CN105074030B - The alloy approach of negative electrode active material composition metal - Google Patents
The alloy approach of negative electrode active material composition metal Download PDFInfo
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- CN105074030B CN105074030B CN201380070821.6A CN201380070821A CN105074030B CN 105074030 B CN105074030 B CN 105074030B CN 201380070821 A CN201380070821 A CN 201380070821A CN 105074030 B CN105074030 B CN 105074030B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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Abstract
The present invention relates to the alloy approach of negative electrode active material composition metal, in more detail, is related to the alloy approach of negative electrode active material composition metal, as the alloy being made up of Si, Ni and transition metal, by SixNiyMz(M is transition metal, x, y, z is respectively atom %) form, composition metal is subjected to alloying in a manner of making above-mentioned x, y, z be 50≤x≤90,1≤y≤49,1≤z≤49 and x+y+z=100, so that non-crystalline areas be present on matrix (Matrix) in alloy, or fine crystal region and non-crystalline areas be present.
Description
Technical field
The present invention relates to the alloy approach of negative electrode active material composition metal, more specifically, it is related to available for filling
The composition metal for the anode active material for lithium secondary battery that discharge of electricity capacity is high and the sustainment rate of capacity is excellent carries out alloy
The method of change.
Background technology
In the past, using lithium metal as the negative electrode active material of lithium battery, but during with lithium metal, due to forming dendrite
(dendrite) short circuit of battery occurs, the danger for having outburst, therefore instead of lithium metal be mostly by the use of carbon system material as
Negative electrode active material.
As above-mentioned active carbon material, there are crystallographic system carbon as graphite and Delanium and soft carbon (soft
) and amorphous carbon as hard carbon (hard carbon) carbon.However, the capacity of above-mentioned amorphous carbon is big, but filling
The problem of non reversibility is so greatly be present in the process of discharge of electricity.As crystallographic system carbon, graphite, theoretical limit can be typically used
Capacity be 372mAh/g, capacity it is high thus can be used as negative electrode active material.
But such graphite or active carbon material it may be said that theoretical capacity some are high but to be also no more than 380mAh/g left
The right side, in high-capacity lithium battery exploitation from now on, there is the problem of can not using above-mentioned negative pole.
In order to improve the problem of such, the material just actively studied now is metal system or intermetallic compound
The negative electrode active material of (intermetallic compounds) system.Aluminium, germanium, silicon, tin, zinc, lead are applied flexibly for example, studying
Deng the lithium battery of metal or semimetal as negative electrode active material.Such material is high power capacity and has high-energy-density, energy
Enough occlusion release more lithium ions compared with the negative electrode active material that make use of carbon-based material, can be manufactured with high power capacity
With the battery of high-energy-density.For example, as it is known that pure silicon has 4017mAh/g high theoretical capacity.
But when compared with carbon-based material, cycle characteristics reduces, practical also to turn into obstacle, this is because, as negative pole
Active material, by above-mentioned silicon etc. directly as occlusion and the h substance of lithium in use, active during charging and discharging
Electric conductivity between material reduces because of the change of volume, or negative electrode active material occurs and shows from what negative electrode collector was peeled off
As.That is, above-mentioned silicon contained in negative electrode active material etc. is by charging come occlusion lithium, so as to volumetric expansion to about 300 to 400%
Left and right, lithium is discharged during electric discharge, and then inanimate matter particle shrinks.
If such charge/discharge cycles are repeated, occur sometimes because of the crackle of negative electrode active material electric exhausted
Edge, life-span drastically reduce, therefore for problem be present during lithium battery.
Therefore, in order to improve the problem of such, following research has been carried out, i.e. use nano-scale rank as silicon particle
Particle, or make silicon that there is porous, so as to which it has buffering effect for Volume Changes.
