CN101728509B - Lithium battery, positive electrode and formation method thereof - Google Patents

Lithium battery, positive electrode and formation method thereof Download PDF

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CN101728509B
CN101728509B CN2008101751182A CN200810175118A CN101728509B CN 101728509 B CN101728509 B CN 101728509B CN 2008101751182 A CN2008101751182 A CN 2008101751182A CN 200810175118 A CN200810175118 A CN 200810175118A CN 101728509 B CN101728509 B CN 101728509B
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positive pole
oxide layer
lithium alloy
alloy oxide
plasma
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CN101728509A (en
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王复民
杨长荣
陈振崇
邱国峰
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Industrial Technology Research Institute ITRI
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Abstract

The invention relates to a positive electrode applied to a lithium battery and a formation method thereof. The formation method comprises the following steps of: firstly, forming a lithium alloy oxide layer on a substrate; and secondly, carrying out additional treatment of high-density low-energy plasma to ensure that even and compact nanometer crystal particles tightly jointed with each other are formed on the upper surface of the lithium alloy oxide layer and an original larger crystal particle structure is maintained inside the lower side. An experiment proves that the positive electrode having the characteristics has a higher capacitance and a longer cycle life, and can further prompt the performance efficacy of the lithium battery.

Description

Lithium battery and anodal and its formation method
Technical field
The present invention relates to lithium battery, relates more specifically to positive pole wherein and forming method thereof.
Background technology
Portable electronic product now such as digital camera, mobile phone, mobile computer need light-weighted battery.In various battery, but electricity ratio conventional batteries that the Unit Weight of the lithium battery of recharge can provide such as lead accumulator, Ni-MH battery, nickel-zinc cell, nickel-cadmium cell Senior Three are doubly.In addition, lithium battery quickly-chargeable.
In lithium battery, positive electrode is generally lithium metal oxide, like LiNiO 2, LiCoO 2, LiMn 2O 4, LiFePO 4, or LiNi xCo 1-xO 2Negative material is generally alloy or the material with carbon element (carbonaceous material) of lithium metal, lithium and other metal like graphite.No matter general form anodal method and be to use thin film preparation process or powder preparing technology, the lithium alloy oxide layer can form inhomogeneous, not fine and close and upper surface that crystal grain is thick, and reduce anodal electric capacity (Capacity, mAh/g) and cycle life.In sum, need new method at present badly and improve the rough problem of anodal upper surface.
Summary of the invention
The object of the present invention is to provide a kind of method that is formed for the positive pole of lithium battery, it can solve the rough defective of anodal upper surface that occurs in the prior art basically.
Another object of the present invention is to provide a kind of upper surface is to engage each other closely and the positive pole of average fine and close nanocrystal.
A purpose more of the present invention provides the lithium battery with above-mentioned positive pole, and this battery is just having higher capacitance and cycle life because of it, thereby further promotes the performance usefulness of lithium battery.
The present invention provides a kind of formation method of positive pole, comprises substrate is provided; Form the lithium alloy oxide layer on substrate; And with the low-energy plasma modification lithium alloy of high density oxide layer, its upper surface is formed engage each other closely and average fine and close nanocrystal, lower inner is then kept former bigger grainiess.
The present invention also provides a kind of positive pole, comprises substrate; And the lithium alloy oxide layer is positioned on the substrate; Wherein the upper surface of lithium alloy oxide layer has and engages each other closely and average fine and close nanocrystal, and lower inner is then kept former bigger grainiess.
The present invention more provides a kind of lithium battery, comprises above-mentioned positive pole; Negative pole; Barrier film, between anodal and this negative pole to define a holding area; Electrolyte solution is positioned at holding area; And encapsulating structure, clad anode, negative pole, barrier film and electrolyte solution.
The invention has the advantages that: the formation method of positive pole of the present invention applies extra low-yield highdensity Cement Composite Treated by Plasma to the lithium alloy oxide layer; Making the upper surface of anodal lithium alloy oxide layer have engages each other closely; Average fine and close; Crystal grain is between the nanocrystal of 3nm~10nm, and lower inner is then kept former bigger grainiess, thereby has overcome the rough defective of anodal upper surface that occurs in the prior art basically.And, just having higher capacitance and selling life owing to of the present invention than long circulation, the lithium battery of using electrode of the present invention also has preferable performance performance thereupon.
