JP2004063400A - Negative electrode material for lithium cell, and its manufacturing method - Google Patents
Negative electrode material for lithium cell, and its manufacturing method Download PDFInfo
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- JP2004063400A JP2004063400A JP2002223182A JP2002223182A JP2004063400A JP 2004063400 A JP2004063400 A JP 2004063400A JP 2002223182 A JP2002223182 A JP 2002223182A JP 2002223182 A JP2002223182 A JP 2002223182A JP 2004063400 A JP2004063400 A JP 2004063400A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 45
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- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 10
- 238000005551 mechanical alloying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims 1
- 238000005204 segregation Methods 0.000 abstract description 2
- 239000011135 tin Substances 0.000 description 36
- 238000009826 distribution Methods 0.000 description 11
- 229910000905 alloy phase Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 238000004125 X-ray microanalysis Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
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- 229910001416 lithium ion Inorganic materials 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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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
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、リチウム電池用負極材料、及びその製造方法に関する。
【０００２】
【従来の技術】
リチウム二次電池は、起電力が高く、高エネルギー密度を有するものであり、近年、移動体通信機器、携帯用電子機器等の主電源としての利用が拡大している。
【０００３】
リチウム電池における負極としては、黒鉛、結晶化度の低い炭素等の各種炭素材料が広く用いられているが、炭素材料からなる電極は、使用可能な電流密度が低く、しかも、理論容量も不十分であり、例えば炭素材料のひとつである黒鉛の理論容量は３７２ｍＡｈ／ｇに過ぎない。
【０００４】
一方、リチウム金属をリチウム二次電池の負極材料とする場合には、炭素材料を用いる場合と比べて理論容量は高くなるものの、充電時に負極にデンドライトが析出し、充放電を繰り返すことによって正極側に達して、内部短絡を起こす恐れがある。また、析出したデンドライトは、比表面積が大きいために反応活性度が高く、その表面で電子伝導性を欠いた溶媒の分解生成物からなる界面被膜を形成し、これにより電池の内部抵抗が高くなって充放電効率を低下させる要因となる。これらの理由で、負極材料としてリチウム金属を用いるリチウム二次電池は、信頼性が低く、サイクル寿命が短いという欠点がある。
【０００５】
電池性能を更に向上させるためには、理論放電容量の大きい物質を負極材料として用いることが望まれる。例えば錫、珪素、銀などの元素、あるいはこれらの窒化物、酸化物等は、リチウムと合金を形成することによってリチウムを吸蔵することができ、その吸蔵量は炭素よりはるかに大きい値を示すことが知られている。
