JP4739462B1 - Si-based alloy negative electrode material with excellent conductivity - Google Patents
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Abstract
【課題】リチウムイオン２次電池やハイブリットキャパシタなど、充放電時にリチウムイオンの移動を伴う蓄電デバイスのＳｉ系合金負極材料を提供する。
【解決手段】Ｓｉ相とＳｉとＣｕとの金属間化合物であるＳｉｘＣｕｙ合金からなるＳｉｘＣｕｙ相の複合相からなる粉体であり、かつＳｉｘＣｕｙ相の組成がｘ＜ｙであることを特徴とする導電性に優れるＳｉ系合金負極材料。上記ＳｉｘＣｕｙ合金である金属間化合物の組成がＳｉＣｕ3であることを特徴とする導電性に優れるＳｉ系合金負極材料。
【選択図】図１The present invention provides a Si-based alloy negative electrode material for an electricity storage device such as a lithium ion secondary battery and a hybrid capacitor that accompanies the movement of lithium ions during charging and discharging.
A conductive material comprising a composite phase of a SixCuy phase composed of a SixCuy alloy which is an intermetallic compound of Si phase and Si and Cu, and the composition of the SixCuy phase is x <y. Si-based alloy negative electrode material with excellent properties. A Si-based alloy negative electrode material having excellent electrical conductivity, wherein the composition of the intermetallic compound which is the SixCuy alloy is SiCu 3 .
[Selection] Figure 1
Description
本発明は、リチウムイオン２次電池やハイブリットキャパシタなど、充放電時にリチウムイオンの移動を伴う蓄電デバイスの導電性に優れるＳｉ系合金負極材料に関するものである。 The present invention relates to a Si-based alloy negative electrode material that is excellent in electrical conductivity of an electricity storage device that moves lithium ions during charge and discharge, such as a lithium ion secondary battery and a hybrid capacitor.
近年、携帯機器の普及に伴い、リチウムイオン電池を中心とした高性能２次電池の開発が盛んに行われている。さらには自動車用や家庭用定置用蓄電デバイスとしてリチウムイオン２次電池やその反応機構を負極に適用したハイブリットキャパシタの開発も盛んになっている。それらの蓄電デバイスの負極材料としては、リチウムイオンを吸蔵・放出することができる、天然黒鉛や人造黒鉛、コークスなどの炭素質材料が用いられている。 In recent years, with the widespread use of portable devices, development of high-performance secondary batteries centered on lithium ion batteries has been actively conducted. Furthermore, lithium-ion secondary batteries as hybrid electric storage devices for automobiles and home use and hybrid capacitors in which the reaction mechanism is applied to the negative electrode are also actively developed. As a negative electrode material for these electricity storage devices, carbonaceous materials such as natural graphite, artificial graphite, and coke that can occlude and release lithium ions are used.
しかし、炭素質材料はリチウムイオンをＣ面間に挿入するため、負極に用いた際の理論容量は３７２ｍＡｈ／ｇが限界であり、高容量化を目的とした炭素質材料に代わる新規材料の探索が盛んに行われている。 However, because carbonaceous materials insert lithium ions between the C-planes, the theoretical capacity when used for the negative electrode is limited to 372 mAh / g, and the search for new materials to replace carbonaceous materials for the purpose of increasing capacity is required. Has been actively conducted.
一方、炭素質材料に代わる材料として、Ｓｉが注目されている。その理由は、ＳｉはＬｉ22Ｓｉ5 で表される化合物を形成して大量のリチウムを吸蔵することができるため、炭素質材料を使用した場合に比較して負極の容量を大幅に増大でき、結果としてリチウムイオン２次電池やハイブリットキャパシタの蓄電容量を増大することができる可能性を持っているためである。 On the other hand, Si has attracted attention as a material that can replace carbonaceous materials. The reason is that since Si can form a compound represented by Li 22 Si 5 and occlude a large amount of lithium, the capacity of the negative electrode can be greatly increased compared to the case where a carbonaceous material is used, As a result, there is a possibility that the storage capacity of the lithium ion secondary battery or the hybrid capacitor can be increased.
しかし、Ｓｉを単独で負極材として使用した場合には、充電時にリチウムと合金化する際の膨張、放電時にリチウムと脱合金化する際の収縮の繰返しによってＳｉ相が微粉化され、使用中に電極基板からＳｉ相が脱落したりＳｉ相間の電気伝導性が取れなくなる等の不具合が生じるために蓄電デバイスとしての寿命が極めて短いといった課題があった。 However, when Si is used alone as a negative electrode material, the Si phase is pulverized by repeated expansion during alloying with lithium during charging and contraction during dealloying with lithium during discharging. There has been a problem that the life of the electricity storage device is extremely short due to problems such as the Si phase dropping off from the electrode substrate and the lack of electrical conductivity between the Si phases.