Description of drawings
Fig. 1 is in the embodiment of the invention, the profile of lithium battery;
Fig. 2 is in the embodiment of the invention, the profile of plasma source;
Fig. 3 a is in the comparing embodiment of the present invention, LiMn 2O 4The electronic diffraction collection of illustrative plates of layer;
Fig. 3 b is in the embodiment of the invention, LiMn 2O 4The electronic diffraction collection of illustrative plates of layer;
Fig. 4 is in the embodiment of the invention and the comparing embodiment, LiMn 2O 4The ESCA collection of illustrative plates of layer;
Fig. 5 is in the embodiment of the invention and the comparing embodiment, LiMn 2O 4The RAMAN collection of illustrative plates of layer;
Fig. 6 is in the comparing embodiment of the present invention, LiMn 2O 4The SEM photo of layer upper surface;
Fig. 7 a is in the embodiment of the invention, LiMn 2O 4The SEM photo of layer upper surface;
Fig. 7 b is in the embodiment of the invention, LiMn 2O 4The TEM light field photo of layer upper surface;
Fig. 8 is in the comparing embodiment of the present invention, the capacitance curve of charge and discharge cycles under the room temperature;
Fig. 9 is in the comparing embodiment of the present invention, the capacitance curve of charge and discharge cycles under the high temperature;
Figure 10 is in the embodiment of the invention, the capacitance curve of charge and discharge cycles under the room temperature; And
Figure 11 is in the embodiment of the invention, the capacitance curve of charge and discharge cycles under the high temperature.Wherein, main element symbol description:
1~positive pole; 2~holding area; 3~negative pole 3;
5~barrier film; 6~encapsulating structure; 7~top electrode;
8~anode shield; 9~closed magnetic field; 10~bottom electrode.
Embodiment
The present invention provides a kind of lithium battery anode and forming method thereof.At first, form lithium metal oxide on substrate.Substrate can be stainless steel, polyamide (polyamide), acrylonitrile-butadiene-styrene copolymer (ABS), mica, glass, PET (PET), polyparaphenylene Ben Bing Er oxazole (PBO) or epoxy resin.Lithium metal oxide is common positive electrode, like LiMnO 2, LiMn 2O 4, LiCoO 2, Li 2Cr 2O 7, Li 2CrO4, LiNiO 2, LiFeO 2, LiNi xCo 1-xO 2, LiFePO 4, LiMn 0.5Ni 0.5O 2, LiMn 1/3Co 1/3Ni 1/3O 2, LiMc 0.5Mn 1.5O 4, or above-mentioned combination, wherein 0<x<1, and Mc is a divalent metal.Generation type has three major types: the compacting of (1) conventional powder; (2) vapour deposition; Melt plating, low pressure gas phase deposition (LPCVD), rapid heat chemical vapour deposition (RTCVD), ald (ALD) or physical vapor deposition (PVD), magnetic control sputtering plating (magnetron sputtering), radio frequency sputter (RF sputtering), radio frequency plasma sputter (RF plasma sputtering) like plasma enhanced chemical vapor deposition (PECVD), laser; (3) the synthetic deposition of chemical solution; As dissolving gel coated, electrochemistry plating, the synthetic deposition of hydro-thermal etc.So far, then form thickness approximately between the thick film lithium alloy oxide layer of the film of 50nm to 2000nm or 2~100 μ m on substrate.
In an embodiment of the present invention, can be known by the SEM photo of tangent plane that the lithium alloy oxide layer that above-mentioned preparation technology forms is not fine and close, the SEM photo of its upper surface is also uneven.If directly said structure is used as positive electrode, its capacitance will significantly reduce for several times at cycle charge discharge.
