CN105074030A - Alloy method for complex metal for negative electrode active material - Google Patents
Alloy method for complex metal for negative electrode active material Download PDFInfo
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- CN105074030A CN105074030A CN201380070821.6A CN201380070821A CN105074030A CN 105074030 A CN105074030 A CN 105074030A CN 201380070821 A CN201380070821 A CN 201380070821A CN 105074030 A CN105074030 A CN 105074030A
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- active material
- negative electrode
- electrode active
- alloy
- metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The present invention relates to an alloy method for a complex metal for a negative electrode active material, and more specifically provides an alloy method for a complex metal for a negative electrode active material, the method producing an alloy of a metal complex such that the alloy comprises Si, Ni and a transition metal, is represented by SixNiyMz (M being a transition metal and x, y and z each being atomic percentages), x, y and z satisfying 50<=x<=90, 1<=y<=49, 1<=z<=49 and x+y+z=100 such that there is an amorphous region or a micro crystal region and an amorphous region on the matrix in the alloy.
Description
Technical field
The present invention relates to the alloy approach of negative electrode active material composition metal, more specifically, relate to and will can be used for the high and composition metal that the is anode active material for lithium secondary battery of the sustainment rate excellence of capacity of charging and discharging capacity and carry out the method for alloying.
Background technology
In the past, use lithium metal as the negative electrode active material of lithium cell, but during with lithium metal, the short circuit of battery occurs owing to forming dendrite (dendrite), there is the danger of outburst, therefore replace lithium metal to be as negative electrode active material mostly with carbon system material.
As above-mentioned carbon system active substance, there is the amorphous carbon that graphite and the such crystallographic system carbon of synthetic graphite and soft carbon (softcarbon) and hard carbon (hardcarbon) are such.But the capacity of above-mentioned amorphous carbon is large, but there is non reversibility problem so greatly in the process of charging and discharging.As crystallographic system carbon, representativity ground uses graphite, and the capacity of theoretical limit is 372mAh/g, and thus capacity height can be used as negative electrode active material.
But such graphite or carbon system active substance can be said some height of theoretical capacity but also be no more than about 380mAh/g, when high-capacity lithium battery exploitation from now on, there is the problem that cannot use above-mentioned negative pole.
In order to improve such problem, the material of positive active research is the negative electrode active material that metal system or intermetallic compound (intermetalliccompounds) are now.Such as, metals such as applying flexibly aluminium, germanium, silicon, tin, zinc, lead or the semi-metal lithium cell as negative electrode active material is being studied.Such material is heavy body and has high-energy-density, the negative electrode active material of occlusion emission and utilization carbonaceous material can compare more lithium ion, can manufacture the battery with heavy body and high-energy-density.Such as, known pure silicon has the high theoretical capacity of 4017mAh/g.
But, time compared with carbonaceous material, cycle characteristics reduces, practically also become obstacle, this is because, as negative electrode active material, when the direct occlusions as lithium such as above-mentioned silicon and h substance are used, electroconductibility in the process of charging and discharging between active substance reduces because of the change of volume, or the phenomenon that generation negative electrode active material is peeled off from negative electrode collector.That is, the above-mentioned silicon contained in negative electrode active material etc. carry out occlusion lithium by charging, thus volumetric expansion is to about about 300 to 400%, discharge lithium then inanimate matter particle contraction during electric discharge.
If repeatedly carry out such charge/discharge cycles, then sometimes because of the crackle of negative electrode active material, electrical isolation occurs, the life-span sharply reduces, therefore having problems for during lithium cell.
Therefore, in order to improve such problem, carried out following research, that is, use the particle of nano-scale rank as silicon particle, or make silicon have porousness, thus it has had buffering effect for volume change.
No. 2004-0063802nd, KR published patent relates to " anode active material for lithium secondary battery and manufacture method and lithium secondary battery " thereof, employs after other metals such as silicon and nickel carry out alloying, makes the method for this metal dissolving; No. 2004-0082876th, KR published patent relates to " manufacture method of porousness silicon and nano-scale silicon particle and the application as negative electrode material for lithium secondary cell ", and disclose following technology, namely, heat-treat after the basic metal of pulverulence or alkaline-earth metal are mixed with the silicon precursor of silicon oxide etc., then carry out stripping with acid.