また、Ｓｉは炭素質材料や金属系材料に比べて電気伝導性が悪く、充放電に伴う電子の効率的な移動が制限されているため、負極材としては炭素質材料など導電性を補う材料と組合せて使用されるが、その場合でも特に初期の充放電や高効率での充放電特性も課題となっている。 In addition, Si has poor electrical conductivity compared to carbonaceous materials and metal-based materials, and the efficient movement of electrons associated with charge / discharge is limited. Therefore, as a negative electrode material, a material that supplements conductivity, such as a carbonaceous material. However, even in that case, initial charge / discharge characteristics and charge / discharge characteristics with high efficiency are also problems.
このようなＳｉ相を負極として利用する際の欠点を解決する方法として、Ｓｉなどの親リチウム相の少なくとも一部をＳｉと遷移金属に代表される金属との金属間化合物で包囲した材料やその製造方法が提案されている。その一つとして、例えば、特開２００１−２９７７５７号公報（特許文献１）や特開平１０−３１２８０４号公報（特許文献２）などが知られている。 As a method for solving the drawbacks when using such a Si phase as a negative electrode, a material in which at least a part of a parent lithium phase such as Si is surrounded by an intermetallic compound of Si and a metal typified by a transition metal, or the like Manufacturing methods have been proposed. For example, Japanese Patent Laid-Open No. 2001-297757 (Patent Document 1) and Japanese Patent Laid-Open No. 10-31804 (Patent Document 2) are known.
また、別の解決方法として、Ｓｉ相を含む活物質の相をリチウムと合金化しないＣｕなどの導電性材料で被覆した電極やその製造方法が提案されている。例えば、特開２００４−２２８０５９号公報（特許文献３）や特開２００５−４４６７２号公報（特許文献４）などが知られている。
しかしながら、上述した活物質の相をＣｕなどの導電性材料で被覆する方法では、Ｓｉ相を含む活物質を電極に形成する工程の前または後にめっきなどの方法で被覆する必要があり、また、被覆膜厚の制御など工業的に手間がかかるという問題がある。 However, in the above-described method of coating the active material phase with a conductive material such as Cu, it is necessary to coat the active material containing the Si phase with a method such as plating before or after the step of forming the active material on the electrode. There is a problem that it takes time and labor from the industrial point of view, such as controlling the coating thickness.
また、Ｓｉなどの親リチウム相の少なくとも一部を金属間化合物で包囲した材料は溶融後の凝固プロセス中に親リチウム相と金属間化合物が形成されるため、工業的に好ましいプロセスといえるが、提案されている元素の組合せではＳｉ相と平衡する殆どの金属間化合物は電気伝導性に劣るＳｉリッチな化合物になるためＣｕめっきに比べて、特に、初期の充放電特性や高効率での充放電特性に劣る欠点があった。また、これまでの提案ではそれらの課題を解決できるような電気伝導性に優れた金属間化合物の組成に関するものはない。 In addition, a material in which at least a part of a parent lithium phase such as Si is surrounded by an intermetallic compound is an industrially preferable process because a parent lithium phase and an intermetallic compound are formed during a solidification process after melting. In the proposed combination of elements, most of the intermetallic compounds that are in equilibrium with the Si phase become Si-rich compounds that are inferior in electrical conductivity. There was a drawback of poor discharge characteristics. In addition, there is no proposal related to the composition of an intermetallic compound excellent in electrical conductivity that can solve these problems.
上述のような問題を解消するために、発明者らは鋭意開発を進めた結果、Ｓｉ相を包囲する金属間化合物として、Ｓｉ相との多くの金属間化合物のなかでもＣｕ元素との金属間化合物が特に電気伝導性に優れたＳｉＣｕ3 を形成することと、Ｓｉ相とＳｉＣｕ3 合金からなる複合相とすることで、Ｓｉの大きな放電容量を活かし、かつＳｉ本来の低い導電性を導電性に優れたＳｉＣｕ3 が補う効果によって、放電容量とサイクル寿命のいずれも良好であることを見出し発明に至った。その発明の要旨は、
（１）Ｓｉ相とＳｉとＣｕとの金属間化合物であるＳｉｘＣｕｙ合金がＳｉＣｕ 3 相の複合相からなる粉体であって、Ｓｉ相を構成するＳｉの１部をＣ，Ｇｅ，Ｓｎ，Ｐｂ，ＡｌおよびＰからなる群から選ばれた１種または２種以上の元素で置換したＳｉを主とするＳｉ相であり、該Ｓｉを主相とするＳｉ相の平均粒径を１０μｍ以下とし、該Ｓｉ相の少なくとも１部をＳｉＣｕ 3 相で取り囲んでなることにより、初期放電容量が１０００ｍＡｈ／ｇ以上で、１００サイクル目の放電容量が３７２ｍＡｈ／ｇ以上であることを特徴とする導電性に優れたＳｉ系合金負極材料にある。
In order to solve the above-mentioned problems, the inventors have made extensive developments. As a result, the intermetallic compound surrounding the Si phase is a metal intermetallic compound with Cu element among many intermetallic compounds with the Si phase. The compound forms SiCu 3 with excellent electrical conductivity and a composite phase composed of Si phase and SiCu 3 alloy, making use of the large discharge capacity of Si and making the inherent low conductivity of Si conductive. the superior SiCu 3 supplements effect, leading to see out the invention that it is better neither of the discharge capacity and cycle life. The gist of the invention is
(1) A SixCuy alloy, which is an intermetallic compound of Si phase and Si and Cu, is a powder composed of a composite phase of SiCu 3 phase, and a part of Si constituting the Si phase is C, Ge, Sn, Pb. , Si and mainly Si substituted with one or more elements selected from the group consisting of Al and P, the average particle size of the Si phase mainly Si is 10 μm or less, By having at least a part of the Si phase surrounded by a SiCu 3 phase, the initial discharge capacity is 1000 mAh / g or more, and the discharge capacity at the 100th cycle is 372 mAh / g or more. Si-based alloy negative electrode material.
