JP2011006724A - Aluminum alloy sheet superior in laser weldability for battery case cover - Google Patents
Aluminum alloy sheet superior in laser weldability for battery case cover Download PDFInfo
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 abstract description 19
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract 1
- 238000003466 welding Methods 0.000 description 24
- 239000000956 alloy Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 13
- 230000035515 penetration Effects 0.000 description 12
- 229910000765 intermetallic Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Laser Beam Processing (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
本発明は、電池ケースの蓋に用いられるアルミニウム合金板、詳しくは、携帯電話やノートパソコンに使用される角型のリチウムイオン電池などのケースの蓋用として好適なレーザ溶接性に優れたアルミニウム合金板に関する。 The present invention relates to an aluminum alloy plate used for a lid of a battery case, and more specifically, an aluminum alloy excellent in laser weldability suitable for use as a lid for a case such as a rectangular lithium ion battery used in a mobile phone or a notebook computer. Regarding the board.
携帯電話やノート型パーソナルコンピュータ等に組み込まれる部品は軽量であることが強く望まれている。このため、これらに使用される角型リチウムイオン電池のケース本体の材料につても、当初の鋼板やステンレス鋼板に代えてＡ３００３アルミニウム合金板が使われるようになっている。 It is strongly desired that parts incorporated in a mobile phone, a notebook personal computer, etc. be lightweight. For this reason, the A3003 aluminum alloy plate is used instead of the original steel plate or stainless steel plate for the material of the case body of the prismatic lithium ion battery used for these.
角型電池ケース本体は、複数の工程の絞りおよびしごき加工を組み合わせて成形される。Ａｌ−Ｍｎ系のＡ３００３アルミニウム合金は、このような複雑な成形工程を採用しても、光沢のある美しい表面状態を維持しながらケースの薄肉化が可能な素材である。そのため、Ａ３００３アルミニウム合金は、電池のケース本体用素材として多用されている。
Ａ３００３よりなるケース本体の開口部は、純アルミニウム系であるＡ１０５０アルミニウム合金よりなる蓋で覆われ、両者はレーザ溶接によって接合されている。
The square battery case body is formed by combining a plurality of processes of drawing and ironing. The Al-Mn-based A3003 aluminum alloy is a material that can reduce the thickness of the case while maintaining a glossy and beautiful surface state even when such a complicated molding process is adopted. Therefore, A3003 aluminum alloy is frequently used as a battery case body material.
The opening of the case body made of A3003 is covered with a lid made of a pure aluminum-based A1050 aluminum alloy, and both are joined by laser welding.
ところで、近年、リチウムイオン電池については、さらに軽量化、高容量化が求められており、角型電池ケースにおいても一層の薄肉化が要請されている。薄肉化は内容積の増加に直結し、電池特性の高容量化を図る重要な要素である。一方、充放電を繰り返すリチウムイオン電池は、その反応時に内部圧力が上昇し、クリープ変形により電池ケースが膨らむという問題がある。このようなフクレによる電池ケース本体の厚み変形量が大きい場合には、故障、破損などによる機器への影響が懸念され、単なる薄肉化はこの問題を助長することになりかねない。そのため、内部圧力によるフクレを抑制する角型電池ケース用アルミニウム材料として、Ａ３００５や、Ｍｎ、Ｃｕ、Ｍｇを含有し、強度を改善したアルミニウム合金が提案されている（特許文献１、特許文献２参照）。 By the way, in recent years, further reduction in weight and capacity has been demanded for lithium ion batteries, and further reduction in thickness has been demanded for square battery cases. Thinning is directly related to the increase in internal volume, and is an important factor for increasing the battery capacity. On the other hand, a lithium ion battery that repeatedly charges and discharges has a problem that the internal pressure increases during the reaction and the battery case expands due to creep deformation. When the thickness deformation amount of the battery case main body due to such swelling is large, there is a concern about the influence on the device due to failure, breakage, etc., and mere thinning may promote this problem. Therefore, an aluminum alloy containing A3005, Mn, Cu, and Mg and having improved strength has been proposed as an aluminum material for a prismatic battery case that suppresses swelling due to internal pressure (see Patent Document 1 and Patent Document 2). ).