KR published patent the 2004-0063802nd is related to " anode active material for lithium secondary battery and its manufacture method
And lithium secondary battery ", use after other metals such as silicon and nickel is carried out alloying, made the method for the metal dissolving；South Korea
Publication the 2004-0082876th is related to the " manufacture method and the conduct secondary electricity of lithium of porous silicon and nano-scale silicon particle
The application of pond negative material ", and disclose following technology, i.e. by the alkali metal of pulverulence or alkaline-earth metal and silica
Deng silicon precursor mixing after be heat-treated, then carry out dissolution with sour.
Above-mentioned patent has following problem, i.e. because the buffering effect to alloying metal that cellular structure is brought can improve
Initial capacity sustainment rate, but the porous silicon particle reduced due to electric conductivity is only used only, so if particle is not a nanometer chi
Very little, then when manufacturing electrode, interparticle electrical conductivity declines, and the characteristic that starting efficiency, capacity maintain reduces.
It is therefore desirable to develop the manufacture method of negative electrode active material composition metal, this method is manufactured using alloying metal
During negative electrode active material, it is possible to increase starting efficiency and capacity maintain characteristic, while even if implementing charging and discharging repeatedly, also can
It is enough to maintain voltage and current amount to nearly constant.
The content of the invention
Therefore, the present invention completes to solve the above problems, and its object is to provide one kind body in charging and discharging
Product is with low uncertainty and the negative electrode active material metal of electric insulation is less likely to occur.
In addition, maintain the negative electrode active material of excellent another object of the present invention is to provide a kind of initial effect and capacity
Matter metal.
To achieve these goals, the present invention provides a kind of alloy approach of negative electrode active material composition metal, as
The alloy being made up of Si, Ni and transition metal, by SixNiyMz(M is transition metal, and x, y, z is respectively atom %) is formed, with
Above-mentioned x, y, z is set to be closed composition metal for 50≤x≤90,1≤y≤49,1≤z≤49 and x+y+z=100 mode
Aurification so that non-crystalline areas be present on the matrix (Matrix) in alloy, or fine crystal region and non-crystalline areas be present.
In addition, the present invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterised in that above-mentioned mistake
It is selected from one or more of Al, Cu, Ti and Fe to cross metal.
In addition, the present invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterised in that above-mentioned non-
The non-crystallization degree in crystalline region domain or the non-crystallization degree of above-mentioned fine crystal region and non-crystalline areas are more than 30%.
In addition, the present invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterised in that above-mentioned
The ゜ of the ゜ of the θ of angle of diffraction 2 of the XRD spectra of composition metal=20~100 scope, non-crystallization degree is 30~45%.
When negative electrode active material made according to the present invention is applied to secondary cell with composition metal, due to charging and discharging
When Volume Changes it is few and be less likely to occur to be electrically insulated, therefore with the effect for extending the life-span.
When negative electrode active material made according to the present invention is applied to secondary cell with composition metal, have starting efficiency and
Capacity maintains the effect of excellent.
Even if negative electrode active material made according to the present invention composition metal is applied to have repeatedly in fact during secondary cell
Can also voltage and current amount be maintained to arrive nearly constant effect by applying charging and discharging.
Brief description of the drawings
Fig. 1 represents the SEM measurement results of the negative electrode active material of embodiments of the invention.
Fig. 2 represents the XRD determining result of the negative electrode active material of embodiments of the invention.
Fig. 3 represents the non-crystallization degree measurement result of the negative electrode active material of embodiments of the invention.
Fig. 4 represents the charging and discharging capacity of the negative electrode active material of embodiments of the invention.
Fig. 5 be the negative electrode active material using embodiments of the invention and the battery that manufactures with 0.5C charging and dischargings repeatedly
After 50 times, the figure of the change of capacity according to circulation is determined.
Embodiment
Hereinafter, described in detail with reference to the accompanying drawing of the present invention.First, in accompanying drawing, it has to be noted that be identical inscape or
Part etc. is represented with identical reference marks as far as possible.In the explanation of the present invention, in order to not obscure the purport of the present invention, omission pair
Related known function or composition illustrate.