Above-mentioned patent has following problem, namely, the buffering effect of the alloy metal brought because of cellular structure can improve initial capacity sustainment rate, but the porousness silicon particle reduced owing to only using electroconductibility, if therefore particle is not nano-scale, then when manufacturing electrode, interparticle specific conductivity declines, and the characteristic that starting efficiency, capacity maintain reduces.
Therefore, require the manufacture method of exploitation negative electrode active material composition metal, when the method utilizes alloyed metal to manufacture negative electrode active material, starting efficiency and capacity maintenance characteristic can be improved, even if repeatedly implement charging and discharging simultaneously, also voltage and current amount can be maintained to almost constant.
Summary of the invention
Therefore, the present invention completes to solve the problem, its object is to provide a kind of when charging and discharging volume change few and the negative electrode active material metal of electrical isolation is less likely to occur.
In addition, another object of the present invention is to provide a kind of initial effect and capacity to maintain the negative electrode active material metal of excellent.
To achieve these goals, the invention provides a kind of alloy approach of negative electrode active material composition metal, as the alloy be made up of Si, Ni and transition metal, by Si
xni
ym
z(M is transition metal, x, y, z is respectively atom %) form, to make that above-mentioned x, y, z is 50≤x≤90,1≤y≤49,1≤z≤49 and x+y+z=100 mode composition metal is carried out alloying, make that the matrix in alloy (Matrix) exists non-crystalline areas, or there is fine crystalline region and non-crystalline areas.
In addition, the invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterized in that, above-mentioned transition metal be selected from Al, Cu, Ti and Fe more than one.
In addition, the invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterized in that, the non-crystallization degree of above-mentioned non-crystalline areas or the non-crystallization degree of above-mentioned fine crystalline region and non-crystalline areas are more than 30%.
In addition, the invention provides a kind of alloy approach of negative electrode active material composition metal, it is characterized in that, in the scope of angle of diffraction 2 θ=20 ゜ ~ 100 ゜ of the XRD spectra of above-mentioned composition metal, non-crystallization degree is 30 ~ 45%.
When negative electrode active material composition metal constructed in accordance is applied to secondary cell, because volume change during charging and discharging is few and electrical isolation is less likely to occur, therefore there is the effect of prolongs life.
When negative electrode active material composition metal constructed in accordance is applied to secondary cell, there is the effect of starting efficiency and capacity maintenance excellent.
Even if there is enforcement charging and discharging repeatedly also voltage and current amount can be maintained to almost constant effect when negative electrode active material composition metal constructed in accordance is applied to secondary cell.
Accompanying drawing explanation
Fig. 1 represents the SEM measurement result 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 utilize the negative electrode active material of embodiments of the invention and the battery that manufactures with after 0.5C repeatedly charging and discharging 50 times, measure the figure of the change of the capacity according to circulation.
Embodiment
Below, describe in detail with reference to accompanying drawing of the present invention.First, in accompanying drawing, should be noted that identical integrant or parts etc. represent by identical reference marks as far as possible.In explanation of the present invention, in order to not fuzzy purport of the present invention, omit illustrating related known function or formation.
The term " about ", " in fact " etc. of the degree used in this specification sheets, can use to point out this numerical value or the meaning close to this numerical value when having intrinsic manufacture and material permissible error in the mentioned meaning, be to understand the present invention, and prevent the improper utilization of infringer from mentioning the disclosure of correct or absolute figure and using.
The unit " % " used in this manual, when not specifying especially in addition, represents " atom % ".
The invention provides a kind of alloy approach of negative electrode active material composition metal, as the alloy be made up of Si, Ni and transition metal, by Si
xni
ym
z(M is transition metal, x, y, z is respectively atom %) form, to make that above-mentioned x, y, z is 50≤x≤90,1≤y≤49,1≤z≤49 and x+y+z=100 mode composition metal is carried out alloying, make that the matrix in alloy (Matrix) exists fine crystalline region and non-crystalline areas.
