JP6688673B2 - Silicon oxide powder negative electrode material - Google Patents
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- JP6688673B2 JP6688673B2 JP2016095100A JP2016095100A JP6688673B2 JP 6688673 B2 JP6688673 B2 JP 6688673B2 JP 2016095100 A JP2016095100 A JP 2016095100A JP 2016095100 A JP2016095100 A JP 2016095100A JP 6688673 B2 JP6688673 B2 JP 6688673B2
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- 239000000843 powder Substances 0.000 title claims description 132
- 239000007773 negative electrode material Substances 0.000 title claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 209
- 239000002245 particle Substances 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 description 82
- 238000000034 method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 238000013507 mapping Methods 0.000 description 13
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000002427 irreversible effect Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910004283 SiO 4 Inorganic materials 0.000 description 6
- 229910000103 lithium hydride Inorganic materials 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 5
- 229910052912 lithium silicate Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011863 silicon-based powder Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 4
- -1 Li 4 SiO 4 Chemical compound 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012506 LiSi Inorganic materials 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
Description
本発明は、リチウムイオン二次電池の負極形成に使用されるＳｉＯx系粉末負極材に関し、より詳しくは、不可逆容量キャンセル処理を受けたＳｉＯx系粉末負極材に関する。なお、本明細書では酸化珪素とＳｉＯxは同義である。 The present invention relates to a SiO x powder negative electrode material used for forming a negative electrode of a lithium ion secondary battery, and more particularly to a SiO x powder negative electrode material that has been subjected to an irreversible capacity cancellation treatment. Note that in this specification, silicon oxide and SiO x have the same meaning.
ＳｉＯxは電気容量が大きく、優れたリチウムイオン二次電池用負極材であることが知られている。このＳｉＯx系粉末負極材は、ＳｉＯx粉末、導電助剤及びバインダーを混合してスラリー化したものを、銅箔等からなる集電体上に塗布し乾燥させることで薄膜状の負極とされる。ここにおけるＳｉＯx粉末は、例えば二酸化珪素と珪素との混合物を加熱して生成した一酸化珪素ガスを冷却し、析出させた後、細かく破砕することにより得られる。このような析出法で製造されるＳｉＯx粉末は、非晶質の部分を多く含み、熱膨張係数を小さくして、サイクル特性を向上させることが知られている。 It is known that SiO x has a large electric capacity and is an excellent negative electrode material for lithium ion secondary batteries. This SiO x powder negative electrode material is formed into a thin film negative electrode by mixing a slurry made by mixing SiO x powder, a conductive additive and a binder, and applying it to a current collector made of copper foil or the like and drying. It The SiO x powder here is obtained, for example, by heating a mixture of silicon dioxide and silicon, cooling the generated silicon monoxide gas, depositing it, and then crushing it finely. It is known that the SiO x powder produced by such a precipitation method contains a large amount of an amorphous portion and has a small thermal expansion coefficient to improve cycle characteristics.
このようなＳｉＯx系粉末負極材の問題点としては、初期効率の低さがあり、これを解消する手法として、Ｌｉドープが知られている。Ｌｉドープは、ＳｉＯx粉末と粉末リチウム源とを混合し、焼成することにより実施される（特許文献１〜４）。ＳｉＯxの粉末粒子にＬｉドープを行うと、充放電に寄与しないリチウム化合物（Ｌｉ4ＳｉＯ4等）が事前に生成され、初回充電時にこのリチウム化合物が生成されるのが抑制されることにより、初期効率の向上が図られる。この処理は不可逆容量のキャンセル処理と呼ばれている。 A problem with such a SiO x -based powder negative electrode material is low initial efficiency, and Li doping is known as a method for solving this problem. Li doping is carried out by mixing a SiO x powder and a powder lithium source and firing the mixture (Patent Documents 1 to 4). When Li-doping is performed on the SiO x powder particles, a lithium compound (Li 4 SiO 4 etc.) that does not contribute to charge and discharge is generated in advance, and by suppressing the generation of this lithium compound at the time of the first charge, The initial efficiency is improved. This processing is called irreversible capacity cancellation processing.