The term " about " of the degree used in this specification, " actually " etc., it is that can be used to carry in the mentioned meaning
The numerical value or the meaning close to the numerical value when being shown with intrinsic manufacture and material allowable error, it is to understand the present invention, and prevents
Infringer is improper to be used using the disclosure for referring to correct or absolute figure.
The unit " % " used in this manual represents " atom % " in the case where not dictating otherwise especially.
The present invention provides a kind of alloy approach of negative electrode active material composition metal, as by Si, Ni and transition gold
Belong to the alloy formed, by SixNiyMz(M is transition metal, and x, y, z is respectively atom %) form so that above-mentioned x, y, z be 50≤
Composition metal is carried out alloying by x≤90,1≤y≤49,1≤z≤49 and x+y+z=100 mode so that in alloy
Matrix (Matrix) on fine crystal region and non-crystalline areas be present.
When charge/discharge cycles are repeated, cracked because of the expansion and diminution of the volume of negative electrode active material,
So as to produce electric insulation, the problem of thus generation time drastically reduces.It is such in order to solve the problems, such as, pass through the matrix in alloy
(Matrix) non-crystalline areas on be present, or fine crystal region and non-crystalline areas be present, so as to relative to Volume Changes
Buffering (buffer) effect, the change of volume during charging and discharging thus, it is possible to suppress secondary cell.
In addition, the manufacture of the composition metal of the present invention contains Si and Ni, due to above-mentioned Ni in Si be present, so as to there is intensity
Excellent and favourable the matrix to high intensity characteristic.
In addition, the composition metal of the present invention can be by SixNiyMzThe alloy of composition is formed, and M is transition metal here, x, y,
Z is respectively the atom % meaning.
It is preferred that above-mentioned x, y, z is atom %, it is made up of 50≤x≤90,1≤y≤49,1≤z≤49, x+y+z=100.
In above range during manufacture composition metal, exist on the matrix (Matrix) in the alloy that non-crystallization degree is more than 30% non-
Crystalline region domain, or fine crystal region and non-crystalline areas be present.
In addition, it is a feature of the present invention that fine crystal region is not present in alloy and when non-crystalline areas be present, in base
The non-crystallization degree of more than 30% above-mentioned non-crystalline areas on body (Matrix) be present, or fine knot be present simultaneously in alloy
When crystalline region domain and non-crystalline areas, more than 30% above-mentioned fine crystal region and the non-crystallization degree of non-crystalline areas be present.On having
State non-crystallization degree makes the diffusion of lithium become easy characteristic for more than 30%.
By making the non-crystallization degree on matrix be more than 30%, utilized in the secondary battery as negative electrode active material
When, can suppress that volumetric expansion occurs in charging.
In addition, above-mentioned transition metal is preferably selected from more than one in Al, Cu, Ti and Fe in the present invention.
Fig. 1 represents the SEM measurement results of the negative electrode active material of embodiments of the invention, and Fig. 2 represents the implementation of the present invention
The XRD determining result of the negative electrode active material of example.
Fig. 1 is shown as embodiments of the invention by Si65.40Ni25.69Cu8.91、Si65.41Ni25.69Ti8.90、
Si65.40Ni25.69Fe8.91And Si65.40Ni25.70Al8.90The composition metal of composition, in the XRD spectra of above-mentioned composition metal
The ゜ of the ゜ of the θ of angle of diffraction 2=20~100 scope, the non-crystallization degree of fine crystal forms 30~45%, thus with above-mentioned compound
Metal can suppress the effect of volumetric expansion when secondary cell charges.
In addition, in the negative electrode active material of one embodiment of the present of invention, the XRD spectra of alloy the θ of angle of diffraction 2=
The ゜ of 20 ゜~100 scope, non-crystallization degree is preferably 30~45%.When above-mentioned non-crystallization degree is 30~45%, body can be suppressed
Long-pending expansion and be less likely to occur to be electrically insulated.