When repeatedly carrying out charge/discharge cycles, because of the volume of negative electrode active material expansion and reduce and crack, thus produce electrical isolation, the problem that sharply reduces of generation time thus.In order to solve such problem, by there is non-crystalline areas on the matrix (Matrix) of alloy, or there is fine crystalline region and non-crystalline areas, thus buffering (buffer) effect had relative to volume change, the change of volume when can suppress the charging and discharging of secondary cell thus.
In addition, the manufacture of composition metal of the present invention contains Si and Ni, owing to there is above-mentioned Ni in Si, thus has excellent strength and the characteristic favourable to the matrix of high strength.
In addition, composition metal of the present invention can by Si
xni
ym
zthe alloy formed is formed, and M is transition metal here, and x, y, z is respectively the meaning of atom %.
Preferred above-mentioned x, y, z is atom %, is made up of 50≤x≤90,1≤y≤49,1≤z≤49, x+y+z=100.When manufacturing composition metal in above-mentioned scope, there is non-crystalline areas in the matrix (Matrix) in the alloy that non-crystallization degree is more than 30%, or there is fine crystalline region and non-crystalline areas.
In addition, the invention is characterized in, when there is not fine crystalline region and there is non-crystalline areas in alloy, at the non-crystallization degree of the above-mentioned non-crystalline areas of the upper existence more than 30% of matrix (Matrix), or when there is fine crystalline region and non-crystalline areas in alloy, there is the above-mentioned fine crystalline region of more than 30% and the non-crystallization degree of non-crystalline areas simultaneously.Above-mentioned non-crystallization degree is had to be more than 30% make the diffusion of lithium become easy characteristic.
By making the non-crystallization degree on matrix be more than 30%, when utilizing as negative electrode active material in the secondary battery, can suppress, when charging, volumetric expansion occurs.
In addition, in the present invention, above-mentioned transition metal is preferably selected from more than one in Al, Cu, Ti and Fe.
Fig. 1 represents the SEM measurement result of the negative electrode active material of embodiments of the invention, and Fig. 2 represents the XRD determining result of the negative electrode active material of embodiments of the invention.
Fig. 1 show as embodiments of the invention by Si
65.40ni
25.69cu
8.91, Si
65.41ni
25.69ti
8.90, Si
65.40ni
25.69fe
8.91, and Si
65.40ni
25.70al
8.90the composition metal formed, in the scope of angle of diffraction 2 θ=20 ゜ ~ 100 ゜ of the XRD spectra of above-mentioned composition metal, the non-crystallization degree of fine crystalline forms 30 ~ 45%, has above-mentioned composition metal can suppress volumetric expansion effect when secondary cell charge thus.
In addition, in the negative electrode active material of one embodiment of the present of invention, in the scope of angle of diffraction 2 θ=20 ゜ ~ 100 ゜ of the XRD spectra of alloy, non-crystallization degree is preferably 30 ~ 45%.When above-mentioned non-crystallization degree is 30 ~ 45%, the expansion of volume can be suppressed and electrical isolation is less likely to occur.
Shown in being calculated as follows of the non-crystallization degree that the present invention utilizes, its performance, in order to measure the non-crystallization degree of Fig. 3 and conscientious investigation area, can try to achieve non-crystallization degree.
Non-crystallization degree %=((entire area-crystallization area) ÷ entire area) × 100
Above-mentioned non-crystallization degree height is the meaning that fine crystalline region or non-crystalline areas are many, and when charging, above-mentioned fine crystalline region or non-crystalline areas are carried out shock absorption and accumulated lithium ion thus, can play the effect of the factor hindering volumetric expansion.
In addition, the method manufacturing negative electrode active material of the present invention is not particularly limited, such as, the various fines manufacture method (having gas atomization, centrifugal gas atomization, plasma body atomization, rotating electrode method, mechanical alloying method etc.) that this field can be utilized known.In the present invention, such as, by Si and the composition mixing forming matrix, after making mixture melting with electric arc scorification etc., the single roller emergency cooling solidification method being used for by above-mentioned melts carrying out spraying to the copper roller rotated is to manufacture active substance.But, the mode used in the present invention is not limited to aforesaid way, except single roller emergency cooling solidification method, as long as can obtain sufficient chilling speed, the manufacture skill and technique (having gas atomization, centrifugal gas atomization, plasma body atomization, rotating electrode method, mechanical alloying method etc.) also by the fines of above-mentioned prompting manufactures.