電池ケースは、上述したごとく、ケース本体と蓋体からなり、レーザ溶接によってケース本体に蓋体を接合している。上記のごとくケース本体の薄肉化を図れば、その材料の強度改善をしても溶接部位の強度が低下してしまう。そのため、電池ケースの薄肉化が進むにつれて、ケース本体と蓋体との接合強度もより高いものとすることが求められている。 As described above, the battery case includes a case body and a lid, and the lid is joined to the case body by laser welding. If the thickness of the case body is reduced as described above, the strength of the welded portion will decrease even if the strength of the material is improved. Therefore, as the battery case becomes thinner, it is required that the bonding strength between the case main body and the lid body be higher.
電池ケースの場合、レーザ溶接をする際に、通常、蓋体の近傍には樹脂パーツが位置している。そのため、溶接時には、樹脂パーツに影響がないよう、できるだけ小さな入熱で接合することが望まれている。それ故、溶接部位に対する入熱（出力）を増やす方策は採ることができない。 In the case of a battery case, resin parts are usually located in the vicinity of the lid when performing laser welding. Therefore, at the time of welding, it is desired to join with as little heat input as possible so that the resin parts are not affected. Therefore, it is not possible to take measures to increase the heat input (output) to the welded part.
さらに、ケース本体の薄肉化、つまり、ケース本体及び蓋体の薄肉化に伴って、レーザ溶接時の溶接割れが生じやすくなる。そこで、電池ケースの蓋体用のアルミニウム材料として、純アルミニウム系と同等の成形加工性を有するとともに、レーザ溶接による溶接強度を向上できるアルミニウム合金材料が要請されている。それには、レーザ溶接時に入熱量を上げなくても、同じ入熱で溶け込み深さが大きくなるアルミニウム合金材料の開発が必要である。 Furthermore, as the case main body becomes thinner, that is, as the case main body and the lid body become thinner, weld cracks during laser welding tend to occur. Thus, there is a demand for an aluminum alloy material for a battery case lid that has a formability equivalent to that of a pure aluminum material and can improve the welding strength by laser welding. To this end, it is necessary to develop an aluminum alloy material that can increase the penetration depth with the same heat input without increasing the heat input during laser welding.
本発明は、かかる要請に基づいてなされたものであって、レーザ溶接時、同じ入熱量で従来の純アルミニウム系材料よりも溶け込み深さを大きくすることができる電池ケース蓋用アルミニウム合金板を提供することにある。 The present invention has been made based on such a demand, and provides an aluminum alloy plate for a battery case lid that can have a greater penetration depth than conventional pure aluminum materials with the same heat input during laser welding. There is to do.
本発明は、Ｓｉ：０．３〜２．０％（質量％、以下同じ）、Ｆｅ：０．５〜１．５％を含有し、さらに、Ｉｎ：０．０１〜０．０５％、Ｂｉ：０．０５〜０．２０％、Ｓｎ：０．０１〜０．０５％の１種または２種以上を含有し、残部がＡｌおよび不可避的不純物からなることを特徴とするレーザ溶接性に優れた電池ケース蓋用アルミニウム合金板にある（請求項１）。 The present invention contains Si: 0.3-2.0% (mass%, hereinafter the same), Fe: 0.5-1.5%, In: 0.01-0.05%, Bi : 0.05 to 0.20%, Sn: 0.01 to 0.05% of one or two or more types, the balance being made of Al and inevitable impurities, excellent laser weldability The battery case lid has an aluminum alloy plate (claim 1).
本発明の電池ケース蓋用アルミニウム合金板は、上記特定の成分組成を有している。これにより、電池ケース蓋として用い、これをレーザ溶接により電池ケース本体とと接合する際に、入熱量を増加させることなく溶け込み深さを大きくすることができ、溶接部の強度を従来の純アルミニウム系材料の場合よりも高めることができる。そして、入熱量を上げる必要がないので、電池の樹脂パーツなどに影響を与えることも回避することができる。そのため、上記電池ケース蓋用アルミニウム合金板として、非常に好適である。特に、広く普及している角型リチウムイオン電池ケースの蓋用として好適である。 The aluminum alloy plate for a battery case lid of the present invention has the above specific component composition. This makes it possible to increase the penetration depth without increasing the amount of heat input when using this as a battery case lid and joining it to the battery case main body by laser welding, and the strength of the welded portion is reduced to that of conventional pure aluminum. It can be higher than the case of the system material. And since it is not necessary to raise the amount of heat input, it can also avoid affecting the resin parts of a battery, etc. Therefore, it is very suitable as the aluminum alloy plate for the battery case lid. In particular, it is suitable for a lid of a widely used prismatic lithium ion battery case.