【０００６】
しかしながら、これらの物質を負極材料とする場合には、充電・放電のサイクルを繰り返すうちに、リチウムの吸蔵・放出に伴う大きな膨張・収縮によって電極そのものの瓦解を生じるようになる。
【０００７】
したがって、上記物質を負極材料とする場合には、大きな初期放電容量は得られるものの、充放電を繰り返すうちに微細化し、その結果、放電容量が大きく低下するという欠点がある。
【０００８】
【発明が解決しようとする課題】
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、高い放電容量を維持しつつ、優れたサイクル特性を発揮できるリチウム電池用負極材料を提供することである。
【０００９】
【課題を解決するための手段】
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、特定の３種類の成分をメカニカルアロイング処理によって合金化して得られる粉末では、Ｌｉ吸蔵量が多い元素やＬｉ吸蔵量が中間的な元素等は均一に分布し、Ｌｉ吸蔵量が少ない元素及びこれを含む金属間化合物については偏析した状態となり、偏析したＬｉ吸蔵量が少ない元素の存在によって、リチウムの吸蔵・放出に伴う膨張及び収縮が緩和されて、電極の劣化を抑制でき、リチウム電池用負極材料として優れた性能を有するものとなることを見出し、ここに本発明を完成するに至った。
【００１０】
即ち、本発明は、下記のリチウム電極用負極材料及びその製造方法を提供するものである。
１． （ｉ）Ａｇ、Ａｌ、Ｂｉ、Ｓｂ及びＺｎから選ばれた少なくとも一種の元素からなるＡ成分、（ｉｉ）Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ及びＷから選ばれた少なくとも一種の元素からなるＢ成分、（ｉｉｉ）Ｓｎ、並びに（ｉｖ）上記（ｉ）〜（ｉｉｉ）の元素の二種以上からなる合金、からなる複合粉末であって、各粉末中において、Ａ成分、Ｓｎ、及びＡ成分とＳｎとの合金は均一に分布し、Ｂ成分及びＢ成分を含む合金は偏析した状態にある複合粉末からなるリチウム電池用負極材料。
２． 複合粉末中の元素の含有率が、Ａ成分５〜６０原子％、Ｂ成分１０〜４５原子％、及びＳｎ２０〜９０原子％である上記項１に記載のリチウム電池用負極材料。
３． Ａ成分がＡｇ、Ｂｉ及びＳｂから選ばれた少なくとも一種の元素であり、Ｂ成分が、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ及びＭｏから選ばれた少なくとも一種の元素である上記項１または２に記載のリチウム電池用負極材料。
４． Ａｇ、Ａｌ、Ｂｉ、Ｓｂ及びＺｎから選ばれた少なくとも一種の元素からなるＡ成分、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ及びＷから選ばれた少なくとも一種の元素からなるＢ成分、及びＳｎからなる原料物質を混合し、メカニカルアロイング処理を行って複合粉末を形成することを特徴とする上記項１〜３のいずれかに記載されたリチウム電池用負極材料の製造方法。
【００１１】
【発明の実施の形態】
本発明のリチウム電極用負極材料の有効成分である複合粉末は、（ｉ）Ａｇ、Ａｌ、Ｂｉ、Ｓｂ及びＺｎから選ばれた少なくとも一種の元素からなるＡ成分、（ｉｉ）Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ及びＷから選ばれた少なくとも一種の元素からなるＢ成分、（ｉｉｉ）Ｓｎ、並びに（ｉｖ）上記（ｉ）〜（ｉｉｉ）の元素の二種以上からなる合金、からなる複合粉末であって、各粉末中において、Ａ成分、Ｓｎ、及びＡ成分とＳｎとの合金は均一に分布し、Ｂ成分、及びＢ成分を含む合金は偏析した状態である。
【００１２】
この様な複合粉末に含まれる元素の内で、Ｓｎはリチウムと化合物を形成し易く、リチウム吸蔵量が多い元素であり、Ａｇ、Ａｌ、Ｂｉ、Ｓｂ及びＺｎから選ばれた少なくとも一種の元素であるＡ成分は、リチウムと化合するが、リチウム吸蔵量が中間的な元素である。また、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ及びＷから選ばれた少なくとも一種の元素であるＢ成分は、リチウムと化合し難く、リチウム吸蔵量が少ない元素である。
【００１３】
上記した複合粉末では、この様なリチウム吸蔵量が多いＳｎ、リチウム吸蔵量が中間的なＡ成分、及びＳｎとＡ成分との合金が均一に分布し、リチウム吸蔵量が小さいＢ成分及びＢ成分を含む合金が偏析した状態である。この様な複合粉末は、リチウム吸蔵量が多いＳｎ、リチウム吸蔵量が中間的なＡ成分、及びＳｎとＡ成分との合金が均一に分布した状態にあることによって、リチウムの吸蔵・放出が容易である。また、リチウムと化合し難くリチウム吸蔵量が少ない元素であるＢ成分及びＢ成分を含む合金が偏析していることによって、リチウムの吸蔵・放出に伴う膨張及び収縮を緩和することができる。その結果、該複合粉末は、放電容量が高く、しかも充放電に伴う劣化が少ないものとなり、リチウム電池用負極材料として用いた場合に、高い放電容量と優れたサイクル特性を両立することができる。