以上述べたように、本発明による電気伝導性に優れたＳｉＣｕ3 を使用することによりＳｉの導電性を補い、良好なサイクル寿命を示す負極材料を確実に得ることができ、放電容量とサイクル寿命のいずれも良好で、２次負極材料の提供を可能とする優れた効果を奏するものである。 As described above, by using SiCu 3 having excellent electrical conductivity according to the present invention, it is possible to supplement the conductivity of Si, and to reliably obtain a negative electrode material having a good cycle life, and to have a discharge capacity and a cycle life. All of these are good and exhibit an excellent effect of enabling the provision of a secondary negative electrode material.
以下、本発明について図面に従って詳細に説明する。
図１は、Ｓｉ−Ｃｕ二元系の状態図を示す。この図に示すように、Ｓｉ−Ｃｕ合金溶融物を冷却すると液相線温度（例えば、Ｓｉ：６４原子％−Ｃｕ：３６原子％の場合は１２００℃）に達した時に初晶としてＳｉが析出し始める。この初晶は液体急冷法やアトマイズ法のように冷却速度が大きければ粒状晶として析出し、温度が固相線温度（８０２℃）に達するとＳｉとＳｉＣｕ3 の共晶反応が起こり凝固が完了する。このように、Ｓｉリッチ側の状態図ではＳｉ相とＳｉＣｕ3 相との共晶反応であり、Ｓｉ相をＳｉＣｕ3 相が取り囲む組織になる。
The present invention will be described in detail below with reference to the drawings.
FIG. 1 shows a phase diagram of the Si—Cu binary system. As shown in this figure, when the Si—Cu alloy melt is cooled, Si is precipitated as the primary crystal when the liquidus temperature is reached (eg, 1200 ° C. in the case of Si: 64 atomic% —Cu: 36 atomic%). Begin to. This primary crystal precipitates as a granular crystal if the cooling rate is high as in the liquid quenching method or the atomizing method, and when the temperature reaches the solidus temperature (802 ° C.), a eutectic reaction between Si and SiCu 3 occurs and solidification is completed. To do. Thus, in the phase diagram on the Si rich side, it is a eutectic reaction between the Si phase and the SiCu 3 phase, and the Si phase surrounds the SiCu 3 phase.
一方、Ｃｕ以外とＳｉとを合金化させる元素の組合せとして、例えばＦｅ−Ｓｉ、Ｎｉ−Ｓｉ、Ｍｎ−Ｓｉ、Ｃｏ−Ｓｉ、Ｃｒ−Ｓｉ、Ｓｉ−Ｗ、Ｍｏ−Ｓｉ、Ｎｂ−Ｓｉ、Ｓｉ−Ｔｉ、Ｓｉ−Ｖ等が考えられる。しかし、これらは、いずれもＦｅＳｉ2 、ＮｉＳｉ2 、ＣｏＳｉ2 、ＣｒＳｉ2 、ＷＳｉ2 、ＭｏＳｉ2 、ＭｎＳｉ2 、ＮｂＳｉ2 、ＴｉＳｉ2 、ＶＳｉ2 と金属元素よりもＳｉリッチな組成が残ることになる。 On the other hand, as a combination of elements that alloy Si other than Cu, for example, Fe-Si, Ni-Si, Mn-Si, Co-Si, Cr-Si, Si-W, Mo-Si, Nb-Si, Si -Ti, Si-V, etc. are conceivable. However, it will both FeSi 2, NiSi 2, CoSi 2 , CrSi 2, WSi 2, MoSi 2, MnSi 2, NbSi 2, TiSi 2, VSi 2 and the Si-rich composition remains than metal elements .
上記のＳｉと遷移元素との組合せで唯一Ｃｕが金属リッチな化合物（ＳｉＣｕ3 ）としてＳｉ相と平衡する。このＣｕリッチな化合物（ＳｉＣｕ3 ）の抵抗値を調べると、ＳｉＣｕ3 ：１６．３×１０-4Ω・ｍ、同様に、ＦｅＳｉ2 ：１０００×１０-4Ω・ｍ、ＮｉＳｉ2 ：５０×１０-4Ω・ｍ、ＣｏＳｉ2 ：１８×１０-4Ω・ｍとＳｉＣｕ3 が他のシリサイド化合物に比べて抵抗値の低いことが分かる。 The combination of Si and the transition element described above equilibrates with the Si phase as the only Cu-rich compound (SiCu 3 ). When the resistance value of this Cu-rich compound (SiCu 3 ) is examined, it is found that SiCu 3 : 16.3 × 10 −4 Ω · m, similarly FeSi 2 : 1000 × 10 −4 Ω · m, NiSi 2 : 50 × It can be seen that 10 −4 Ω · m, CoSi 2 : 18 × 10 −4 Ω · m and SiCu 3 have lower resistance values than other silicide compounds.