In order to improve the problems referred to above, after forming the lithium alloy oxide layer, carry out committed step of the present invention.The present invention applies extra Cement Composite Treated by Plasma to the lithium alloy oxide layer, and characteristics are that low-yield high-density plasma is handled.After this handled, the upper surface of lithium alloy oxide layer had and engages each other closely, and average fine and close, crystal grain is between the nanocrystal of 3nm~10nm, and lower inner is then kept former bigger grainiess.Can know that through ESCA and X-Ray diffracting spectrum the surface before and after the Cement Composite Treated by Plasma has identical chemical composition and crystalline texture, only changes the surface microstructure size.Cement Composite Treated by Plasma does not make the lithium alloy oxide layer produce unnecessary reactions such as redox, and RAMAN spectrum shows the generation of upper surface nanocrystalline structure simultaneously.Above-mentioned plasma preparation technology's source can be radio frequency plasma or microwave plasma, and its power is looked and is processed material size and decides, and being processed the power density of bearing on the surface is 0.8W/cm 2To 5W/cm 2Between.If power is less than 0.8W/cm 2The time, will cross because of plasma density and low can't produce treatment effect, but if power greater than 4W/cm 2The time, high-energy will take place, highdensity plasma collapse material surface or cause the phenomenon of grain coarsening.Above-mentioned plasma preparation technology's atmosphere is preferably noble gas such as argon gas, to avoid producing unnecessary reaction.If the positive electrode that is processed contains the high oxidation state metal like the cobalt of 3~4 valencys or manganese etc., then also can use oxygen.Low-yield for making plasma reach high density, plasma chamber can add anode shield, inductive coupler coils, closed magnetic field, and its purpose makes plasma density between 10 11~10 13Cm -3, electron temperature is between 1~2eV, and if if relevant parameter can't produce treatment effect low excessively, but when too high, high-energy will take place, the highdensity plasma collapse material surface or the phenomenon of phase change significantly.Plasma preparation technology's time is between between the 5min to 60min, if will uniform treatment less than 5min, but if will influence processed material inside greater than 60min, causes plasma collapse.This plasma preparation technology belongs to low temperature preparation technology, is processed the material temperature and is controlled at and is lower than 150 ℃.If greater than 150 ℃ of flexible substrates that will destroy non-refractory.
It should be noted that; Though partly form the lithium alloy oxide layer with board in the known skill with plasma device; But its plasma is in order to preparation technologies such as assistant depositing or sputters; After deposition or sputter finish, also end thereupon, and above-mentionedly still have rough upper surface with the auxiliary lithium alloy oxide layer that forms of plasma.Though partly known skill imposes additional plasma and handles the lithium alloy oxide layer; But the plasma source design and the plasma parameter that do not have present technique; Accurate control and treatment result; Change the overall structure that is processed material on the contrary, cause phenomenons such as grain coarsening, phase change, destruction, do not have the effect that promotes battery performance.
In an embodiment of the present invention, substrate adopts material such as stainless steel than rigidity or to carry out high tempering preparation technology after the processing before above-mentioned plasma reason.Above-mentioned high tempering preparation technology as if lower less than 300 ℃ of relatively poor capacitances of material crystallinity, but if will produce the high temperature dephasign greater than 700 ℃ between 300 to 700 ℃.
Lithium metal oxide layer through plasma treated surface can be used as anode material of lithium battery.Above-mentioned positive electrode can be used but be not limited to lithium battery shown in Figure 1.In Fig. 1, has barrier film 5 between positive pole 1 and the negative pole 3, in order to definition holding area 2.In holding area 2, contain electrolyte solution.In addition, outside said structure encapsulating structure 6, in order to clad anode 1, negative pole 3, barrier film 5 and electrolyte solution.
Negative pole 3 comprises carbide and lithium alloy.Carbide can be toner body, graphite, carbon fiber, CNT or above-mentioned mixture.In an embodiment of the present invention, carbide is a toner body, and particle diameter is approximately between 5 μ m to 30 μ m.Lithium alloy can be LiAl, LiZn, Li 3Bi, Li3Cd, Li 3Sb, Li 4Si, Li 4.4Pb, Li 4.4Sn, LiC 6, Li 3FeN 2, Li 2.6Co 0.4N, Li 2.6Cu 0.4N or above-mentioned combination.Except above-mentioned two kinds of materials, negative pole 3 can further comprise metal oxide such as SnO, SnO 2, GeO, GeO 2, In 2O, In 2O 3, PbO, PbO 2, Pb 2O 3, Pb 3O 4, Ag 2O, AgO, Ag 2O 3, Sb 2O 3, Sb 2O 4, Sb 2O 5, SiO, ZnO, CoO, NiO, FeO or above-mentioned combination.In addition, negative pole 3 can further have macromolecule sticker (polymer binder), in order to increase the engineering properties of electrode.The proper polymer sticker can be Kynoar (polyvinylidene fluoride; Abbreviation PVDF), styrene butadiene ribber (styrene-butadiene rubber is called for short SBR), polyamide (polyamide), melmac (melamine resin) or above-mentioned composition.