【００１４】
尚、リチウム吸蔵量が少ない元素であるＢ成分及びＢ成分を含む合金が偏析した状態とは、例えば、各粉末についてＸ線マイクロアナリシス法によって元素分析をした場合に、Ｂ成分が粒子全体に均一に分布することなく、Ｂ成分の分布状態が不均一な状態をいう。
【００１５】
上記した複合粉末に含まれる成分の内で、ＳｎとＡ成分との合金とは、ＳｎにＡ成分が固溶した合金相、ＳｎとＡ成分の金属間化合物相、Ａ成分にＳｎが固溶した合金相などから形成され、通常、組成が連続的に変化するものである。
【００１６】
また、Ｂ成分を含む合金とは、ＳｎにＢ成分が固溶した合金相、ＳｎとＢ成分の金属間化合物相、Ｂ成分にＳｎが固溶した合金相などから形成されるＢ成分とＳｎとの合金；Ａ成分にＢ成分が固溶した合金相、Ａ成分とＢ成分の金属間化合物相、Ｂ成分にＡ成分が固溶した合金相などから形成されるＡ成分とＢ成分との合金；ＳｎにＡ成分とＢ成分が固溶した合金相、Ａ成分にＳｎとＢ成分が固溶した合金相、Ｂ成分にＳｎとＡ成分が固溶した合金相、Ｓｎ、Ａ成分及びＢ成分の金属間化合物相などから形成されるＡ成分、Ｂ成分及びＳｎの合金等を意味する。
【００１７】
上記複合粉末では、各元素の割合は、Ａ成分５〜６０原子％、Ｂ成分１０〜４５原子％、及びＳｎ２０〜９０原子％であるであることが好ましく、Ａ成分１０〜４０原子％程度、Ｂ成分５〜４０原子％程度、及びＳｎ３５〜７０原子％程度であることがより好ましい。
【００１８】
本発明では、特に、Ａ成分としては、Ａｇ、Ｂｉ及びＳｂから選ばれた少なくとも一種の成分が好ましく、Ｂ成分としては、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ及びＭｏから選ばれた少なくとも一種の成分が好ましい。
【００１９】
本発明の複合粉末は、その大きさについては、特に限定的ではないが、後述するメカニカルアロイング法で製造した場合に、通常、１μｍ程度以下の微細な一次粒子が生成し、一次粒子は凝集して二次凝集物となっており、二次凝集物の粒度は、通常はレ−ザ回折法による粒径で最大が３８〜１５０μｍ程度であり、２０〜１０５μｍ程度であることがより好ましい。また、該二次凝集物の平均粒径は、４５μｍ程度以下であることが好ましく、１０μｍ程度以下であることがより好ましい。
【００２０】
上記した複合粉末における元素の分布状態は、この様な二次凝集物についての元素の分布状態である。
【００２１】
本発明負極材料の有効成分である上記した複合粉末は、Ａ成分、Ｂ成分及びＳｎからなる原料物質を混合し、メカニカルアロイング処理を行って、好ましくは一次粒子径を１μｍ以下とすることによって製造することができる。メカニカルアロイング処理における遠心加速度（投入エネルギー）は、５〜２０Ｇ程度であることが好ましく、７〜１５Ｇ程度であることがより好ましい。
【００２２】
メカニカルアロイング処理自体は公知の方法をそのまま適用すれば良い。例えば、原料混合物を機械的接合力により混合・付着を繰返しながら複合化（一部合金化）させることによって目的とする複合粉末を得ることができる。使用する装置としては、一般に粉体分野で使用される混合機、分散機、粉砕機等をそのまま使用することができる。具体的には、ライカイ機、ボ−ルミル、振動ミル、アジテ−タ−ミル等が例示される。特に、ネットワ−ク間に存在する電池活物質を主成分とする粉末の積み重なりを少なくするためには、複合化操作中に重なり合ったり、凝集したりした粉末を１粒子づつに効率良く分散させる必要があるので、せん断力を与えることのできる混合機を用いることが望ましい。これらの装置の操作条件は特に限定されるものではない。
【００２３】
上記した複合粉末からなる本発明の負極材料は、リチウム電池用の負極材料として有用である。リチウム電池用負極の具体的な構成は、負極材料として本発明材料を用いる他は、公知のものと同様でよい。例えば、必要に応じて樹脂系バインダ−、導電助材等を配合し、銅箔集電体等の公知の集電体上に電極層を形成させて一体化することによって負極を作製することができる。さらに、公知のリチウムイオン電池の電池要素（正極、セパレ−タ−、電解液等）を用い、公知のリチウムイオン電池の組立方法に従ってリチウムイオン電池を製造することができる。
【００２４】
【発明の効果】
本発明の負極材料は、優れた放電容量を有し、しかも充放電を繰り返した場合にも微粉化や担持体からの脱落が無く、炭素材料と同等のサイクル特性を維持することができる。