不可逆容量をキャンセルする以外の電池性能向上手段としては、ＳｉＯx粉末の粒子表面に導電性炭素を被覆するＣコートがあり、これによりサイクル特性の向上が図られる。特許文献３ではＬｉドープ後にＣコートが実施され、特許文献４ではＣコート後にＬｉドープが実施されている。 As a means for improving battery performance other than canceling the irreversible capacity, there is a C coat that coats conductive carbon on the particle surface of the SiO x powder, which improves the cycle characteristics. In Patent Document 3, C coating is performed after Li doping, and in Patent Document 4, Li doping is performed after C coating.
また、Ｌｉドープ以外の不可逆容量キャンセル処理としては、Ｍｇドープが知られている（特許文献５）。ＳｉＯx粉末にＭｇドープを行うと、充放電に寄与しないマグネシウム化合物（Ｍｇ2ＳｉＯ4等）が事前に生成され、初回充電時にリチウム化合物が生成されるのが抑制されることにより、初期効率の向上が図られる。 In addition, Mg doping is known as an irreversible capacity canceling treatment other than Li doping (Patent Document 5). When Mg doping is performed on the SiO x powder, a magnesium compound (Mg 2 SiO 4 etc.) that does not contribute to charge and discharge is generated in advance, and the generation of a lithium compound at the time of the first charge is suppressed, thereby reducing the initial efficiency. Improvement is achieved.
加えて、Ｍｇ2ＳｉＯ4等の珪酸マグネシウムは、Ｌｉ4ＳｉＯ4等の珪酸リチウムに比べて格子定数が大きいためにＬｉイオン伝導度が高い。このため、Ｍｇドープを受けたＳｉＯx系粉末負極材は、Ｌｉドープを受けたＳｉＯx系粉末負極材と比べ、出力特性、具体的には急速充放電特性に優れることが報告されている。 In addition, since magnesium silicate such as Mg 2 SiO 4 has a larger lattice constant than lithium silicate such as Li 4 SiO 4, it has a high Li ion conductivity. For this reason, it has been reported that the Mg x -doped SiO x powder negative electrode material is superior to the Li-doped SiO x powder negative electrode material in output characteristics, specifically, rapid charge and discharge characteristics.
しかしながら、ＭｇはＬｉに比べて重い。このため、Ｍｇドープを受けたＳｉＯx系粉末負極材は、Ｌｉドープを受けたＳｉＯx系粉末負極材に比べて重量あたりの容量を低下させるという問題がある。 However, Mg is heavier than Li. Therefore, there is a problem that the Mg-doped SiO x powder negative electrode material has a lower capacity per weight than the Li-doped SiO x powder negative electrode material.
ＳｉＯx系粉末負極材の用途として現在は情報端末機器用電池が一般的であるが、将来的には自動車等の輸送機器用電池も考えられている。輸送機器用電池用途の場合、大容量電池の搭載が前提となるため、急速充放電特性の高さが大きな利点となる反面、重量あたりの容量の低さは大きな欠点となることから、初期特性やサイクル特性の高さのみならず、急速充放電特性の高さ、更には重量あたりの容量の大きさまでも含めた総合的な電池性能が求められることになる。 Currently, batteries for information terminal equipment are generally used as the applications of the SiO x powder negative electrode material, but batteries for transportation equipment such as automobiles are also considered in the future. In the case of batteries for transportation equipment, it is premised that a large-capacity battery is installed, so while high charge / discharge characteristics are a major advantage, low capacity per weight is a major drawback. In addition to high cycle characteristics, high charge / discharge characteristics, and overall battery performance, including high capacity per weight, is required.