本発明の電池ケース蓋用アルミニウム合金板における合金成分の意義およびその限定理由について説明する。
Ｓｉ：０．３〜２．０％、
Ｓｉは、ＡｌやＦｅと結合して金属間化合物を形成し、レーザ溶接時の溶け込み深さを向上させる効果がある。そのためのＳｉ含有量は、０．３％以上、２．０％以下の範囲である。Ｓｉ含有量が０．３％未満の場合は、金属間化合物の形成が不充分であり、溶け込み深さが向上しない。その含有量が２．０％超えの場合は、鋳造時に１００μｍ以上の粗大な晶出物（金属間化合物）を形成し、製板の状態でも１５μｍ以上の金属間化合物として存在することになり、割れ感受性が大きくなってしまい、レーザ溶接時に割れやすくなる。
The significance of the alloy component in the aluminum alloy plate for battery case cover of the present invention and the reason for limitation thereof will be described.
Si: 0.3 to 2.0%,
Si combines with Al and Fe to form an intermetallic compound, and has the effect of improving the penetration depth during laser welding. Therefore, the Si content is in the range of 0.3% to 2.0%. When the Si content is less than 0.3%, the formation of intermetallic compounds is insufficient and the penetration depth does not improve. When the content exceeds 2.0%, a coarse crystallized product (intermetallic compound) of 100 μm or more is formed at the time of casting, and it is present as an intermetallic compound of 15 μm or more even in the state of plate making. Crack susceptibility is increased, and it becomes easier to crack during laser welding.
Ｆｅ：０．５〜１．５％、
ＦｅもＡｌやＳｉと結合して金属間化合物を形成し、レーザ溶接時の溶け込み深さを向上させる効果がある。そのためのＦｅ含有量は、０．５％以上、１．５％以下の範囲である。Ｆｅ含有量が０．５％未満の場合は、金属間化合物の形成が不充分であり、溶け込み深さが向上しない。その含有量が１．５％超えの場合は、鋳造時に１００μｍ以上の粗大な晶出物（金属間化合物）を形成し、製板の状態でも１．５μｍ以上の金属間化合物として存在することになり、割れ感受性が大きくなってしまい、レーザ溶接時に割れやすくなる。
Fe: 0.5 to 1.5%,
Fe also binds to Al and Si to form an intermetallic compound, and has the effect of improving the penetration depth during laser welding. Therefore, the Fe content is in the range of 0.5% to 1.5%. When the Fe content is less than 0.5%, the formation of intermetallic compounds is insufficient, and the penetration depth does not improve. When the content exceeds 1.5%, a coarse crystallized product (intermetallic compound) of 100 μm or more is formed at the time of casting, and it exists as an intermetallic compound of 1.5 μm or more even in the state of sheeting. As a result, cracking susceptibility is increased and cracking is liable to occur during laser welding.