In addition, the negative electrode active material in one embodiment of the present of invention can be utilized to manufacture secondary cell, but as positive pole in secondary cell, can be intercalation compound containing lithiumation, further, inorganic sulfur (S8, elementalsulfur) and chalcogenide compound (sulfurcompound) can also be used in addition, as above-mentioned chalcogenide compound, Li can be illustrated
2s
n(n>=1), the Li be dissolved in catholyte (Catholyte)
2s
n(n>=1), organosulfur compound or carbon-sulphur polymkeric substance ((C
2s
f)
n: f=2.5 to 50, n>=2) etc.
In addition, the electrolytical kind contained in secondary cell of the present invention is not particularly limited similarly, can adopt common means well known in the art.In an example of the present invention, above-mentioned electrolytic solution can contain Non-aqueous Organic Solvents and lithium salts.Above-mentioned lithium salts is dissolved in organic solvent, can be used as the supply source of lithium ion in battery, can promote the movement of lithium ion between positive pole and negative pole.As the example of the lithium salts that can use in the present invention, can enumerate containing LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiCF
3sO
3, LiN (CF
3sO
2)
3, Li (CF
3sO
2)
2n, LiC
4f
9sO
3, LiClO
4, LiAlO
4, LiAlCl
4, LiN (C
xf
2x+1sO
2) (C
yf
2y+1sO
2) one or two or more kinds of (here, x and y is natural number), LiCl, LiI and dioxalic acid lithium tetraborate (lithiumbisoxalateborate) etc. be as the lithium salts supporting (supporting) electrolytic salt.In ionogen, the concentration of lithium salts can change according to purposes, usually uses in the scope of 0.1M ~ 2.0M.
In addition, above-mentioned organic solvent has the effect of the medium of the ionic transfer involved by electrochemical reaction that can make battery, so as its example, can enumerate benzene, toluene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, Isosorbide-5-Nitrae-difluorobenzene, 1,2,3-trifluoro-benzene, 1,2,4-trifluoro-benzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, Isosorbide-5-Nitrae-dichlorobenzene, 1，2，3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene (iodobenzene), 1,2-diiodo-benzene, 1,3-diiodo-benzene, Isosorbide-5-Nitrae-diiodo-benzene, 1，2，3-triiodobenzene, 1,2,4-phenyl triiodide, toluene fluoride, 1,2-difluoro toluene, 1,3-difluoro toluene, Isosorbide-5-Nitrae-difluoro toluene, 1,2,3-phenylfluoroform, 1,2,4-phenylfluoroform, toluene(mono)chloride, 1,2-toluene dichloride, 1,3-toluene dichloride, Isosorbide-5-Nitrae-toluene dichloride, 1,2,3-trichlorotoluene zotrichloride, 1,2,4-trichlorotoluene zotrichloride, toluene iodide, 1,2-bis-toluene iodide, 1,3-bis-toluene iodide, Isosorbide-5-Nitrae-two toluene iodide, 1,2,3-tri-toluene iodide, 1,2,4-tri-toluene iodide, (here, R is the straight-chain of carbonatoms 2 ~ 50 to R-CN, the alkyl of branched or ring texture, above-mentioned alkyl can contain double bond, aromatic ring or ehter bond etc.), dimethyl formamide, dimethyl acetate, dimethylbenzene, hexanaphthene, tetrahydrofuran (THF), 2-methyltetrahydrofuran, pimelinketone, ethanol, Virahol, methylcarbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl ester, propylene carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, glycol dimethyl ether, DOX, diglyme, tetraethylene glycol dimethyl ether, NSC 11801, propylene carbonate, gamma-butyrolactone, tetramethylene sulfone (sulfolane), valerolactone, decalactone or mevalonolactone
one or two or more kinds, but be not limited to these.
Secondary cell of the present invention, except above-mentioned key element, also can contain the common key elements such as separator, tank, battery container or packing ring further, its concrete kind is not particularly limited equally.