本発明の目的は、初期特性やサイクル特性の高さのみならず、急速充放電特性の高さ、更には重量あたりの容量の大きさまでも含めた総合的な電池性能の向上に有効なＳｉＯx系粉末負極材を提供することにある。 The object of the present invention is to improve not only the initial characteristics and the cycle characteristics but also the characteristics of the rapid charge / discharge characteristics, and further, the SiO x effective for improving the overall battery performance including the capacity per weight. An object is to provide a powdered negative electrode material.
上記目的を達成するために、本発明者はＳｉＯx系粉末負極材に対するＬｉドープとＭｇドープの得失について詳細に比較検討した。その結果、以下の事実が判明した。 In order to achieve the above object, the present inventor conducted a detailed comparative study on the advantages and disadvantages of Li-doping and Mg-doping with respect to the SiO x -based powder negative electrode material. As a result, the following facts were revealed.
Ｌｉドープを受けたＳｉＯx系粉末負極材は初期効率の改善に有効であるが、一方で空気、水、その他の溶媒に対する活性が高くなり、ハンドリング性を悪化させるだけでなく、バインダーを用いてスラリー化する際に、水系バインダーを用いた場合には溶媒である水がＬｉと反応し、また非水溶剤系バインダーであるポリイミドを使用した場合にもポリイミドがＬｉと反応することにより、スラリーの安定性が低下し、サイクル特性を悪化させる原因となる。 The Li-doped SiO x powder negative electrode material is effective in improving the initial efficiency, but on the other hand, the activity against air, water, and other solvents becomes high, which not only deteriorates the handling property, but also uses a binder. When making a slurry, water that is a solvent reacts with Li when an aqueous binder is used, and when a polyimide that is a non-aqueous solvent binder is used, the polyimide also reacts with Li to form a slurry. Stability is reduced, which causes deterioration of cycle characteristics.
これは、Ｌｉ源とＳｉＯxの反応が表面反応であるために、Ｌｉドープを受けたＳｉＯxの表面に活性の高いＬｉが多く残っているためと考えられる。すなわち、ＳｉＯxとＬｉの表面反応においては、Ｌｉ2Ｓｉ2Ｏ5、Ｌｉ2ＳｉＯ3、Ｌｉ4ＳｉＯ4といった珪酸リチウム、更にはＬｉＳｉ合金などが発生すると考えられるが、いずれもＳｉＯxに比べて活性が高く、空気中のハンドリングにおいて注意を要するだけでなく、特に水系バインダー中での溶出及び副反応が現行の負極製造プロセス上では問題となり、特にサイクル特性の悪化の原因となるのである。 It is considered that this is because a large amount of highly active Li remains on the surface of the Li-doped SiO x because the reaction between the Li source and SiO x is a surface reaction. That is, in the surface reaction of the SiO x and Li, Li 2 Si 2 O 5 , Li 2 SiO 3, Li 4 lithium silicate such SiO 4, but further believed that such LiSi alloy occurs, both compared to the SiO x In addition to being highly active and requiring attention in handling in air, elution and side reactions especially in an aqueous binder become a problem in the current negative electrode manufacturing process and cause deterioration of cycle characteristics in particular.
これに対し、ＳｉＯxにＭｇをドープした際に生成するＭｇＳｉＯ3やＭｇ2ＳｉＯ4といった珪酸マグネシウムは、珪酸リチウムに比べ水や有機溶媒に対して安定であり、且つ珪酸リチウムと同等以上のＬｉイオン伝導性を有することから、ＳｉＯxへのＭｇドープは不可逆容量をキャンセルしつつ、また急速充放電特性を高めつつ、スラリー化した際の安定性を確保し、サイクル特性の確保に有効な手段と考えられる。 On the other hand, magnesium silicates such as MgSiO 3 and Mg 2 SiO 4 produced when SiO x is doped with Mg are more stable to water and organic solvents than lithium silicate, and have the same or higher Li content than lithium silicate. Since it has ionic conductivity, Mg doping to SiO x cancels the irreversible capacity and enhances the rapid charge and discharge characteristics, and also secures stability when slurried and is an effective means for securing cycle characteristics. it is conceivable that.