ＳｉＣｕ3 の抵抗値が最も低かった要因は二つあり、一つ目はＳｉＣｕ3 が他のシリサイド化合物に比べて金属リッチな組成であることである。二つ目として、原料の遷移金属元素に注目すると、Ｃｕ：１．７３×１０-4Ω・ｍ、Ｆｅ：１０×１０-4Ω・ｍ、Ｎｉ：１１．８×１０-4Ω・ｍ、Ｃｏ：９．７１×１０-4Ω・ｍ、と単体Ｃｕは他の遷移金属元素と比較しても極めて抵抗値が低く、Ｓｉと最も抵抗値が低くなる遷移金属の組合せであったことである。 There are two factors that have the lowest resistance value of SiCu 3 , and the first is that SiCu 3 has a metal-rich composition compared to other silicide compounds. Secondly, when focusing on the transition metal element of the raw material, Cu: 1.73 × 10 −4 Ω · m, Fe: 10 × 10 −4 Ω · m, Ni: 11.8 × 10 −4 Ω · m , Co: 9.71 × 10 −4 Ω · m, and simple substance Cu had a very low resistance value compared to other transition metal elements, and was a combination of Si and the transition metal having the lowest resistance value It is.
上述のことからも分かるように、遷移金属シリサイド化合物の中で最も低い抵抗値をとるＳｉと遷移金属元素の組合せはＳｉとＣｕである。これは遷移金属シリサイド化合物の原料である単体Ｃｕが他の単体遷移金属元素と比較しても極めて抵抗値が低く、かつＳｉ相とＳｉとの遷移金属元素の組合せでは決して得られないＳｉとＣｕ元素との金属リッチな化合物相（ＳｉｘＣｕｙ（ｘ＜ｙ））、例えば、ＳｉＣｕ3 相の形成が可能であることからである。このように最も抵抗値が低いことから、ＳｉＣｕ3 は上記したＳｉリッチな金属間化合物（ＦｅＳｉ2 、ＮｉＳｉ2 、ＣｏＳｉ2 、ＣｒＳｉ2 、ＷＳｉ2 、ＭｏＳｉ2 、ＭｎＳｉ2 、ＮｂＳｉ2 、ＴｉＳｉ2 、ＶＳｉ2 ）よりも高い電気伝導性を示すことが分かる。 As can be seen from the above, the combination of Si and transition metal element having the lowest resistance value among the transition metal silicide compounds is Si and Cu. This is because Si and Cu, which are raw materials of transition metal silicide compounds, have extremely low resistance values compared to other single transition metal elements, and can never be obtained by a combination of transition metal elements of Si phase and Si. This is because a metal-rich compound phase with the element (SixCuy (x <y)), for example, a SiCu 3 phase can be formed. Thus, since the resistance value is the lowest, SiCu 3 is an Si-rich intermetallic compound (FeSi 2 , NiSi 2 , CoSi 2 , CrSi 2 , WSi 2 , MoSi 2 , MnSi 2 , NbSi 2 , TiSi 2 , It can be seen that the electric conductivity is higher than that of VSi 2 ).
上記のことより、Ｓｉとの遷移金属元素との組合せで唯一ＣｕだけがＳｉ相と金属リッチな化合物（ＳｉＣｕ3 ）相を共晶反応により析出することが分かり、かつこのＳｉＣｕ3 はＳｉ−Ｃｕ二元系状態図からＳｉリッチな組成（例えば、Ｓｉ：６４原子％−Ｃｕ：３６原子％）においてはＳｉ相をＳｉＣｕ3 相が取り囲む組織になっていることも分かっている。このことによりＳｉと他の遷移金属元素との組合せをはるかに上回る電気伝導性を持つＳｉＣｕ3 相をＳｉ相の回りに析出させることで、ＳｉＣｕ3 相がＳｉの乏しい電気伝導性を補う役割を果してくれる。 From the above, it can be seen that only Cu in the combination of Si and the transition metal element precipitates the Si phase and the metal-rich compound (SiCu 3 ) phase by eutectic reaction, and this SiCu 3 is Si—Cu. It is also known from the binary phase diagram that in a Si-rich composition (for example, Si: 64 atom% -Cu: 36 atom%), the Si phase surrounds the SiCu 3 phase. This allows the SiCu 3 phase to precipitate around the Si phase, which has a much higher electrical conductivity than the combination of Si and other transition metal elements, so that the SiCu 3 phase plays a role in supplementing the poor electrical conductivity of Si. He will do it.