【００２５】
このため、本発明の負極材料は、安定した長寿命の充放電サイクル特性を発揮できるものとして有用性の高いものである。
【００２６】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。
【００２７】
実施例１〜１９
（１）複合粉末の合成
下記表１に示す各比率（原子％）となるように金属粉末を混合し、滑剤としてステアリン酸「Ｆ２０００」（新日本理化製）を０．５質量％添加し、フリッチェ製遊星ボ−ルミルに投入し、メカニカルアロイング処理を行うことにより複合粉末を得た。
（２）電極・電池の作製及び評価
ポリビニリデンフルオライド（ＰＶｄＦ）をＮ−メチルピロリドン（ＮＭＰ）に溶解させたペ−スト１０質量％、複合粉末８５質量％及びカ−ボンブラック５質量％を添加、混合し、スラリ−を調製した。
【００２８】
次いで、電解銅箔（福田金属箔粉工業製）に上記スラリ−をのせて、ドクタ−ブレ−ドでラミネ−トし、シ−ト化した。この作製したシ−トを１０分間、８０℃で乾燥させ、ＮＭＰを揮発させた後、ロ−ルプレスをして、強固に密着接合させた。これを１ｃｍ２の円形ポンチで抜き取り、これを１２０℃で１２時間以上の真空乾燥させて試験電極とした。
【００２９】
ドライボックス中で、試験電極をカソ−ドとし、金属リチウムをアノ−ドとし、１モルのＬｉＰＦ６／エチレンカ−ボネ−ト（ＥＣ）＋ジメチルカ−ボネ−ト（ＤＭＣ）（ＥＣ：ＤＭＣ＝１：２（体積比））溶液を電解液とし、コイン型電池（ＣＲ２０３２タイプ）を作製した。
【００３０】
放電容量評価は次のようにして実施した。まず、上記電池を、０．２ｍＡ／ｃｍ２ の定電流で０Ｖに達するまで放電し、１０分間の休止後、０．２０ｍＡ／ｃｍ２ の定電流で１．０Ｖに達するまで充電させた。これを、１サイクルとして、繰り返し充放電を行って放電容量を調べた。各実施例の複合粉末について、サイクル数と放電容量を表１に示す。尚、表１には、比較として、表１の比較例１〜１６に記載した２成分系合金、又は比較例１７〜３２に記載した単独金属を負極材料として用いた場合についてもサイクル数と放電容量を示す。
【００３１】
【表１】
表１から明らかなように、各実施例の複合粉末を用いた場合には、初期放電容量が高く、しかも５０サイクル後の放電容量も十分維持されていることが判る。
【００３３】
また、実施例２の複合粉末（Ｓｎ／Ａｇ／Ｆｅ（原子％）＝４８／３６．４／１５．６）の断面の走査電子顕微鏡写真（ＳＥＭ）及びＸ線マイクロアナリシス法による各元素の分布状態を示す分布図を図１に示し、実施例３の複合粉末（Ｓｎ／Ａｇ／Ｆｅ（原子％）＝４８／２６／２６）の断面の走査電子顕微鏡写真（ＳＥＭ）及びＸ線マイクロアナリシス法による各元素の分布状態を示す分布図を図２に示す。図１及び図２より、実施例２及び３の各複合粒子では、Ａｇ及びＳｎは粒子全体に均一に分布しているのに対して、Ｂ成分であるＦｅは部分的に偏析していることが判る。
【００３４】
また、実施例２の複合粉末（Ｓｎ／Ａｇ／Ｆｅ（原子％）＝４８／３６．４／１５．６）について、放電容量とサイクル数との関係のグラフを図３に示す。図３には、比較として、Ａｇ／Ｓｎ（原子％）＝５２／４８の複合粉末を負極材料として用いた場合の結果、及びＳｎ、Ａｇ及びＦｅの各金属を単独で負極材料として用いた場合の結果についても示す。
【００３５】
図３から明らかなように、実施例２の複合粉末を用いた負極材料は、優れたサイクル特性を有することが判る。
【００３６】
更に、図４には、実施例３の複合粉末（Ｓｎ／Ａｇ／Ｆｅ（原子％）＝４８／２６／２６）を負極材料として使用し、３００サイクルまで充放電を繰り返した場合について放電容量とサイクル数との関係のグラフを示す。
【００３７】
図４から、実施例３の複合粉末を負極材料として用いる場合には、初期容量が５５０ｍＡｈ／ｇ程度であって、３００サイクル後でも２００ｍＡｈ／ｇの容量を維持しており、優れたサイクル寿命を有することが判る。
【図面の簡単な説明】
【図１】実施例２で得られた複合粉末の断面の走査電子顕微鏡写真（ＳＥＭ）及びＸ線マイクロアナリシス法による各元素の分布状態を示す分布図。
【図２】実施例３で得られた複合粉末の断面の走査電子顕微鏡写真（ＳＥＭ）及びＸ線マイクロアナリシス法による各元素の分布状態を示す分布図。
【図３】実施例２で得られた複合粉末について、放電容量とサイクル数との関係を表すグラフ。
【図４】実施例３で得られた複合粉末について、放電容量とサイクル数との関係を表すグラフ。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a negative electrode material for a lithium battery and a method for producing the same.