ただし、負極活物質そのものの特性としては、ＭｇドープはＬｉドープやドープなしの場合に比べて悪化する。なぜなら、Ｍｇドープの場合、充放電中の活物質の構造変化によるサイクル特性の悪化が懸念されるからであり、より具体的には、珪酸マグネシウムは充放電の過程でＬｉと反応して酸化マグネシウムと珪酸リチウムに分解するため、長期的にはサイクル特性悪化の懸念があるのである。 However, as the characteristics of the negative electrode active material itself, Mg doping is deteriorated as compared with the case of Li doping or undoped. This is because, in the case of Mg doping, there is concern that the cycle characteristics may deteriorate due to the structural change of the active material during charging / discharging, and more specifically, magnesium silicate reacts with Li during charging / discharging to react with magnesium oxide. Since it decomposes into lithium silicate, there is a concern that cycle characteristics will deteriorate in the long term.
換言するならば、Ｌｉドープはサイクル特性の悪化を招くが、それは活物質そのものの特性ではなく、スラリー化の工程でＬｉがバインダーと反応することによる特殊事情である。 In other words, Li doping causes deterioration of cycle characteristics, which is not a characteristic of the active material itself but a special circumstance due to Li reacting with the binder in the process of slurry formation.
これらのことから、本発明者はＳｉＯx粉末に対するＬｉドープとＭｇドープの併用を立案した。ＬｉドープとＭｇドープの併用によると、Ｍｇドープのみの場合に比べてＭｇドープ量が減少することから重量あたりの容量が増加する。また、Ｌｉドープのみの場合に比べて急速充放電特性が向上する。そして何よりも、Ｌｉドープの弱点であるバインダーに対する反応性の高さをＭｇドープが補い、Ｌｉドープの長所である活物質としての特性の良さを引き出すことにより、何れの単独ドープの場合よりもサイクル特性を向上させ得ることが判明し、その結果として、初期特性やサイクル特性の高さのみならず、急速充放電特性の高さ、更には重量あたりの容量の大きさまでも含めた総合的な電池性能の向上に非常に有効なことが明らかになった。 Based on these facts, the present inventor has proposed the combined use of Li doping and Mg doping for SiO x powder. When both Li-doped and Mg-doped are used, the amount of Mg-doped is reduced as compared with the case of only Mg-doped, so that the capacity per weight is increased. Further, the rapid charge / discharge characteristics are improved as compared with the case of only Li doping. And above all, Mg-doping compensates for the high reactivity with respect to the binder, which is the weak point of Li-doping, and draws out the good characteristics as an active material, which is the advantage of Li-doping, so that the cycle is longer than in the case of any single dope. It has been found that the characteristics can be improved, and as a result, not only the height of initial characteristics and cycle characteristics but also the height of rapid charging / discharging characteristics, and further the total capacity including the capacity per weight is comprehensive. It became clear that it was very effective in improving the performance.
ちなみに、本来の目的である不可逆容量キャンセル効果及び初期効率に関しては両者の間に大きな差はない。 By the way, there is no big difference between the two with respect to the original purpose of the irreversible capacity canceling effect and the initial efficiency.
本発明のＳｉＯx系粉末負極材はかかる知見を基礎として完成されたものであり、リチウム二次電池の負極形成に使用されるＳｉＯx系粉末負極材であって、ＬｉxＭｇyＳｉＯzの組成式で表され、ここでｘ、ｙ及びｚは正の実数であって下記条件を満たし、かつレーザ式回折式の粒度分布測定装置によって測定したメディアン径（Ｄ50）が０．５μｍ以上３０μｍ以下であるものである。
０．５≦ｚ≦１．５
ｚ／５≦ｘ＋ｙ≦ｚ
ｚ／１００≦ｘ かつｚ／１００≦ｙ
SiO x based powder negative electrode material of the present invention has been completed on the basis of these findings, a SiO x based powder negative electrode material for use in forming the negative electrode of a lithium secondary battery, the Li x Mg y SiO z It is represented by a composition formula, where x, y and z are positive real numbers and satisfy the following conditions, and the median diameter (D 50 ) measured by a laser diffraction type particle size distribution measuring device is 0.5 μm or more and 30 μm or more. It is the following.