さらに、ＳｉＣｕ3 相はリチウムと合金化しないことにより、ＳｉＣｕ3 相自身は充電（負極にリチウムが入る）−放電（負極からリチウムが出ていく）が繰り返されても体積膨張・収縮はせず、それどころかＳｉＣｕ3 相はＳｉに比べて硬度が低いためＳｉとリチウムとの反応により生じるＳｉの大きな体積膨張・収縮の変化による応力を緩和する相とも成り得る。 Furthermore, since the SiCu 3 phase is not alloyed with lithium, the SiCu 3 phase itself does not expand or contract even if it is repeatedly charged (lithium enters the negative electrode) -discharge (lithium comes out from the negative electrode). On the contrary, since the SiCu 3 phase has a lower hardness than Si, it can also be a phase that relieves stress due to a large volume expansion / contraction change of Si caused by the reaction between Si and lithium.
また、Ｓｉは主相であり、Ｌｉと可逆的に化合・隔離することができる１または２以上の元素から構成される相の群である。このような元素である、Ｃ，Ｇｅ，Ｓｎ，Ｐｂ，ＡｌおよびＰからなる群から選ばれた１種または２種以上の元素を、Ｓｉの一部として置換しても良く、これら元素が置換型の固溶体をなすとき、その組成比は特に限定しないが、Ｃ，Ｇｅ，Ｓｎ，Ｐｂ，Ａｌ，Ｐの割合はこれらをＭとすると、Ｓｉを１とした場合、Ｓｉに置換するＭの合計は０．５未満が好ましい。 Si is a main phase, and is a group of phases composed of one or more elements that can be reversibly combined and sequestered with Li. One or more elements selected from the group consisting of C, Ge, Sn, Pb, Al and P, which are such elements, may be substituted as part of Si, and these elements may be substituted. When forming a solid solution of a mold, the composition ratio is not particularly limited, but the ratio of C, Ge, Sn, Pb, Al, P is M, where these are M, and when Si is 1, the total of M substituted for Si Is preferably less than 0.5.
さらに、Ｓｉと金属間化合物を形成するＣｕとの合金であるＳｉｘＣｕｙ合金において、ＳｉｘＣｕｙ相の組成がｘ＜ｙであることが必要である。例えば、ＦｅＳｉ2 では、Ｆｅリッチとはならない。Ｆｅ元素とＳｉとの合金では、Ｓｉリッチな化合物相を形成してしまうことから、電気伝導性が劣り、かつ、充放電の繰り返しで生じるＳｉの微細化によるＳｉ相間の電気伝導性の低下防止を十分に発揮させることができないため、ＳｉｘＣｕｙ相の組成がｘ＜ｙであることにした。好ましくはｘ＝１、ｙ＝３とする。 Further, in the SixCuy alloy, which is an alloy of Si and Cu that forms an intermetallic compound, the composition of the SixCuy phase needs to be x <y. For example, FeSi 2 does not become Fe rich. Since an alloy of Fe element and Si forms a Si-rich compound phase, the electrical conductivity is inferior, and the electrical conductivity between Si phases is prevented from being lowered due to the refinement of Si caused by repeated charge and discharge. Therefore, the composition of the SixCuy phase is set to x <y. Preferably, x = 1 and y = 3.
また、Ｓｉ相またはＳｉを主相とするＳｉ相の平均粒径としては、１０μｍ以下、好ましくは５μｍ以下とする。これは平均粒径が大きければサイクル寿命が低下するからである。Ｓｉとリチウムの反応は電解液の接触部で起こる。最大粒径が１０μｍを超える大きなＳｉ粒子では、初期充電反応の間にリチウムとの反応が電解液の接触するＳｉ粒子表層部のみの反応に止まり、電解液が染み込むまでに時間がかかるリチウムとＳｉ内部の反応が行なわれなくなってしまう。 Further, the average particle diameter of the Si phase or Si phase having Si as the main phase is 10 μm or less, preferably 5 μm or less. This is because if the average particle size is large, the cycle life is reduced. The reaction between Si and lithium occurs at the contact portion of the electrolyte. For large Si particles having a maximum particle size exceeding 10 μm, the reaction with lithium during the initial charging reaction stops only at the surface part of the Si particle in contact with the electrolytic solution, and it takes time until the electrolytic solution penetrates. The internal reaction will not be performed.
そして、初期のＳｉへのリチウムの挿入反応により起こるＳｉ表面と内部の体積膨張・収縮差により生じる応力に耐え切れなくなり、表層Ｓｉが割れ、そのＳｉが集電体から剥離したり、集電性がとれない電気的に孤立したＳｉアイランドになってしまうことで次のサイクルからそれらのＳｉが利用できなくなってしまう。また、その時、割れ方によっては未反応のＳｉを含んだまま集電体から剥離したり、集電のとれない電気的に孤立した状態になってしまう恐れもある。さらに、表層のＳｉがなくなり、新たな未反応Ｓｉ面が出てくることで上記の現象の繰り返しになり、初期数サイクルのうちに容量が急激に低下してしまう。 And, it becomes impossible to withstand the stress caused by the volume expansion / contraction difference between the Si surface and the internal volume caused by the insertion reaction of lithium into the initial Si, the surface layer Si cracks, and the Si peels off from the current collector, By becoming an electrically isolated Si island that cannot be removed, those Si cannot be used from the next cycle. At that time, depending on the cracking method, there is a risk of peeling from the current collector while containing unreacted Si or becoming an electrically isolated state where current cannot be collected. Furthermore, when the surface Si disappears and a new unreacted Si surface appears, the above phenomenon is repeated, and the capacity rapidly decreases in the initial few cycles.