Ｉｎ：０．０１〜０．０５％、
Ｂｉ：０．０５〜０．２０％、
Ｓｎ：０．０１〜０．０５％、
Ｉｎ、Ｓｎ、Ｂｉは、アルミニウムよりも低融点の金属元素であり、アルミニウムマトリックス中にほとんど固溶せず、第２相としてマトリックス中に分散する。この分散がレーザ溶接時の溶け込み深さに効果のあることを本発明者が見いだした。Ｉｎは０．０１〜０．０５％で、Ｂｉは０．０５〜０．２０％で、Ｓｎは０．０１〜０．０５％でその効果がある。それぞれ下限を下回るとその効果が得られず、上限を上回る場合は、レーザ溶接時の割れ感受性が大きくなってしまい、レーザ溶接時に割れやすくなる。Ｉｎ、Ｓｎ、Ｂｉはそれぞれ単独含有でもよいし、２種あるいは３種を組み合わせて含有してもよい。
In: 0.01 to 0.05%,
Bi: 0.05-0.20%,
Sn: 0.01 to 0.05%,
In, Sn, and Bi are metal elements having a melting point lower than that of aluminum, hardly dissolve in the aluminum matrix, and are dispersed in the matrix as the second phase. The present inventor has found that this dispersion has an effect on the penetration depth during laser welding. In is 0.01 to 0.05%, Bi is 0.05 to 0.20%, and Sn is 0.01 to 0.05%. If the value is below the lower limit, the effect cannot be obtained. If the value exceeds the upper limit, the cracking sensitivity at the time of laser welding is increased, and cracking is likely at the time of laser welding. In, Sn, and Bi may be contained alone or in combination of two or three.
Ｆｅ、Ｓｉ及びＩｎ、Ｓｎ、Ｂｉの１種または２種以上以外の残部は、上述したごとく、Ａｌおよび不可避的不純物である。ここで、不可避的不純物は、合金の製造上の問題から取り除くことが困難な成分である。
例えば、Ｃｕ、Ｍｎ、Ｍｇ、Ｃｒ、Ｚｎについては０．１％以下、好ましくは０．０５％以下までは不可避的不純物として含むことができる。
なお、Ｆｅ、Ｓｉ及びＩｎ、Ｓｎ、Ｂｉの１種または２種以上の上述した作用効果を阻害しない限り、微量（０．０３％以下）の範囲で他の元素を故意に添加した場合であっても、これは上記不可避的不純物と同等に扱うことができる。
The balance other than Fe, Si and In, Sn, or Bi other than one or more is Al and inevitable impurities as described above. Here, inevitable impurities are components that are difficult to remove due to problems in manufacturing the alloy.
For example, Cu, Mn, Mg, Cr and Zn can be included as inevitable impurities up to 0.1% or less, preferably up to 0.05% or less.
It should be noted that unless one or more of the above-described effects of Fe, Si, In, Sn, and Bi were inhibited, other elements were intentionally added in a small amount (0.03% or less). However, this can be handled in the same way as the above inevitable impurities.
また、さらに、Ｔｉ：０．００５〜０．１５％、Ｂ：５〜５００ｐｐｍを含有していることが好ましい（請求項２）。Ｔｉ、Ｂは、鋳造組織を微細化して、製品の成形性を安定化させることができるので、上記範囲において添加することが好ましい。 Furthermore, it is preferable that Ti: 0.005 to 0.15% and B: 5 to 500 ppm are contained (Claim 2). Since Ti and B can refine the cast structure and stabilize the moldability of the product, it is preferable to add Ti and B in the above range.
（実施例１）
本発明の実施例にかかる電池ケース蓋用アルミニウム合金板につき、比較例と対比して説明する。
本例の実施例としては、表１に示す合金Ｎｏ．１〜１４の合金を準備した。これらは、いずれも、Ｓｉ：０．３〜２．０％（質量％、以下同じ）、Ｆｅ：０．５〜１．５％を含有し、さらに、Ｉｎ：０．０１〜０．０５％、Ｂｉ：０．０５〜０．２０％、Ｓｎ：０．０１〜０．０５％の１種または２種以上を含有し、残部がＡｌおよび不可避的不純物からなる。
Example 1
An aluminum alloy plate for a battery case cover according to an embodiment of the present invention will be described in comparison with a comparative example.
As an example of this example, alloy no. 1 to 14 alloys were prepared. These all contain Si: 0.3-2.0% (mass%, the same applies hereinafter), Fe: 0.5-1.5%, and In: 0.01-0.05% , Bi: 0.05 to 0.20%, Sn: 0.01 to 0.05%, or two or more kinds, and the balance is made of Al and inevitable impurities.