0.5 ≦ z ≦ 1.5
z / 5 ≦ x + y ≦ z
z / 100≤x and z / 100≤y
すなわち、本発明のＳｉＯx系粉末負極材は、ＬｉとＭｇの両方がドープされたＳｉＯx粉末であり、ＬｉとＭｇの両方がドープされると、Ｍｇドープ単独の場合に比べて重量あたりの容量が増加する。また、Ｌｉドープ単独の場合に比べて、珪酸化合物のＬｉイオン伝導度が高くなることにより急速充放電特性が向上する。そして何よりも、いずれのドープの場合に比べてもサイクル特性が向上する。 That is, the SiO x -based powder negative electrode material of the present invention is a SiO x powder doped with both Li and Mg, and when both Li and Mg are doped, the weight per unit weight is higher than that in the case of Mg doping alone. Capacity increases. Further, as compared with the case of Li doping alone, the Li ion conductivity of the silicic acid compound is increased, so that the rapid charge / discharge characteristics are improved. Above all, the cycle characteristics are improved as compared with the case of any of the dopes.
ここで、ｚはＯ量（Ｏ／Ｓｉ比）である。これが０．５未満だと負極材がＳｉに近くなりすぎ、酸素に対する活性が高くなって安定性が低下し、反対にこれが１．５超だと酸素過多により初期効率が低下し、電池性能が低下する。したがって、ｚは０．５以上１．５以下とした。 Here, z is the O amount (O / Si ratio). If it is less than 0.5, the negative electrode material becomes too close to Si, and the activity against oxygen becomes high and the stability decreases. On the contrary, if it exceeds 1.5, the initial efficiency decreases due to excess oxygen and the battery performance becomes poor. descend. Therefore, z is set to 0.5 or more and 1.5 or less.
また、ｘ＋ｙはＬｉとＭｇの合計ドープ量である。これがｚ／５未満だとＬｉドープ及びＭｇドープによる不可逆容量キャンセル効果が薄く、反対にこれがｚ超だと活性の高いＬｉ−Ｓｉ合金やＭｇ−Ｓｉ合金が生成し、取り扱い上の問題を生じたり、スラリー溶媒及びバインダーとの反応性が高くなることにより電池性能に悪影響を与えたりする。したがって、ｘ＋ｙはｚ／５以上ｚ以下とした。これはＬｉとＭｇの両方による不可逆容量キャンセル率が２０〜１００％であることを意味する。 Further, x + y is the total doping amount of Li and Mg. If it is less than z / 5, the irreversible capacity canceling effect due to Li doping and Mg doping is thin, while if it exceeds z, a highly active Li-Si alloy or Mg-Si alloy is generated, which causes a handling problem. The high reactivity with the slurry solvent and the binder may adversely affect the battery performance. Therefore, x + y is set to z / 5 or more and z or less. This means that the irreversible capacity cancellation rate due to both Li and Mg is 20 to 100%.
また、Ｌｉドープ量（Ｌｉ／Ｓｉ比）であるｘ、及びＭｇドープ量（Ｍｇ／Ｓｉ比）であるｙは、いずれもｚ／１００以上であることが必要である。いずれか一方がｚ／１００未満であると、併用の効果が薄い。Ｌｉドープ量及びＭｇドープ量がそれぞれ最低でも１％の不可逆容量キャンセル率を担うということである。好ましくはｘ及びｙともにｚ／２０以上である。 Further, both the Li doping amount (Li / Si ratio) x and the Mg doping amount (Mg / Si ratio) y need to be z / 100 or more. If either one is less than z / 100, the combined effect is small. This means that the Li doping amount and the Mg doping amount each bear an irreversible capacity cancellation rate of at least 1%. Both x and y are preferably z / 20 or more.