[0002]
[Prior art]
A lithium secondary battery has a high electromotive force and a high energy density, and in recent years, its use as a main power source for mobile communication devices, portable electronic devices, and the like has been expanding.
[0003]
Various carbon materials such as graphite and low crystallinity carbon are widely used as a negative electrode in a lithium battery, but an electrode made of a carbon material has a low usable current density and an insufficient theoretical capacity. For example, the theoretical capacity of graphite, which is one of the carbon materials, is only 372 mAh / g.
[0004]
On the other hand, when lithium metal is used as the negative electrode material of a lithium secondary battery, although the theoretical capacity is higher than when a carbon material is used, dendrite precipitates on the negative electrode during charging, and charging and discharging are repeated, thereby increasing the positive electrode side. To cause internal short circuit. In addition, the precipitated dendrite has a high specific activity due to its large specific surface area, and forms an interfacial coating made of a decomposition product of a solvent lacking electron conductivity on its surface, thereby increasing the internal resistance of the battery. This causes a reduction in charge / discharge efficiency. For these reasons, a lithium secondary battery using lithium metal as a negative electrode material has disadvantages of low reliability and short cycle life.
[0005]
In order to further improve battery performance, it is desired to use a substance having a large theoretical discharge capacity as a negative electrode material. For example, elements such as tin, silicon, and silver, or nitrides and oxides thereof, can occlude lithium by forming an alloy with lithium, and the amount of occlusion shows a value much larger than that of carbon. It has been known.
[0006]
However, when these materials are used as the negative electrode material, the electrode itself collapses due to the large expansion and contraction accompanying the occlusion and release of lithium during repeated charge and discharge cycles.
[0007]
Therefore, when the above-mentioned substance is used as a negative electrode material, a large initial discharge capacity can be obtained, but there is a disadvantage that the charge / discharge is repeated to make finer, and as a result, the discharge capacity is greatly reduced.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned state of the art, and its main object is to provide a negative electrode material for a lithium battery that can exhibit excellent cycle characteristics while maintaining a high discharge capacity. is there.
[0009]
[Means for Solving the Problems]
The present inventor has made intensive studies to achieve the above-mentioned object. As a result, in a powder obtained by alloying the three specific components by mechanical alloying, elements having a large Li occlusion amount or elements having an intermediate Li occlusion amount are uniformly distributed, and the Li occlusion amount is small. The element and the intermetallic compound containing the element are in a segregated state, and the presence of the segregated element having a small Li occlusion amount reduces expansion and contraction accompanying occlusion and release of lithium, thereby suppressing deterioration of the electrode and preventing lithium deterioration. The inventors have found that the material has excellent performance as a negative electrode material for a battery, and have now completed the present invention.
[0010]
That is, the present invention provides the following negative electrode material for a lithium electrode and a method for producing the same.
1. (I) A component consisting of at least one element selected from Ag, Al, Bi, Sb and Zn; (ii) selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo and W A composite powder comprising: a B component composed of at least one element; (iii) Sn; and (iv) an alloy composed of two or more of the above-mentioned elements (i) to (iii). A negative electrode material for a lithium battery comprising a composite powder in which the component A, Sn, and the alloy of the component A and Sn are uniformly distributed, and the component B and the alloy containing the component B are in a segregated state.