比較例としては、表１に示す合金Ｎｏ．１５〜２２を準備した。これらの合金は、成分範囲が上記適正範囲から外れたものである。
実施例の合金Ｎｏ．１〜１４及び比較例の合金Ｎｏ．１５〜２２は、いずれも、半連続鋳造により造塊した。なお、いずれの合金も、鋳造組織微細化のために、Ｔｉ：０．０１％とＢ：５０ｐｐｍを添加した。得られた鋳塊に、均質化処理、熱間圧延、冷間圧延を施して、厚さ０．８ｍｍの板材とした。その後、板材に対し３８０℃の温度で３時間保持する最終熱処理を行い、得られた板材を試験材とした。
As a comparative example, alloy No. shown in Table 1 was used. 15-22 were prepared. In these alloys, the component range is out of the appropriate range.
Alloy No. of Example 1 to 14 and Comparative Example Alloy Nos. 15 to 22 were all ingoted by semi-continuous casting. In each alloy, Ti: 0.01% and B: 50 ppm were added to refine the cast structure. The obtained ingot was subjected to homogenization treatment, hot rolling, and cold rolling to obtain a plate material having a thickness of 0.8 mm. Thereafter, final heat treatment was performed on the plate material at a temperature of 380 ° C. for 3 hours, and the obtained plate material was used as a test material.
各合金の試験材について、次の方法により、レーザ溶接時の割れ感受性の評価を行った。
・レーザ溶接機：半導体励起パルス発信型ＹＡＧレーザ（片岡製作所製ＨＰ３００β）、
・レーザ出力：２１０Ｗ、
・溶接方法：上記試験材と同じ厚さのＪＩＳ１０５０のＯ材からなる板材を準備し、これを上記試験材に突き合わせて、その突き合わせ部にレーザ溶接のスポットを照射し、このスポットと突き合わせ部を９００ｍｍ／分で相対移動させてレーザ溶接した。
About the test material of each alloy, the crack sensitivity at the time of laser welding was evaluated by the following method.
Laser welding machine: Semiconductor excitation pulse transmission type YAG laser (HP300β manufactured by Kataoka Seisakusho),
・ Laser output: 210 W
-Welding method: A plate material made of JIS 1050 O material having the same thickness as the above test material is prepared, and this is abutted against the above test material, and a laser welding spot is irradiated to the abutting portion. Laser welding was performed with relative movement at 900 mm / min.
・溶け込み深さ評価方法：溶接継手断面を溶接方向に２ｃｍ間隔で５断面顕微鏡観察し、その最大溶け込み深さの平均値を算出した。溶け込み深さが１４０μｍ以上を合格とし、１４０μｍ未満は溶接不良として不合格と判断した。
・割れ感受性評価方法：溶接継手部位に割れが発生しているかどうかを、当該溶接継手部位の断面を顕微鏡観察することにより確認し、割れが無い場合は合格、一方、割れがある場合は、割れ感受性が高いことから不合格とした。
-Penetration depth evaluation method: The cross section of the welded joint was observed with a five-section microscope at intervals of 2 cm in the welding direction, and the average value of the maximum penetration depth was calculated. A penetration depth of 140 μm or more was judged as acceptable, and a depth of less than 140 μm was judged as unacceptable as poor welding.
・ Crack susceptibility evaluation method: Check whether the welded joint part is cracked by observing the cross section of the welded joint part under a microscope. It was rejected because of its high sensitivity.
評価結果を表１に示す。
表１から知られるように、本発明の実施例としての合金Ｎｏ．１〜１４は、いずれも溶け込み深さが１４０μｍ以上であり、かつ、割れがないのに対して、比較例としての合金Ｎｏ．１５〜２２は、溶け込み深さが１４０μｍ未満か、割れ発生のいずれかに該当し、不合格となった。
この結果から、本発明の合金は、レーザ溶接性に優れ、電池ケース蓋用アルミニウム合金板として好適であることがわかる。
The evaluation results are shown in Table 1.
As can be seen from Table 1, alloy no. Nos. 1 to 14 have a penetration depth of 140 μm or more and no cracks, whereas alloy No. 1 as a comparative example. Nos. 15 to 22 corresponded to either the penetration depth of less than 140 μm or the occurrence of cracks, and failed.
From this result, it can be seen that the alloy of the present invention is excellent in laser weldability and suitable as an aluminum alloy plate for a battery case lid.
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| WO2017190588A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser cladding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017190588A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser cladding |
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