上記のことから、Ｓｉの平均粒径が大きいと、初期充電反応の間にリチウムとの反応が電解液の接触するＳｉ粒子表層部のみの反応に止まってしまうことが分かっている。そこで、Ｓｉ粒子を微粒子にし、反応するＳｉの比表面積を大きくすることであらかじめ電解液が接触するＳｉ表面積を増やす対策を行なう。これにより、初期のリチウムとＳｉの反応率を増やし、未反応Ｓｉがなくなる粒子サイズまで微細相とし、Ｓｉが集電体から剥離したり、集電性がとれない電気的に孤立したＳｉアイランドを防ぎ、上述したＳｉの剥離・電気的孤立現象の繰り返しによる初期数サイクルの容量の急激な低下を改善する。したがって、その上限を１０μｍとした。粒径の下限値は小さい程好ましい。 From the above, it has been found that when the average particle size of Si is large, the reaction with lithium stops during the initial charge reaction only in the surface layer portion of the Si particle in contact with the electrolyte. Therefore, measures are taken in advance to increase the Si surface area with which the electrolytic solution comes into contact by making Si particles fine particles and increasing the specific surface area of the reacting Si. This increases the initial reaction rate between lithium and Si, makes it a fine phase up to a particle size where there is no unreacted Si, and removes Si from the current collector or electrically isolated Si islands that cannot collect current. This prevents a sudden drop in the capacity of the initial few cycles due to the repetition of the above-described Si peeling and electrical isolation phenomenon. Therefore, the upper limit is set to 10 μm. The smaller the lower limit of the particle size, the better.
図２は、Ｓｉ−Ｃｕ合金粉末の断面ＳＥＭ画像を示す。この図に示すように、黒色の部分が埋め込み樹脂１、灰色の部分がＳｉ相２、白色の部分がＳｉＣｕ3 相３である。特に中央のＳｉ−Ｃｕ粒子に注目すると、粒子内部のＡ部分では灰色のＳｉ相２が白色のＳｉＣｕ3 相に取り囲まれた状態になっている。しかし、粒子表面部分のＢ部分では灰色のＳｉ相２が粒子表面に剥ぎ出しになっている様子がわかる。このように、Ｓｉ相の少なくとも１部がＳｉｘＣｕｙ相で取り囲んでいることにある。 FIG. 2 shows a cross-sectional SEM image of the Si—Cu alloy powder. As shown in this figure, the black portion is the embedded resin 1, the gray portion is the Si phase 2, and the white portion is the SiCu 3 phase 3. In particular, when attention is paid to the central Si—Cu particle, the gray Si phase 2 is surrounded by the white SiCu 3 phase in the portion A inside the particle. However, it can be seen that in the portion B of the particle surface portion, the gray Si phase 2 is exposed on the particle surface. Thus, at least a part of the Si phase is surrounded by the SixCuy phase.
以下、本発明について実施例により具体的に説明する。
表１に示す組成の負極材料の鱗片状粉末を、以下に述べるようにして液体急冷法とメカニカルミリングにより作製した。所定組成の原料を底部に細孔を設けた石英管内に入れ、Ａｒ雰囲気中で高周波溶解して溶湯を形成し、この溶湯を回転する銅ロール表面に出湯後、銅ロールにより急冷効果により急冷リボンを作製した。その後、作製リボンをジルコニアポット容器内にジルコニアボールとともにＡｒ雰囲気中にて密閉し、メカニカルミリングにより粉末化した。得られた負極材料の負極性能を評価するため、各負極材料の粉末を平均粒径を１０μｍ以下に分級して負極を作製した。上記負極の単極での電極性能を評価するために、対極にリチウム金属を用いた、いわゆる二極式コイン型セルを用いた。
Hereinafter, the present invention will be specifically described with reference to examples.
A flaky powder of a negative electrode material having the composition shown in Table 1 was prepared by a liquid quenching method and mechanical milling as described below. A raw material having a predetermined composition is placed in a quartz tube having pores at the bottom, melted at a high frequency in an Ar atmosphere to form a molten metal, and after the molten metal is discharged onto the surface of a rotating copper roll, the ribbon is quenched by a rapid cooling effect by the copper roll Was made. Thereafter, the produced ribbon was sealed in a zirconia pot container together with zirconia balls in an Ar atmosphere, and powdered by mechanical milling. In order to evaluate the negative electrode performance of the obtained negative electrode material, the powder of each negative electrode material was classified into an average particle size of 10 μm or less to prepare a negative electrode. In order to evaluate the electrode performance of the negative electrode as a single electrode, a so-called bipolar coin-type cell using lithium metal as a counter electrode was used.