2. Item 4. The negative electrode material for a lithium battery according to the above item 1, wherein the content of the element in the composite powder is 5 to 60 atomic% of the A component, 10 to 45 atomic% of the B component, and 20 to 90 atomic% of Sn.
3. 3. The above item 1 or 2, wherein the A component is at least one element selected from Ag, Bi and Sb, and the B component is at least one element selected from Fe, Co, Ni, Cu and Mo. Anode material for lithium battery.
4. A component consisting of at least one element selected from Ag, Al, Bi, Sb and Zn, and at least one element selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo and W The negative electrode material for a lithium battery as described in any one of the above items 1 to 3, wherein a composite powder is formed by mixing a raw material substance consisting of the component B and Sn and performing a mechanical alloying treatment. Method.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The composite powder, which is an active component of the negative electrode material for a lithium electrode of the present invention, comprises (i) an A component comprising at least one element selected from Ag, Al, Bi, Sb, and Zn; and (ii) Ti, V, Cr. , Mn, Fe, Co, Ni, Cu, Mo and W, a B component comprising at least one element selected from the group consisting of: (iii) Sn; and (iv) two or more of the above elements (i) to (iii). In each powder, the A component, Sn, and the alloy of the A component and Sn are uniformly distributed, and the B component, and the alloy containing the B component are segregated in each powder. is there.
[0012]
Among the elements contained in such a composite powder, Sn is an element that easily forms a compound with lithium and has a large lithium storage amount, and is at least one element selected from Ag, Al, Bi, Sb, and Zn. Certain component A is an element that combines with lithium but has an intermediate lithium storage capacity. Further, the B component, which is at least one element selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, and W, is an element that hardly combines with lithium and has a small amount of lithium occlusion.
[0013]
In the above-described composite powder, Sn having a large lithium storage amount, A component having an intermediate lithium storage amount, and an alloy of Sn and A component are uniformly distributed, and B component and B component having a small lithium storage amount are used. Is a state in which the alloy containing is segregated. Such a composite powder is easy to occlude and release lithium because Sn having a large lithium storage amount, an A component having an intermediate lithium storage amount, and an alloy of Sn and the A component are uniformly distributed. It is. In addition, the segregation of the component B and the alloy containing the component B, which are elements that hardly combine with lithium and have a small amount of lithium occlusion, can reduce expansion and contraction accompanying occlusion and release of lithium. As a result, the composite powder has a high discharge capacity and little deterioration due to charge and discharge, and when used as a negative electrode material for a lithium battery, can achieve both a high discharge capacity and excellent cycle characteristics.
[0014]
The state in which the component B having a small lithium storage amount and the alloy containing the component B are segregated means, for example, that when the elemental analysis is performed on each powder by the X-ray microanalysis method, the component B is uniform over the entire particles. And the distribution state of the B component is non-uniform.
[0015]
Among the components contained in the above composite powder, the alloy of Sn and A component is an alloy phase in which A component is dissolved in Sn, an intermetallic compound phase of Sn and A component, and a solid solution of Sn in A component. It is formed from an alloyed phase or the like, and usually has a continuously changing composition.
[0016]
The alloy containing the B component includes an alloy phase in which the B component is dissolved in Sn, an intermetallic compound phase of Sn and the B component, an alloy phase in which Sn is dissolved in the B component, and the like. An alloy phase in which the B component is dissolved in the A component, an intermetallic compound phase of the A component and the B component, and an A phase and a B component formed from an alloy phase in which the A component is dissolved in the B component. Alloy; alloy phase in which A component and B component are dissolved in Sn, alloy phase in which Sn and B component are dissolved in A component, alloy phase in which Sn and A component are dissolved in B component, Sn, A component and B An alloy of the A component, the B component, and Sn formed from the intermetallic compound phase of the component and the like.
[0017]
In the above composite powder, the proportion of each element is preferably 5 to 60 atomic% of the A component, 10 to 45 atomic% of the B component, and 20 to 90 atomic% of Sn, and about 10 to 40 atomic% of the A component. More preferably, the B component is about 5 to 40 atom% and Sn is about 35 to 70 atom%.
[0018]
In the present invention, the A component is particularly preferably at least one component selected from Ag, Bi and Sb, and the B component is at least one component selected from Fe, Co, Ni, Cu and Mo. preferable.