Being calculated as follows for the non-crystallization degree that the present invention is utilized is shown, and it is showed, in order to determine Fig. 3 non-crystallization degree
And from the point of view of conscientious investigation area, non-crystallization degree can be tried to achieve.
Non-crystallization degree %=((entire area-crystallization area) ÷ entire areas) × 100
Above-mentioned non-crystallization degree height is the meaning more than fine crystal region or non-crystalline areas, thus above-mentioned fine in charging
Crystal region or non-crystalline areas carry out cushioning effect and accumulate lithium ion, can play a part of hindering the factor of volumetric expansion.
In addition, the method for the negative electrode active material of the manufacture present invention is not particularly limited, for example, public using field institute
The various attritive powder manufacture methods known (have gas atomization, centrifugal gas atomization, plasma atomization, rotation electrode
Method, mechanical alloying method etc.).In the present invention, for example, Si and the composition for forming matrix are mixed, make to mix with electric arc fusion method etc.
After polymer melt, above-mentioned fused mass is manufactured into active matter for the single roller emergency cooling solidification method sprayed to the copper roller of rotation
Matter.But the mode used in the present invention is not limited to aforesaid way, in addition to single roller emergency cooling solidification method, as long as can obtain
Sufficient chilling speed, also (can there are gas atomization, centrifugal gas to be atomized by the manufacture skill and technique of the attritive powder of above-mentioned prompting
Method, plasma atomization, rotary electrode method, mechanical alloying method etc.) manufactured.
In addition, secondary cell, but secondary electricity can be manufactured using the negative electrode active material in one embodiment of the present of invention
Positive pole is used as in pond, lithiumation inlaid scheme can be contained, also, inorganic sulfur (S8, elemental also can be used in addition
Sulfur) and chalcogenide compound (sulfur compound), as above-mentioned chalcogenide compound, Li can be illustrated2Sn(n >=1), dissolving
Li in catholyte (Catholyte)2Sn(n >=1), organosulfur compound or carbon-sulphur polymer ((C2Sf)n:F=2.5
To 50, n >=2) etc..
In addition, the species of the electrolyte contained in the secondary cell of the present invention is similarly not particularly limited, can use
Common means well known in the art.Above-mentioned electrolyte can contain Non-aqueous Organic Solvents and lithium in the example of the present invention
Salt.Above-mentioned lithium salts is dissolved in organic solvent, can be used as the supply source of lithium ion in battery, can promote lithium ion just
Movement between pole and negative pole.As the example for the lithium salts that can be used in the present invention, can enumerate containing LiPF6、LiBF4、
LiSbF6、LiAsF6、LiCF3SO3、LiN(CF3SO2)3、Li(CF3SO2)2N、LiC4F9SO3、LiClO4、LiAlO4、LiAlCl4、
LiN(CxF2x+1SO2)(CyF2y+1SO2) (here, x and y is natural number), LiCl, LiI and dioxalic acid lithium borate (lithium
Bisoxalate borate) etc. one or two or more kinds of lithium salts as support (supporting) electrolytic salt.In electrolyte
The concentration of lithium salts can be changed according to purposes, generally be used in the range of 0.1M~2.0M.