まず、負極活物質（Ｓｉ−Ｃｕなど）・導電材（アセチレンブラック）・結着材（ポリフッ化ビニリデン）を電子天秤で秤量し、分散液（Ｎ−メチルピロリドン）と共に混合スラリー状態とした後、集電体（Ｃｕ箔）上に均一に塗布した。塗布後、真空乾燥機で減圧乾燥し溶媒を蒸発させた後、コインセルにあった形状に打ち抜いた。対極のリチウムも同様に金属リチウム箔をコインセルにあった形状に打ち抜いた。 First, a negative electrode active material (such as Si-Cu), a conductive material (acetylene black), a binder (polyvinylidene fluoride) is weighed with an electronic balance, and mixed with a dispersion (N-methylpyrrolidone). It apply | coated uniformly on the electrical power collector (Cu foil). After coating, the solvent was evaporated by drying under reduced pressure with a vacuum dryer, and then punched into a shape suitable for a coin cell. Similarly, lithium for the counter electrode was punched into a shape suitable for the coin cell.
リチウムイオン電池に使用する電解液（エチレンカーボネートとジメチルカーボネートの３：７混合溶媒を用い、支持電解質にはＬｉＰＦ6 （六フッ化リン酸リチウム）を用い、電解液に対して１モル溶解した）は露点管理された不活性雰囲気中で取り扱う必要があるため、セルの組立ては全て不活性雰囲気のグローブボックス内で行った。セパレータはコインセルにあった形状に切り抜いた後、セパレータ内に電解液を十分浸透させるために、減圧下で数時間電解液中に保持した。その後、前工程で打ち抜いた負極・セパレータ・対極リチウムの順に組合せ、電池内部を電解液で十分満たした形で構築した。 Electrolytic solution used for lithium ion batteries (3: 7 mixed solvent of ethylene carbonate and dimethyl carbonate was used, LiPF 6 (lithium hexafluorophosphate) was used as the supporting electrolyte, and 1 mol was dissolved in the electrolytic solution) Since the cell must be handled in an inert atmosphere with dew point control, the cells were all assembled in an inert atmosphere glove box. The separator was cut out into a shape suitable for a coin cell, and then held in the electrolyte for several hours under reduced pressure in order to sufficiently permeate the electrolyte into the separator. Thereafter, the negative electrode, separator, and counter electrode lithium punched in the previous process were combined in this order, and the battery was fully filled with the electrolyte.
充電容量、放電容量の測定として、上記二極式セルを用い、温度２５℃、充電は０．５０ｍＡ／ｃｍ2 の電流密度で、金属リチウム極と同等の電位（０Ｖ）になるまで行い、同じ電流値（０．５０ｍＡ／ｃｍ2 ）で放電を１．５Ｖまで行い、この充電−放電を１サイクルとした。このときの１サイクル目の充電容量を初期容量値として評価した。この評価で得られた放電容量、すなわち負極が放出するリチウム量が負極の質量当たり１０００ｍＡｈ／ｇ以上（これを体積当たりに換算すると約４０００ｍＡｈ／ｃｍ3 以上）を合格とした。 The measurement of charge capacity and discharge capacity was performed using the above-mentioned bipolar cell, at a temperature of 25 ° C., and charged at a current density of 0.50 mA / cm 2 until the same potential (0 V) as that of the metal lithium electrode. Discharge was performed up to 1.5 V at a current value (0.50 mA / cm 2 ), and this charge-discharge was taken as one cycle. The charge capacity at the first cycle at this time was evaluated as the initial capacity value. The discharge capacity obtained by this evaluation, that is, the amount of lithium released from the negative electrode was 1000 mAh / g or more per mass of the negative electrode (about 4000 mAh / cm 3 or more when converted to volume), and passed.
また、サイクル寿命として、上記１サイクル目の放電容量を測定すると共に、その負極材料を用いた負極の放電容量とし、１００サイクル目の放電容量を測定して、サイクル寿命の目安とした。この評価で得られた１００サイクル目の放電容量（負極が放出するリチウム量）が現状のグラファイト電極の理論放電容量である３７２ｍＡｈ／ｇ以上、すなわち約８６７ｍＡｈ／ｃｍ3 以上を合格とした。こうして得られた１サイクル目の放電容量と１００サイクル目の放電容量の結果を表２に示す。 Further, as the cycle life, the discharge capacity of the first cycle was measured, and the discharge capacity of the negative electrode using the negative electrode material was measured. The discharge capacity of the 100th cycle was measured, and used as a measure of the cycle life. The discharge capacity at the 100th cycle (the amount of lithium released from the negative electrode) obtained by this evaluation was 372 mAh / g or higher, which is the theoretical discharge capacity of the current graphite electrode, that is, about 867 mAh / cm 3 or higher. Table 2 shows the results of the discharge capacity at the first cycle and the discharge capacity at the 100th cycle thus obtained.