Above-mentioned barrier film 5 is an insulating material, can be polyethylene (PE), polypropylene (PP) or above-mentioned sandwich construction such as PE/PP/PE.
The Main Ingredients and Appearance of above-mentioned electrolyte solution is organic solvent, lithium salts and additive.Organic solvent can be γ-butyl lactone (γ-butyrolactone; Abbreviation GBL), ethylene carbonate (ethylene carbonate is called for short EC), propene carbonate (propylene carbonate is called for short PC), diethyl carbonate (diethyl carbonate; Vehicle economy C), propyl acetate (propyl acetate; Abbreviation PA), dimethyl carbonate (dimethyl carbonate is called for short DMC), methyl ethyl carbonate (ethylmethyl carbonate is called for short EMC) or above-mentioned combination.Lithium salts can be LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiClO 4, LiAlCl 4, LiGaCl 4, LiNO 3, LiC (SO 2CF 3) 3, LiN (SO 2CF 3) 2, LiSCN, LiO 3SCF 2CF 3, LiC 6F 5SO 3, LiO 2CCF 3, LiSO 3F, LiB (C 6H 5) 4, LiCF 3SO 3, or above-mentioned combination.Additive comprises common vinylene carbonate (vinylene carbonate, be called for short VC), also can further contain the inventor in the patent of application a little earlier (Taiwan application number: the 96145902) compound of described maleimide system.
The plasma source design that plasma surface treatment is used is like Fig. 2; Top electrode 7 is single pole plate or inductance coil or microwave generator, and anode shield 8 is set between last bottom crown, through adjustable electric capacity and ground end coupling; Sealed in external enclosed magnetic field 9 is processed material and places lower electrode plate 10.
Because of the present invention just having higher capacitance and selling life than long circulation, the lithium battery of using above-mentioned electrode also has preferable performance performance thereupon.
For let state on the present invention with other purpose, characteristic and advantage can be more obviously understandable, explain as follows with embodiment.
[embodiment]
Anodal preparation:
Comparing embodiment 1
Form the thick LiMn of 500nm with the magnetic control sputtering plating method 2O 4On 304 stainless steel substrates (available from Yong Faxin Industrial Co., Ltd), then carry out 600 ℃ of tempering steps.Above-mentioned LiMn 2O 4The collection of illustrative plates that electronic diffraction is carried out on layer process FIB (Focused Ion Beam) cutting-out top layer is shown in Fig. 3 a, and the ESCA collection of illustrative plates is as shown in Figure 4, and the RAMAN collection of illustrative plates is as shown in Figure 5, and the SEM photo of upper surface is as shown in Figure 6.Can know by Fig. 6, without the LiMn of additional plasma processing 2O 4The upper surface of layer is uneven and crystal grain is thick.
Embodiment 1
Form the thick LiMn of 500nm with the magnetic control sputtering plating method 2O 4On stainless steel substrate.Behind the sputter, then carry out 600 ℃ of tempering steps.Follow RF plasma processing LiMn 2O 4Layer, the power that this plasma is handled are that 30 watts, atmosphere are that to be lower than 100 ℃, time be 30min for argon gas, temperature.LiMn after the above-mentioned Cement Composite Treated by Plasma 2O 4Its ESCA collection of illustrative plates of layer is as shown in Figure 4, and the RAMAN collection of illustrative plates is as shown in Figure 5.