In addition, secondary cell of the present invention contains above-mentioned key element, can with the common mode in this field and shape manufacture.As the example of the shape that secondary cell of the present invention can have, tubular, horn shape, coin or bag-shaped etc. can be enumerated, but be not limited to this.
Below, be described in more detail the present invention by embodiments of the invention, scope of the present invention is not limited to the embodiment of following prompting.
Embodiment 1
The method manufacturing negative electrode active material of the present invention is not particularly limited, such as, the manufacture skill and technique of known various fines in this field (having gas atomization, centrifugal gas atomization, plasma body atomization, rotating electrode method, mechanical alloying method etc.) can be utilized.Mix the composition of Si and formation matrix in embodiment 1, after making mixture melting with electric arc scorification etc., the single roller emergency cooling solidification method being used for by above-mentioned melts carrying out spraying to the copper roller rotated is to manufacture active substance.
The mode used in the present invention is not limited to aforesaid way, except single roller emergency cooling solidification method, as long as can obtain sufficient chilling speed, the manufacture skill and technique (having gas atomization, centrifugal gas atomization, plasma body atomization, rotating electrode method, mechanical alloying method etc.) also by the fines of above-mentioned prompting manufactures.
At Si
xni
ym
zalloy in make transition metal be that Cu is to become Si
65.40ni
25.69cu
8.91mode manufacture composite alloy, measure the non-crystallization degree relative to above-mentioned alloy, and then when utilizing composite alloy to manufacture the secondary cell of coin shapes, can be used as negative electrode active material and be used.
Embodiment 2
At Si
xni
ym
zalloy in make transition metal be that Ti forms Si
65.41ni
25.69ti
8.90, in addition, implement similarly to Example 1.
Embodiment 3
At Si
xni
ym
zalloy in make transition metal be that Fe forms Si
65.40ni
25.69fe
8.91, in addition, implement similarly to Example 1.
Embodiment 4
At Si
xni
ym
zalloy in make transition metal be that Al forms Si
65.40ni
25.70al
8.90, in addition, implement similarly to Example 1.
Comparative example 1
Manufacture and form Si
60fe
14al
26alloy, now, manufacture Si
60fe
14al
26use as negative electrode active material.
Comparative example 2
At Si
xni
ym
zalloy in make transition metal be that Ti forms Si
40ni
20ti
40, in addition, implement similarly to Example 1.
Comparative example 3
At Si
xni
ym
zalloy in make transition metal be that Fe forms Si
45ni
25fe
30, in addition, implement similarly to Example 1.
Comparative example 4
At Si
xni
ym
zalloy in make transition metal be that Al forms Si
48ni
30al
22.In addition, implement similarly to Example 1.
1.SEM analyzes
Carry out SEM (ScanningElectronMicroscopy) to the negative electrode active material manufactured to analyze.Fig. 1 is the SEM photo amplified by the negative electrode active material of embodiment 1 ~ embodiment 4.
Can confirm that the dispersed precipitation of Si phase is on matrix (Matrix) in above-mentioned negative electrode active material.
2.XRD analyzes
Cuk α line XRD determining is carried out, by shown in Figure 2 for its result to the negative electrode active material manufactured in embodiment 1 ~ 4.The angle measured during analysis is 20 degree ~ 100 degree, and finding speed is set as per minute 5.7 degree.
3. charging and discharging capacity
Utilize the negative electrode active material manufactured in embodiment 1 ~ embodiment 4 and comparative example 1 ~ comparative example 4 to manufacture the secondary cell of coin shapes, after implementing the evaluation of charging and discharging, the results are shown in Fig. 4.When manufacturing the pole plate of coin shapes, the ratio of the mixing of active substance, conductive agent (agent of SuperP series of conductive) and tackiness agent (PI series of binders) manufactures in the mode becoming weight ratio 77:15:2:6 (active substance: additive: conductive agent: tackiness agent).Relative to the pole plate manufactured, after implementing 1 time with 0.5C, measure charging and discharging, described in result table 1 described as follows.
4. the mensuration of non-crystallization degree
The mensuration of non-crystallization degree can utilize and adopt the calculating formula of the non-crystallization degree of the XRD spectra of alloy to try to achieve.