Ｌｉドープ量とＭｇドープ量の割合に関しては、Ｍｇドープ量よりＬｉドープ量が多いことが望まれる。なぜなら、活物質としての素性はＭｇをドープしたＳｉＯxよりＬｉをドープしたＳｉＯxのほうが良いこと、Ｍｇは比較的少量のドープでもＬｉのスラリー化工程での反応性の高さによる諸問題を効果的に抑制できること、Ｌｉの割合が大きいほどドープ元素の占める重量が小さくなり、重量あたりの容量が増大することなどによる。 Regarding the ratio of the Li doping amount and the Mg doping amount, it is desired that the Li doping amount is larger than the Mg doping amount. This is because it is better for SiO x feature is doped with Li from SiO x doped with Mg as an active material, Mg is the problems due to high reactivity in the slurry process of the Li even a relatively small amount of dope The reason is that the weight can be effectively suppressed, the weight occupied by the doping element becomes smaller as the proportion of Li increases, and the capacity per weight increases.
特に好ましいＭｇのドープ形態は、ＳｉＯx粉末粒子の表面に限定的にＭｇドープ層を形成することである。具体的には、粒子表面でのＯに対するＭｇのモル比ｙｓ／ｚｓを、粒子内部でのＯに対するＭｇのモル比ｙｉ／ｚｉの５倍以上とすること、すなわちｙｓ／ｚｓ≧（ｙｉ／ｚｉ）・５とすることである。そうすることにより、ＬｉドープＳｉＯxを効率的に安定化させることが出来、Ｍｇドープ量の減少が可能となることにより、重量あたりの容量を増大させつつ、他の電池性能、特にサイクル特性の向上が可能となる。 A particularly preferred Mg-doped form is to form a limited Mg-doped layer on the surface of SiO x powder particles. Specifically, the molar ratio ys / zs of Mg to O on the surface of the particles should be 5 times or more the molar ratio yi / zi of Mg to O inside the particles, that is, ys / zs ≧ (yi / zi ) ・ 5. By doing so, Li-doped SiO x can be efficiently stabilized, and the amount of Mg-doped can be reduced, so that the capacity per weight can be increased and other battery performance, especially cycle characteristics, can be improved. It is possible to improve.
これら以外に重要な因子としてはＳｉＯx粉末の粒子径がある。この粒子径は、大きすぎると充放電中の粒子の膨張の影響が大きくなりすぎてサイクル特性が悪化し、また小さすぎると表面積が大きくなりすぎて電解液との反応によるクーロン効率の低下、及び空気との反応性の増大を招くので、レーザ回折式の粒度分布測定装置によって測定したメディアン径（Ｄ50）で表して０．５μｍ以上３０μｍ以下であることが必要であり、１μｍ以上１５μｍ以下が好ましい。 An important factor other than these is the particle size of SiO x powder. If the particle size is too large, the effect of the expansion of the particles during charging / discharging becomes too large and the cycle characteristics deteriorate, and if too small, the surface area becomes too large and the Coulomb efficiency decreases due to the reaction with the electrolytic solution, and Since it causes an increase in reactivity with air, it is necessary that the median diameter (D 50 ) measured by a laser diffraction particle size distribution measuring device is 0.5 μm or more and 30 μm or less, and 1 μm or more and 15 μm or less. preferable.
また、粉末粒子の表面は、その少なくとも一部分を導電性の炭素によって被覆することが、電極中での導電性の観点から望ましく、その被覆量は、ＳｉＯx粉末全体の質量に対する炭素の重量比率で表して０．５〜２０ｗｔ％であることが望ましい。被覆量が０．５ｗｔ％未満であると導電性付与の効果が乏しく、十分な充放電特性が得られない。反対に被覆量が２０ｗｔ％を超えると粉末全体に占めるＳｉＯx粉末の重量が少なくなることによる容量低下が懸念される。 Further, it is desirable that at least a part of the surface of the powder particles is coated with conductive carbon from the viewpoint of conductivity in the electrode, and the coating amount is a weight ratio of carbon to the mass of the entire SiO x powder. It is desirable that the content is 0.5 to 20 wt%. If the coating amount is less than 0.5 wt%, the effect of imparting conductivity is poor and sufficient charge / discharge characteristics cannot be obtained. On the other hand, if the coating amount exceeds 20 wt%, there is a concern that the capacity may be reduced due to the weight of the SiO x powder occupying the entire powder being reduced.