In addition, above-mentioned organic solvent has the medium of the ion movement involved by the reaction for the electrochemistry that can make battery
Effect, so as its example, can enumerate benzene, toluene, fluorobenzene, 1,2- difluorobenzenes, 1,3- difluorobenzenes, Isosorbide-5-Nitrae-difluorobenzene, 1,
2,3- trifluoro-benzenes, 1,2,4- trifluoro-benzenes, chlorobenzene, 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, 1,2,3- trichloro-benzenes, 1,
2,4- trichloro-benzenes, iodobenzene (iodobenzene), 1,2- diiodo-benzenes, 1,3- diiodo-benzenes, 1,4- diiodo-benzenes, 1,2,3- triiodo-benzenes, 1,
2,4- triiodo-benzenes, toluene fluoride, 1,2- difluoro toluenes, 1,3- difluoro toluenes, 1,4- difluoro toluenes, 1,2,3- benzotrifluorides, 1,2,
4- benzotrifluorides, chlorotoluene, 1,2- dichlorotoleune, 1,3- dichlorotoleune, 1,4- dichlorotoleune, 1,2,3- benzotrichlorides, 1,2,
4- benzotrichlorides, iodotoluene, the iodotoluenes of 1,2- bis-, the iodotoluenes of 1,3- bis-, the iodotoluenes of 1,4- bis-, the iodotoluenes of 1,2,3- tri-, 1,2,
(here, R is the alkyl of the straight-chain of carbon number 2~50, branched or cyclic structure, above-mentioned alkyl by the iodotoluenes of 4- tri-, R-CN
Double bond, aromatic ring or ehter bond etc. can be contained), dimethylformamide, dimethyl acetate, dimethylbenzene, hexamethylene, tetrahydrochysene furan
Mutter, 2- methyltetrahydrofurans, cyclohexanone, ethanol, isopropanol, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, carbonic acid
Methyl propyl ester, propene carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxy second
Alkane, 1,3- dioxolanes, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propene carbonate, gamma-butyrolacton, ring
Fourth sulfone (sulfolane), valerolactone, decalactone or mevalonolactoneOne or two or more kinds,
But it is not limited to these.
The secondary cell of the present invention, in addition to above-mentioned key element, can also further contain separator, tank, battery container or pad
The common key elements such as circle, its specific species is also without special limitation.
In addition, the present invention secondary cell contain above-mentioned key element, can by the field it is common in a manner of and shape manufacture.
The example of shape that secondary cell as the present invention can have, tubular, horn shape, coin or bag-shaped etc. can be enumerated, but
It is not limited to this.
Hereinafter, the present invention is described in more detail by embodiments of the invention, the scope of the present invention is not limited to following promptings
Embodiment.
Embodiment 1
The method for manufacturing the negative electrode active material of the present invention is not particularly limited, for example, using known in this field
The manufacture skill and technique of various attritive powders (have gas atomization, centrifugal gas atomization, plasma atomization, rotation electrode
Method, mechanical alloying method etc.).Mix Si in embodiment 1 and form the composition of matrix, melt mixture with electric arc fusion method etc.
After melting, above-mentioned fused mass is manufactured into active material for the single roller emergency cooling solidification method sprayed to the copper roller of rotation.
The mode used in the present invention is not limited to aforesaid way, in addition to single roller emergency cooling solidification method, as long as can obtain
Sufficient chilling speed, also (can there are gas atomization, centrifugal gas to be atomized by the manufacture skill and technique of the attritive powder of above-mentioned prompting
Method, plasma atomization, rotary electrode method, mechanical alloying method etc.) manufactured.
In SixNiyMzAlloy in make transition metal for Cu with as Si65.40Ni25.69Cu8.91Mode manufacture compound conjunction
Gold, determines the non-crystallization degree relative to above-mentioned alloy, and then during using composite alloy to manufacture the secondary cell of coin shapes,
It can be used as negative electrode active material.
Embodiment 2
In SixNiyMzAlloy in transition metal is formed Si for Ti65.41Ni25.69Ti8.90, in addition, with implementation
Example 1 is similarly implemented.
Embodiment 3
In SixNiyMzAlloy in transition metal is formed Si for Fe65.40Ni25.69Fe8.91, in addition, with implementation
Example 1 is similarly implemented.
Embodiment 4
In SixNiyMzAlloy in transition metal is formed Si for Al65.40Ni25.70Al8.90, in addition, with implementation
Example 1 is similarly implemented.
Comparative example 1
Manufacture forms Si60Fe14Al26Alloy, now, manufacture Si60Fe14Al26Used as negative electrode active material.
Comparative example 2
In SixNiyMzAlloy in transition metal is formed Si for Ti40Ni20Ti40, it is in addition, same with embodiment 1
Implement sample.