Non-crystallization degree %=((entire area-crystallization area) ÷ entire area) × 100
Non-crystallization degree is higher, mean that non-crystalline areas becomes many, or fine crystalline region and non-crystalline areas becomes many, and the expansion key element can regarding region because carrying out shock absorption and volume thus as reduces.
Described in the non-crystallization degree table 1 described as follows of embodiment 1 ~ embodiment 4 and comparative example 1 ~ comparative example 4.
Table 1
[table 1]
When utilizing the alloy of comparative example 1 ~ comparative example 4 to manufacture negative electrode active material, non-crystallization degree is less than 30%, can judge the expansion producing large volume compared with embodiment thus.
5. the characteristic measurement of cycle life
With 0.5C repeatedly 50 charging and dischargings measure the characteristic of cycle lives, its result is as shown in Figure 5.Above-mentioned charging and discharging mode is carried out based on the charging and discharging mode for active material for lithium secondary battery generally known in this field.
As shown in Figure 5, after charging and discharging repeatedly, voltage and current amount also almost remains constant, can confirm thus to carry out reversible charging and discharging.To the negative electrode active material of embodiments of the invention etc. with after 0.5C repeatedly charging and discharging 50 times, measure the change because of the capacity caused that circulates, after charging and discharging can be confirmed repeatedly, also there is no the minimizing of loading capacity sharply.
The present invention described above is not limited to above-described embodiment and accompanying drawing, and those skilled in the art understand can carry out various displacement, distortion and change in the scope of the thought not departing from technology of the present invention.
Claims (4)
1. an alloy approach for negative electrode active material composition metal, is characterized in that, as the alloy be made up of Si, Ni and transition metal, by Si
xni
ym
zform, wherein, M is transition metal, and x, y, z is respectively atom %,
To make that described x, y, z is 50≤x≤90,1≤y≤49,1≤z≤49 and x+y+z=100 mode composition metal is carried out alloying, make that the matrix in alloy exists non-crystalline areas, or there is fine crystalline region and non-crystalline areas.
2. the alloy approach of negative electrode active material composition metal according to claim 1, is characterized in that, described transition metal be selected from Al, Cu, Ti and Fe more than one.
3. the alloy approach of negative electrode active material composition metal according to claim 1, is characterized in that, the non-crystallization degree of described non-crystalline areas or the non-crystallization degree of described fine crystalline region and non-crystalline areas are more than 30%.
4. the alloy approach of negative electrode active material composition metal according to claim 1, is characterized in that, in the scope of angle of diffraction 2 θ=20 ゜ ~ 100 ゜ of the XRD spectra of described composition metal, non-crystallization degree is 30 ~ 45%.
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| 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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| 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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| KR100637488B1 (en) | 2005-02-25 | 2006-10-20 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery and rechargeable lithium battery comprising same |
| CN102272983B (en) * | 2008-12-30 | 2014-02-19 | 株式会社Lg化学 | Active cathode substance for secondary battery |
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| JP2001338646A (en) * | 2000-05-26 | 2001-12-07 | Sanyo Electric Co Ltd | Lithium secondary battery negative electrode |
| KR20050090220A (en) * | 2004-03-08 | 2005-09-13 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery, method of preparing the same, and lithium secondary battery comprising the same |
| CN1728420A (en) * | 2004-11-15 | 2006-02-01 | 松下电器产业株式会社 | Nonaqueous electrolitc secondary cell |
| JP2006324210A (en) * | 2005-05-20 | 2006-11-30 | Fukuda Metal Foil & Powder Co Ltd | Negative electrode material for lithium secondary battery and its manufacturing method |
| CN101322266A (en) * | 2005-12-01 | 2008-12-10 | 3M创新有限公司 | Electrode compositions based on an amorphous alloy having a high silicon content |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101490559B1 (en) | 2015-02-06 |
| WO2014092349A1 (en) | 2014-06-19 |
| KR20140080580A (en) | 2014-07-01 |
| CN105074030B (en) | 2017-11-14 |
| JP6092423B2 (en) | 2017-03-08 |
| JP2016508280A (en) | 2016-03-17 |
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