本発明のＳｉＯx系粉末負極材は、ＬｉドープとＭｇドープの併用により、Ｍｇドープ単独の場合に比べて重量あたりの容量が増加し、またＬｉドープ単独の場合に比べて急速充放電特性が向上するのみならず、いずれのドープの場合に比べてもサイクル特性が向上することにより、初期特性やサイクル特性の高さ、急速充放電特性の高さ、更には重量あたりの容量の大きさまでも含めた総合的な電池性能の向上に有効である。 The SiO x -based powder negative electrode material of the present invention has a capacity per weight increased as compared with the case of Mg doping alone by the combined use of Li doping and Mg doping, and has a rapid charge / discharge characteristic as compared with the case of Li doping alone. Not only is it improved, but the cycle characteristics are also improved compared to the case of either dope, so that the initial characteristics and cycle characteristics are high, the rapid charge and discharge characteristics are high, and even the capacity per weight is large. It is effective in improving the overall battery performance including the above.
以下に本発明の実施形態を説明する。本実施形態のＳｉＯx系粉末負極材は次のようなドープ法により製造可能である。 Embodiments of the present invention will be described below. The SiO x powder negative electrode material of this embodiment can be manufactured by the following doping method.
第１のドープ法は、ＳｉＯx系粉末にＬｉをドープし、その粉末に更にＭｇをドープする方法である。具体的には、ＳｉＯx粉末と粉末Ｌｉ源とを混合して焼成した後、その焼成粉末に粉末Ｍｇ源を混合して焼成する。或いは、ＳｉＯx粉末に電気化学的にＬｉをドープした後、その粉末に更に電気化学的にＭｇをドープする。 The first doping method is a method of doping SiO x powder with Li and further doping the powder with Mg. Specifically, after the SiO x powder and the powder Li source are mixed and fired, the powder Mg source is mixed with the fired powder and fired. Alternatively, after the SiO x powder is electrochemically doped with Li, the powder is further electrochemically doped with Mg.
第２のドープ法は、ＳｉＯx系粉末にＭｇをドープし、その粉末に更にＬｉをドープする方法である。具体的には、ＳｉＯx粉末と粉末Ｍｇ源とを混合して焼成した後、その焼成粉末に粉末Ｌｉ源を混合して焼成する。或いは、ＳｉＯx粉末に電気化学的にＭｇをドープした後、その粉末に更に電気化学的にＬｉをドープする。 The second doping method is a method of doping Mg into the SiO x powder and further doping the powder with Li. Specifically, after the SiO x powder and the powder Mg source are mixed and fired, the powder Li source is mixed with the fired powder and fired. Alternatively, after the SiO x powder is electrochemically doped with Mg, the powder is further electrochemically doped with Li.
第３のドープ法は、ＳｉＯx系粉末にＬｉとＭｇを同時にドープする方法である。具体的には、ＳｉＯx系粉末に対して粉末Ｌｉ源と粉末Ｍｇ源を混合して焼成する。 The third doping method is a method of simultaneously doping Li and Mg into SiO x powder. Specifically, the SiO x powder is mixed with a powder Li source and a powder Mg source and fired.
第４のドープ法は、ＳｉＯx系粉末の製造過程でＬｉとＭｇを同時に混合する方法である。具体的には、ＳｉとＳｉＯ2系粉末と粉末Ｌｉ源と粉末Ｍｇ源とを混合して減圧下で熱処理し、基材に蒸着させる。 The fourth doping method is a method of simultaneously mixing Li and Mg in the production process of the SiO x powder. Specifically, Si, a SiO 2 -based powder, a powder Li source, and a powder Mg source are mixed, heat-treated under reduced pressure, and vapor-deposited on a substrate.