Embodiment 2
Similar with embodiment 1, difference is that the power of Cement Composite Treated by Plasma is increased to 50 watts.LiMn after the above-mentioned Cement Composite Treated by Plasma 2O 4Layer also pass through FIB (Focused Ion Beam) downcut carry out electronic diffraction in the top layer collection of illustrative plates shown in Fig. 3 b, the ESCA collection of illustrative plates is as shown in Figure 4, the RAMAN collection of illustrative plates is as shown in Figure 5, the SEM photo of upper surface is shown in Fig. 7 a.Can know by Fig. 7 a, through the LiMn of additional plasma processing 2O 4The upper surface of layer is on average fine and close.Because superfine little and nanocrystal fluid-tight engagement generates in the surface, so SEM can't effectively resolve, and Fig. 7 b be the TEM light field image at position, identical top layer with Fig. 3 b, the nanocrystalline structure of demonstration fluid-tight engagement.
Embodiment 3
Similar with embodiment 1, difference is that the power of Cement Composite Treated by Plasma is increased to 80 watts.LiMn after the above-mentioned Cement Composite Treated by Plasma 2O 4Its ESCA collection of illustrative plates of layer is as shown in Figure 4, and the RAMAN collection of illustrative plates is as shown in Figure 5.
Can know that by the electronic diffraction spectrum of Fig. 3, the ESCA collection of illustrative plates comparison of Fig. 4 comparing embodiment 1 does not change because of plasma preparation technology with the chemical constitution of the surface molecular of embodiment 1-3.Yet the RAMAN collection of illustrative plates of Fig. 5 shows through the low-energy Cement Composite Treated by Plasma of overpopulation, since the surface layer grain nanometerization, wave number 630~660cm -1Between peak value move toward lower wave number.SEM and TEM photo by Fig. 6,7a and 7b can know that Cement Composite Treated by Plasma has effectively been improved the surperficial average degree and the density of lithium alloy oxide layer, and bring out the generation of nano surface crystal grain.
Electrically measure (battery capacity and cycle life):
Comparing embodiment 1
The electrode of comparing embodiment 1 is inserted electrolyte solution (1M LiPF 6EC/EMC), with 0.3mA/mg just/negative current, 1.5-4.5 (V vs.Li/Li +) voltage under room temperature (25 ℃), discharge and recharge experiment, measure its capacitance (mAh/g).As shown in Figure 8, the curve that discharges and recharges for the first time is rightmost curve, and its capacitance is 140mAh/g.Along with the increase of cycle-index, curve begins to move to left, the only surplus 115mAh/g of the 20th time capacitance.
The electrode of comparing embodiment 1 is inserted electrolyte solution (1M LiPF 6EC/EMC), with 0.3mA/mg just/negative current, 2.0-4.5 (V vs.Li/Li +) voltage under high temperature (55 ℃), discharge and recharge experiment, measure its capacitance (mAh/g).The curve that discharge and recharge the first time as shown in Figure 9 is rightmost curve, and its capacitance is 400mAh/g.Along with the increase of cycle-index, curve begins to move to left, the only surplus 200mAh/g of the 20th time capacitance.
Embodiment 2
The electrode of embodiment 2 is inserted electrolyte solution (1M LiPF 6EC/EMC), with 0.3mA/mg just/negative current, 2.0-4.5 (V vs.Li/Li +) voltage under room temperature (25 ℃), discharge and recharge experiment, measure its capacitance (mAh/g).Shown in figure 10, the first time, the charging and discharging curve to the 20 time almost overlapped, and all maintained 140mAh/g.
The electrode of embodiment 2 is inserted electrolyte solution (1M LiPF 6EC/EMC), with 0.3mA/mg just/negative current, 1.5-4.5 (V vs.Li/Li +) voltage under high temperature (55 ℃), discharge and recharge experiment, measure its capacitance (mAh/g).The curve that discharges and recharges for the second time is rightmost curve, and its capacitance is 500mAh/g, and is also higher than the capacitance 410mAh/g that discharges and recharges for the first time.But along with the increase of cycle-index, curve begins to move to left, and the 20th time capacitance still has 370mAh/g.
Comparison by Fig. 8-11 can know, and is no matter under the operating environment of high temperature or room temperature, all preferable through the cycle life and the capacitance of the lithium alloy oxide layer of plasma treated surface.