[0019]
The composite powder of the present invention is not particularly limited in its size, but when manufactured by a mechanical alloying method described below, usually, fine primary particles of about 1 μm or less are generated, and the primary particles are aggregated. The secondary agglomerates usually have a maximum particle size of about 38 to 150 μm, more preferably about 20 to 105 μm, as determined by laser diffraction. Further, the average particle size of the secondary aggregate is preferably about 45 μm or less, more preferably about 10 μm or less.
[0020]
The distribution state of the elements in the composite powder described above is the distribution state of the elements in such a secondary aggregate.
[0021]
The above-mentioned composite powder, which is an effective component of the negative electrode material of the present invention, is obtained by mixing the raw materials consisting of the A component, the B component, and Sn and performing a mechanical alloying treatment, preferably to reduce the primary particle diameter to 1 μm or less. Can be manufactured. The centrifugal acceleration (input energy) in the mechanical alloying processing is preferably about 5 to 20 G, and more preferably about 7 to 15 G.
[0022]
For the mechanical alloying process itself, a known method may be applied as it is. For example, a desired composite powder can be obtained by compounding (partially alloying) the raw material mixture while repeating mixing and adhesion by mechanical bonding force. As a device to be used, a mixer, a disperser, a pulverizer and the like generally used in the field of powder can be used as they are. Specifically, a raikai machine, a ball mill, a vibration mill, an agitator mill and the like are exemplified. In particular, in order to reduce the stacking of the powders mainly composed of the battery active material existing between the networks, it is necessary to efficiently disperse the powders that have overlapped or aggregated during the compounding operation one by one. Therefore, it is desirable to use a mixer capable of giving a shearing force. The operating conditions of these devices are not particularly limited.
[0023]
The negative electrode material of the present invention comprising the above composite powder is useful as a negative electrode material for a lithium battery. The specific configuration of the negative electrode for a lithium battery may be the same as a known one except that the material of the present invention is used as a negative electrode material. For example, it is possible to prepare a negative electrode by blending a resin-based binder, a conductive auxiliary material, and the like as necessary, forming an electrode layer on a known current collector such as a copper foil current collector, and integrating them. it can. Furthermore, a lithium ion battery can be manufactured by using a known lithium ion battery battery element (a positive electrode, a separator, an electrolytic solution, etc.) according to a known lithium ion battery assembling method.
[0024]
【The invention's effect】
The negative electrode material of the present invention has excellent discharge capacity, and does not suffer from pulverization or falling off from the carrier even after repeated charge and discharge, and can maintain cycle characteristics equivalent to those of a carbon material.
[0025]
Therefore, the negative electrode material of the present invention is highly useful as a material capable of exhibiting stable and long life charge-discharge cycle characteristics.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0027]
Examples 1 to 19
(1) Synthesis of composite powder The metal powder was mixed so as to have each ratio (atomic%) shown in Table 1 below, and 0.5% by mass of stearic acid "F2000" (manufactured by Shin Nippon Rika) was added as a lubricant, The mixture was charged into a planetary ball mill manufactured by Fricche and subjected to mechanical alloying to obtain a composite powder.
(2) Preparation and evaluation of electrodes and
[0028]
Next, the above slurry was placed on an electrolytic copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd.), and laminated with a doctor blade to form a sheet. The produced sheet was dried at 80 ° C. for 10 minutes to evaporate NMP, and then roll-pressed to firmly adhere. This was extracted with a 1 cm 2 circular punch, and this was vacuum-dried at 120 ° C. for 12 hours or more to obtain a test electrode.
[0029]
In a dry box, a test electrode is a cathode, metallic lithium is an anode, and 1 mol of LiPF 6 / ethylene carbonate (EC) + dimethyl carbonate (DMC) (EC: DMC = 1) : 2 (volume ratio)) as an electrolytic solution to prepare a coin-type battery (CR2032 type).
[0030]
The discharge capacity evaluation was performed as follows. First, the battery was discharged at a constant current of 0.2 mA / cm 2 until the voltage reached 0 V, and after a pause of 10 minutes, charged at a constant current of 0.20 mA / cm 2 until the voltage reached 1.0 V. This was defined as one cycle, and charge and discharge were repeatedly performed to check the discharge capacity. Table 1 shows the number of cycles and discharge capacity of the composite powder of each example. Table 1 shows, as a comparison, the cycle number and the discharge even when the binary alloys described in Comparative Examples 1 to 16 of Table 1 or the single metal described in Comparative Examples 17 to 32 were used as the negative electrode material. Indicates the capacity.