Comparative example 3
In SixNiyMzAlloy in transition metal is formed Si for Fe45Ni25Fe30, it is in addition, same with embodiment 1
Implement sample.
Comparative example 4
In SixNiyMzAlloy in transition metal is formed Si for Al48Ni30Al22.In addition, it is same with embodiment 1
Implement sample.
1.SEM is analyzed
SEM (Scanning Electron Microscopy) analyses are carried out to the negative electrode active material of manufacture.Fig. 1 be by
The SEM photograph of the negative electrode active material amplification of 1~embodiment of embodiment 4.
It can confirm that the dispersed precipitation of Si phases is on matrix (Matrix) in above-mentioned negative electrode active material.
2.XRD is analyzed
Cuk α line XRD determinings are carried out to the negative electrode active material manufactured in embodiment 1~4, its result is shown in fig. 2
Go out.The angle determined during analysis is 20 degree~100 degree, and finding speed is set as 5.7 degree per minute.
3. charging and discharging capacity
Manufactured using the negative electrode active material manufactured in 1~embodiment of embodiment 4 and 1~comparative example of comparative example 4
The secondary cell of coin shapes, after the evaluation for implementing charging and discharging, it the results are shown in Fig. 4.In the pole of manufacture coin shapes
During plate, the ratio of active material, conductive agent (agent of Super P series of conductive) and the mixing of adhesive (PI series of binders) with
As weight than 77:15:2:6 (active materials:Additive:Conductive agent:Adhesive) mode manufactured.Relative to having manufactured
Pole plate, with 0.5C implement 1 time after, determine charging and discharging, as a result described in table 1 described as follows.
4. the measure of non-crystallization degree
The measure of non-crystallization degree can be tried to achieve using the calculating formula of the non-crystallization degree of the XRD spectra using alloy.
Non-crystallization degree %=((entire area-crystallization area) ÷ entire areas) × 100
Non-crystallization degree is higher, it is meant that non-crystalline areas becomes more, or fine crystal region and non-crystalline areas become more, thus
It can regard as because carrying out the region of cushioning effect and the reduction of the expansion key element of volume.
Described in the non-crystallization degree of 1~embodiment of embodiment 4 and 1~comparative example of comparative example 4 table 1 described as follows.
Table 1
[table 1]
During using the alloy of 1~comparative example of comparative example 4 to manufacture negative electrode active material, non-crystallization degree is less than 30%, by
This can determine whether the expansion that big volume is produced compared with embodiment.
5. the characteristic measurement of cycle life
It is as shown in Figure 5 with the characteristic of 0.5C 50 charging and dischargings measure cycle lives repeatedly, its result.Above-mentioned charging
Discharge mode be based on the charging and discharging mode for active material for lithium secondary battery well known to general in the field and
Carry out.
As shown in figure 5, voltage and current amount also almost remains constant after charging and discharging repeatedly, thus can confirm can
Carry out reversible charging and discharging.To the negative electrode active materials of embodiments of the invention etc. with 0.5C charging and discharging 50 times repeatedly
Afterwards, the change of the capacity caused by circulation is determined, also subtracting without discharge capacity drastically can be confirmed after charging and discharging repeatedly
It is few.
Present invention mentioned above is not limited to above-described embodiment and accompanying drawing, those skilled in the art
Various displacements, deformation and change can be carried out in the range of the thought of technology of the present invention is not departed from by understanding.