Though the present invention with several embodiment openly as above; Right its is not in order to limit the present invention; Has common knowledge the knowledgeable in the technical field under any; Do not breaking away from the spirit and scope of the present invention, when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking the accompanying Claim book scope person of defining.

Claims (10)

1. the formation method of a positive pole comprises:
One substrate is provided;
Form a lithium alloy oxide layer on this substrate; And
With this lithium alloy oxide layer of high density low energy plasma modification, its upper surface is formed engage each other closely and average fine and close nanocrystal, lower inner is then kept former bigger grainiess,
The power density that the power of this high density low energy plasma puts on this lithium alloy oxide layer upper surface is 0.8W/cm 2To 5W/cm 2Between, the density of this high density low energy plasma is between 10 11~10 13Cm -3, and the electron temperature of this high density low energy plasma is between between 1~2eV.
2. the formation method of positive pole according to claim 1, wherein this substrate comprises stainless steel, polyamide, acrylonitrile-butadiene-styrene copolymer, mica, glass, PET, polyparaphenylene Ben Bing Er oxazole or epoxy resin.
3. the formation method of positive pole according to claim 1, wherein this lithium alloy oxide comprises LiMnO 2, LiMn 2O 4, LiCoO 2, Li 2Cr 2O 7, Li 2CrO4, LiNiO 2, LiFeO 2, LiNi xCo 1-xO 2, LiFePO 4, LiMn 0.5Ni 0.5O 2, LiMn 1/3Co 1/3Ni 1/3O 2, LiMc 0.5Mn 1.5O 4, or above-mentioned combination, wherein 0<x<1, and Mc is a divalent metal.
4. the formation method of positive pole according to claim 1 wherein forms the step of this lithium alloy oxide layer on this substrate and comprises the synthetic deposition of pressed by powder, vapour deposition or chemical solution.
5. the formation method of positive pole according to claim 1; Wherein in the step with this this lithium alloy oxide layer of high density low energy plasma modification; Its plasma chamber that adopts has an anode shield, inductive coupler coils, reaches closed magnetic field, so that this high density low energy plasma to be provided.
6. the formation method of positive pole according to claim 1, wherein this high density low energy plasma comprises radio frequency plasma or microwave plasma.
7. positive pole, the formation method of positive pole according to claim 1 forms, and comprising:
One substrate; And
One lithium alloy oxide layer is positioned on this substrate;
Wherein the upper surface of this lithium alloy oxide layer has and engages each other closely and average fine and close nanocrystal, and lower inner is then kept bigger grainiess.
8. positive pole according to claim 7, wherein this substrate comprises stainless steel, polyamide, acrylonitrile-butadiene-styrene copolymer, mica, glass, PET, polyparaphenylene Ben Bing Er oxazole or epoxy resin.
9. positive pole according to claim 7, wherein this lithium alloy oxide layer comprises LiMnO 2, LiMn 2O 4, LiCoO 2, Li 2Cr 2O 7, Li 2CrO4, LiNiO 2, LiFeO 2, LiNi xCo 1-xO 2, LiFePO 4, LiMn 0.5Ni 0.5O 2, LiMn 1/3Co 1/3Ni 1/3O 2, LiMc 0.5Mn 1.5O 4, or above-mentioned combination, wherein 0<x<1, and Mc is a divalent metal.
10. lithium battery comprises:
Positive pole as claimed in claim 7;
One negative pole;
One barrier film, between this positive pole and this negative pole to define a holding area;
One electrolyte solution is positioned at this holding area; And
One encapsulating structure, coating should positive poles, this negative pole, this barrier film and this electrolyte solution.
CN2008101751182A 2008-10-27 2008-10-27 Lithium battery, positive electrode and formation method thereof Active CN101728509B (en)

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AU2020264446A1 (en) 2019-04-30 2021-11-18 6K Inc. Mechanically alloyed powder feedstock
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US11590568B2 (en) 2019-12-19 2023-02-28 6K Inc. Process for producing spheroidized powder from feedstock materials
KR20230029836A (en) 2020-06-25 2023-03-03 6케이 인크. Microcomposite alloy structure
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