本発明例Ｎｏ．１〜８は１サイクル目の放電容量が１０００ｍＡｈ／ｇ以上、すなわち約４０００ｍＡｈ／ｃｍ3 以上を示し、電池負極として合格である。また、１００サイクル後の放電容量は現状のグラファイト電極の容量である３７２ｍＡｈ／ｇ以上、すなわち約８６７ｍＡｈ／ｃｍ3 を上回る値を示したことからサイクル寿命評価においても合格である。同じ組成であっても比較例Ｎｏ．９、１０においては、Ｓｉ相サイズの平均粒径が１０μｍを超えているため１００サイクル後の放電容量が小さくなり、本発明の条件を満たさない。 Invention Example No. 1 to 8 show discharge capacities of the first cycle of 1000 mAh / g or more, that is, about 4000 mAh / cm 3 or more, and are acceptable as battery negative electrodes. Further, the discharge capacity after 100 cycles showed a value exceeding 372 mAh / g which is the capacity of the current graphite electrode, that is, a value exceeding about 867 mAh / cm 3 . Even with the same composition, Comparative Example No. In Nos . 9 and 10 , since the average particle size of the Si phase size exceeds 10 μm, the discharge capacity after 100 cycles is small, and the conditions of the present invention are not satisfied.
比較例Ｎｏ．１１〜２０は、遷移金属シリサイト相（ＮｉＳｉ2 、ＦｅＳｉ2 、ＭｎＳｉ2 、ＣｏＳｉ2 、ＣｒＳｉ2 、ＷＳｉ2 、ＭｏＳｉ2 、ＮｂＳｉ2 、ＴｉＳｉ2 、ＶＳｉ2 ）が遷移金属元素（Ｎｉ、Ｆｅ、Ｍｎ、Ｃｏ、Ｃｒ、Ｗ、Ｍｏ、Ｎｂ、Ｔｉ、Ｖ）に比較して、Ｓｉリッチのために電気伝導性が劣るため、初期の放電特性が悪い。同様に１００サイクル後の放電容量も悪い。 Comparative Example No. 11-20, transition metal silicide phase (NiSi 2, FeSi 2, MnSi 2, CoSi 2, CrSi 2, WSi 2, MoSi 2, NbSi 2, TiSi 2, VSi 2) transition metal elements (Ni, Fe, Compared with Mn, Co, Cr, W, Mo, Nb, Ti, and V), the electrical discharge is inferior because of Si-rich, so the initial discharge characteristics are poor. Similarly, the discharge capacity after 100 cycles is also bad.
比較例Ｎｏ．１１〜２０は、いずれもＳｉリッチな金属間化合物組成であることから、本発明例のようなＳｉＣｕ3 と比較して電気伝導性が低く、充放電によるＳｉとＬｉの反応効率が悪く、Ｓｉ相間の電気伝導性の低下を招き、充放電寿命も劣る。これに対し、本発明例Ｎｏ．１〜８は、いずれも本発明の条件を満足することから、高い電気伝導性をもち、かつリチウムと反応しないことにより充放電時のＳｉとＬｉの反応によるＳｉの体積膨張・収縮の応力を緩和する相となると共に、充放電の繰り返しで生じるＳｉの微細化によるＳｉ相間の電気伝導性の低下も防止でき、充放電寿命を向上させることができるものである。 Comparative Example No. Since 11 to 20 are all Si-rich intermetallic compound compositions, the electrical conductivity is low compared to SiCu 3 as in the present invention example, the reaction efficiency of Si and Li due to charge and discharge is poor, and Si The electrical conductivity between phases is lowered, and the charge / discharge life is also inferior. On the other hand, the present invention example No. Nos. 1 to 8 satisfy the conditions of the present invention, so that they have high electrical conductivity and do not react with lithium, so that the volume expansion / contraction stress of Si due to the reaction between Si and Li during charge / discharge can be reduced. While becoming a phase which eases, the electrical conductivity fall between Si phases by the refinement | miniaturization of Si which arises by repetition of charging / discharging can also be prevented, and a charging / discharging lifetime can be improved.
以上のように、金属リッチな化合物相はＳｉ金属間化合物の中でも非常に高い熱伝導性を示すため、合金溶湯から凝固する際の熱伝導性に優れており初晶のＳｉ相の成長を抑えて微細にすることができる。また、ＳｉＣｕ3 相は電気伝導性に優れており、相乗効果で充放電容量や充放電寿命ともに向上する極めて優れた効果を奏するものである。 As described above, the metal-rich compound phase exhibits extremely high thermal conductivity among Si intermetallic compounds, so it has excellent thermal conductivity when solidified from molten alloy and suppresses the growth of the primary Si phase. Can be made fine. Further, the SiCu 3 phase is excellent in electrical conductivity, and exhibits a very excellent effect of improving both the charge / discharge capacity and the charge / discharge life due to a synergistic effect.
１ 埋め込み樹脂
２ Ｓｉ相
３ ＳｉＣｕ3 相
特許出願人 山陽特殊製鋼株式会社
代理人 弁理士 椎 名 彊
1 Embedded resin 2 Si phase 3 SiCu 3 phase
Patent applicant Sanyo Special Steel Co., Ltd.
Attorney: Attorney Shiina
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