[0031]
[Table 1]
As is evident from Table 1, when the composite powder of each example was used, the initial discharge capacity was high and the discharge capacity after 50 cycles was sufficiently maintained.
[0033]
Further, a scanning electron micrograph (SEM) of a cross section of the composite powder of Example 2 (Sn / Ag / Fe (at.%) = 48 / 36.4 / 15.6) and distribution of each element by an X-ray microanalysis method FIG. 1 shows a distribution diagram showing the state, and a scanning electron micrograph (SEM) and an X-ray microanalysis method of a cross section of the composite powder of Example 3 (Sn / Ag / Fe (atomic%) = 48/26/26) FIG. 2 is a distribution diagram showing the distribution state of each element according to FIG. From FIGS. 1 and 2, in each of the composite particles of Examples 2 and 3, Ag and Sn are uniformly distributed throughout the particles, whereas Fe as the B component is partially segregated. I understand.
[0034]
FIG. 3 is a graph showing the relationship between the discharge capacity and the number of cycles for the composite powder of Example 2 (Sn / Ag / Fe (at.%) = 48 / 36.4 / 15.6). FIG. 3 shows, as a comparison, a result when a composite powder of Ag / Sn (atomic%) = 52/48 was used as a negative electrode material, and a case where each metal of Sn, Ag and Fe was used alone as a negative electrode material. The results are also shown.
[0035]
As is clear from FIG. 3, the negative electrode material using the composite powder of Example 2 has excellent cycle characteristics.
[0036]
Further, FIG. 4 shows the discharge capacity and the discharge capacity when the composite powder of Example 3 (Sn / Ag / Fe (atomic%) = 48/26/26) was used as a negative electrode material and charging and discharging were repeated up to 300 cycles. 4 shows a graph of the relationship with the number of cycles.
[0037]
From FIG. 4, when the composite powder of Example 3 is used as a negative electrode material, the initial capacity is about 550 mAh / g, and the capacity of 200 mAh / g is maintained even after 300 cycles, and excellent cycle life is obtained. It turns out that it has.
[Brief description of the drawings]
FIG. 1 is a scanning electron micrograph (SEM) of a cross section of a composite powder obtained in Example 2 and a distribution diagram showing a distribution state of each element by an X-ray microanalysis method.
FIG. 2 is a scanning electron micrograph (SEM) of a cross section of the composite powder obtained in Example 3 and a distribution diagram showing a distribution state of each element by an X-ray microanalysis method.
FIG. 3 is a graph showing the relationship between the discharge capacity and the number of cycles for the composite powder obtained in Example 2.
FIG. 4 is a graph showing the relationship between the discharge capacity and the number of cycles for the composite powder obtained in Example 3.
Claims (4)
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| JP2007095563A (en) * | 2005-09-29 | 2007-04-12 | Sony Corp | Negative electrode and battery |
| US7807292B2 (en) | 2006-05-17 | 2010-10-05 | Sony Corporation | Secondary battery |
| KR101366966B1 (en) | 2009-12-25 | 2014-02-24 | 쥬오 덴끼 고교 가부시키가이샤 | Negative electrode material for a nonaqueous electrolyte secondary battery, and manufacturing method therefor |
| CN112585699A (en) * | 2018-08-21 | 2021-03-30 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
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| JP2007095563A (en) * | 2005-09-29 | 2007-04-12 | Sony Corp | Negative electrode and battery |
| US7807292B2 (en) | 2006-05-17 | 2010-10-05 | Sony Corporation | Secondary battery |
| US8168320B2 (en) | 2006-05-17 | 2012-05-01 | Sony Corporation | Secondary battery |
| KR101366966B1 (en) | 2009-12-25 | 2014-02-24 | 쥬오 덴끼 고교 가부시키가이샤 | Negative electrode material for a nonaqueous electrolyte secondary battery, and manufacturing method therefor |
| CN112585699A (en) * | 2018-08-21 | 2021-03-30 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN112585699B (en) * | 2018-08-21 | 2022-05-13 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
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