Claims (1)
1. a kind of alloy approach of negative electrode active material composition metal, it is characterised in that as by Si, Ni and transition metal
The alloy of composition, by SixNiyMzForm, wherein, M is the transition metal selected from Al, Cu, Ti and Fe, and x, y, z is respectively original
Sub- %,
Composition metal is subjected to alloying, non-crystalline areas be present on the matrix in alloy,
Wherein SixNiyMzSelected from Si65.40Ni25.69Cu8.91、Si65.41Ni25.69Ti8.90、Si65.40Ni25.69Fe8.91With
Si65.40Ni25.70Al8.90,
In the ゜ of the ゜ of the θ of angle of diffraction 2=20~100 of the XRD spectra of composition metal scope, Si65.40Ni25.69Cu8.91、
Si65.41Ni25.69Ti8.90、Si65.40Ni25.69Fe8.91And Si65.40Ni25.70Al8.90The non-crystallization degree point of corresponding non-crystalline areas
Not Wei 32%, 43%, 42% and 45%,
Wherein non-crystallization degree meets below equation：
Non-crystallization degree %=((entire area-crystallization area) ÷ entire areas) × 100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120144165A KR101490559B1 (en) | 2012-12-12 | 2012-12-12 | Alloy method of complex metal for negative active material |
| KR10-2012-0144165 | 2012-12-12 | ||
| PCT/KR2013/010440 WO2014092349A1 (en) | 2012-12-12 | 2013-11-18 | Alloy method for complex metal for negative electrode active material |
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| CN105074030B true CN105074030B (en) | 2017-11-14 |
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| KR (1) | KR101490559B1 (en) |
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| JP6178350B2 (en) * | 2014-11-25 | 2017-08-09 | イルジン エレクトリック カンパニー リミテッド | Negative electrode active material for secondary battery and secondary battery using the same |
| KR101670431B1 (en) | 2015-01-07 | 2016-11-10 | 일진전기 주식회사 | Negative active material for secondary battery and the secondary battery comprising the same |
| JP6699473B2 (en) * | 2015-09-14 | 2020-05-27 | トヨタ自動車株式会社 | All-solid-state battery system and manufacturing method thereof |
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| CN1728420A (en) * | 2004-11-15 | 2006-02-01 | 松下电器产业株式会社 | Nonaqueous electrolitc secondary cell |
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| JP3846661B2 (en) * | 1997-02-24 | 2006-11-15 | 日立マクセル株式会社 | Lithium secondary battery |
| JP3733292B2 (en) * | 1998-09-18 | 2006-01-11 | キヤノン株式会社 | Electrode material for negative electrode of lithium secondary battery, electrode structure using the electrode material, lithium secondary battery using the electrode structure, and method for producing the electrode structure and the lithium secondary battery |
| JP4144997B2 (en) * | 2000-05-26 | 2008-09-03 | 三洋電機株式会社 | Negative electrode for lithium secondary battery |
| KR100578872B1 (en) * | 2004-03-08 | 2006-05-11 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery, method of preparing the same, and lithium secondary battery comprising the same |
| KR100637488B1 (en) | 2005-02-25 | 2006-10-20 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery and rechargeable lithium battery comprising same |
| JP4911444B2 (en) * | 2005-05-20 | 2012-04-04 | 福田金属箔粉工業株式会社 | Negative electrode material for lithium secondary battery and method for producing the same |
| WO2007064531A1 (en) * | 2005-12-01 | 2007-06-07 | 3M Innovative Properties Company | Electrode compositions based on an amorphous alloy having a high silicon content |
| EP2375476B1 (en) * | 2008-12-30 | 2017-04-12 | LG Chem, Ltd. | Active anode substance for secondary battery |
| JP2012156028A (en) * | 2011-01-27 | 2012-08-16 | Idemitsu Kosan Co Ltd | Amorphous alloy, negative electrode material for secondary battery comprising the same, negative electrode for secondary battery containing the same, and secondary battery |
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| CN1728420A (en) * | 2004-11-15 | 2006-02-01 | 松下电器产业株式会社 | Nonaqueous electrolitc secondary cell |
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| JP6092423B2 (en) | 2017-03-08 |
| JP2016508280A (en) | 2016-03-17 |
| KR101490559B1 (en) | 2015-02-06 |
| KR20140080580A (en) | 2014-07-01 |
| CN105074030A (en) | 2015-11-18 |
| WO2014092349A1 (en) | 2014-06-19 |
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