.
The charge/discharge test of the anode in (comparing embodiment 1-5) secondary cell
Adopt the anode among the comparative preparation embodiment 1-5 to measure charge/discharge capacity.In comparative preparation embodiment 1-2, the carbon nano-fiber by the growth of hydridization at random prepares anode.In comparative preparation embodiment 3, prepare anode by native graphite.In comparative preparation embodiment 4, the carbon nano-fiber by the growth of hydridization at random prepares anode.In comparative preparation embodiment 5, prepare anode by the hydridization carbon nanotubes grown.
Adopt the half-cell of assembling, carry out 30 charge (12min circulation, circulation in 1 hour, circulation in 10 hours).In circulation each time, measure the degree of keeping of charge/discharge capacity.Table 2 has shown the degree of keeping of charge/discharge capacity.
Table 2
Claims (9)
1. lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization of being used for by the preparation of following step, described step comprises:
I) metallic catalyst of nano particle size is dispersed in the surface of anode material of the compound of graphite and amorphous silicon; And
Ii) by chemical vapour deposition technique growth carbon nano-fiber, wherein said carbon nano-fiber with the form growth of rattan and be centered around described active material of positive electrode surface around,
Be the compound that the amorphous silicon of the graphite of 1-50wt% and 50-99wt% prepares described graphite and amorphous silicon wherein by weight ratio.
2. according to claim 1ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, the structure of wherein said carbon nano-fiber is plate object structure or the herringbone structure with described anode active material hybridizing.
3. according to claim 1ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, the increment of wherein said carbon nano-fiber is 1-200 weight portions with respect to the described active material of positive electrode of 100 weight portions, the diameter of described carbon nano-fiber is 5-300nm, draw ratio is 10-10000, and the thickness of the described carbon nano-fiber on the described active material of positive electrode is 5-1000nm.
4. according to claim 3ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, the increment of wherein said carbon nano-fiber is 5-100 weight portions with respect to the described active material of positive electrode of 100 weight portions, the diameter of described carbon nano-fiber is 5-100nm, draw ratio is 10-1000, and the thickness of the described carbon nano-fiber on the described active material of positive electrode is 10-500nm.
5. according to claim 4ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, the increment of wherein said carbon nano-fiber is 10-80 weight portions with respect to the described active material of positive electrode of 100 weight portions, the diameter of described carbon nano-fiber is 5-50nm, draw ratio is 10-100, and the thickness of the described carbon nano-fiber on the described active material of positive electrode is 15-200nm.
6. according to claim 1ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, wherein in the presence of metallic catalyst, the carbon source that utilization is selected from carbon monoxide, methane, acetylene or ethene prepares described carbon nano-fiber by chemical vapour deposition technique, and described metallic catalyst comprise be selected from Fe, Co, Ni, Cu, Mg Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In at least a, described metallic catalyst is the form of alkoxide, oxide, chloride, nitrate or carbonate.
7. according to claim 6ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, wherein adopt the described catalyst of sol-gel process, the precipitation method, hydrothermal method, spraying heating, spray drying process or Prepared by Ball Milling carried catalyst form.
8. according to claim 1ly be used for lithium secondary battery and active material of positive electrode carbon nano-fiber hydridization, wherein said carbon nano-fiber prepares by following step, and described step comprises:
I) under 300-650 ℃, utilize the active material of positive electrode particle of the compound of the mist heating graphite of helium and hydrogen and amorphous silicon; And
Ii) under 400-800 ℃, with the mist of helium and hydrogen, in the presence of the carbon monoxide-olefin polymeric that makes by nickel nitrate and carbonic hydroammonium, utilize the carbon source that is selected from carbon monoxide, methane, acetylene or ethene, by the vapour deposition process described carbon nano-fiber of growing.
9. lithium secondary battery by active material of positive electrode according to claim 1 preparation.
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| KR1020060066215A KR100835883B1 (en) | 2006-07-14 | 2006-07-14 | Negative electrode material hybridizing carbon nanofiber for lithium ion secondary battery |
| KR1020060066215 | 2006-07-14 | ||
| KR1020070060218 | 2007-06-20 |
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Cited By (2)
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| CN108091823A (en) * | 2016-11-22 | 2018-05-29 | 本田技研工业株式会社 | Electrode composition layer and battery |
| WO2020125282A1 (en) * | 2018-12-21 | 2020-06-25 | 浙江伏打科技有限公司 | Carbon-bound lithium ion conductor-carbon composite cathode material having carbon fiber structure and fabrication method therefor |
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| KR100905691B1 (en) * | 2007-06-20 | 2009-07-03 | 금호석유화학 주식회사 | Anode active material hybridizing carbon nanofiber for lithium secondary battery |
| KR101002539B1 (en) * | 2008-04-29 | 2010-12-17 | 삼성에스디아이 주식회사 | Negative electrode active material for lithium rechargeable battery and lithium rechargeable battery comprising the same |
| KR101113008B1 (en) * | 2008-08-04 | 2012-03-13 | (주)썬텔 | Silicon anode composite active material for lithium secondary battery |
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| KR100350535B1 (en) * | 1999-12-10 | 2002-08-28 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| JP2004303613A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Negative electrode material, negative electrode using the same, and lithium ion secondary battery using the negative electrode |
| WO2005031898A1 (en) * | 2003-09-26 | 2005-04-07 | Jfe Chemical Corporation | Composite particle and, utilizing the same, negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery |
| KR100566028B1 (en) * | 2003-12-24 | 2006-03-30 | 전자부품연구원 | Composite Materials including Carbon nanofibers for Anode Active Material of Lithium Secondary Batteries and Method for manufacturing the same |
-
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| CN108091823A (en) * | 2016-11-22 | 2018-05-29 | 本田技研工业株式会社 | Electrode composition layer and battery |
| WO2020125282A1 (en) * | 2018-12-21 | 2020-06-25 | 浙江伏打科技有限公司 | Carbon-bound lithium ion conductor-carbon composite cathode material having carbon fiber structure and fabrication method therefor |
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