いずれのドープ法によっても、ＬｉドープとＭｇドープが併用されたＳｉＯx系粉末負極材の製造が可能であるが、Ｍｇドープ層を粒子表面に限定的に形成する観点からは、第１〜第３の方法が好ましい。 By any of the doping methods, it is possible to manufacture a SiO x powder negative electrode material in which Li doping and Mg doping are used in combination, but from the viewpoint of forming the Mg doped layer on the particle surface only, the first to the first Method 3 is preferred.
粉末Ｌｉ源としては、水素化リチウム（ＬｉＨ）、酸化リチウム（Ｌｉ2Ｏ）、水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ2ＣＯ3）などの使用が可能である。また、粉末Ｍｇ源としては、水素化マグネシウム（ＭｇＨ2）、酸化マグネシウム（ＭｇＯ）、水酸化マグネシウム（Ｍｇ（ＯＨ）2）、炭酸マグネシウム（ＭｇＣＯ3）などの使用が可能である。 As the powder Li source, lithium hydride (LiH), lithium oxide (Li 2 O), lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ) or the like can be used. As the powder Mg source, magnesium hydride (MgH 2 ), magnesium oxide (MgO), magnesium hydroxide (Mg (OH) 2 ), magnesium carbonate (MgCO 3 ), or the like can be used.
両ドープ前の粉末、又は両ドープ後の粉末、若しくは両ドープ間の粉末に対して、必要に応じて導電性炭素皮膜被覆のためのＣコートを行う。このＣコートは、炭素源として炭化水素ガスを用いた熱ＣＶＤ法、例えばアルゴンとプロパンの混合ガス雰囲気中での加熱処理により行う。 The powder before the both dopes, the powder after the both dopes, or the powder between the both dopes is subjected to C coating for coating the conductive carbon film, if necessary. This C coating is performed by a thermal CVD method using a hydrocarbon gas as a carbon source, for example, a heat treatment in a mixed gas atmosphere of argon and propane.
（実施例１）
本発明のＳｉＯx系粉末負極材を第４のドープ法により製造した。具体的には以下のとおりである。
(Example 1)
The SiO x powder negative electrode material of the present invention was manufactured by the fourth doping method. Specifically, it is as follows.
Ｓｉ粉末とＳｉＯ2粉末と粉末Ｌｉ源であるＬｉＯ2粉末と粉末Ｍｇ源であるＭｇＯ粉末とをモル比で１３：７：２：４の比率で混合した。その混合粉末を減圧下で１４００℃で焼成して昇華させた。昇華したガスを石英の基材上に蒸着させた。蒸着物を回収して粉砕した。粉砕により得た粉末に対して、アルゴンとプロパンの混合ガスを炭素源とする熱ＣＶＤにより８５０℃でＣコートを行った。 Si powder, SiO 2 powder, powder Li source LiO 2 powder, and powder Mg source MgO powder were mixed at a molar ratio of 13: 7: 2: 4. The mixed powder was calcined under reduced pressure at 1400 ° C. to be sublimated. The sublimed gas was deposited on a quartz substrate. The deposit was collected and crushed. The powder obtained by pulverization was subjected to C coating at 850 ° C. by thermal CVD using a mixed gas of argon and propane as a carbon source.
得られた粉末に対して、Ｓｉ、Ｏ及びＬｉの各元素についての分析を行った。Ｓｉ及びＬｉについては、ＩＣＰ発光分光分析によって含有率を求めた。Ｏについては、LECO社製TC-436を使用して、不活性ガス融解−赤外線吸収法（inert gas fusion infrared absorption method;GFA ）により含有率を測定した。その結果、蒸着物の組成はＬｉxＭｇyＳｉＯz（ｘ＝０．２、ｙ＝０．２、ｚ＝１）であることが分かった。また、Ｃコート量は１．０ｗｔ％、メディアン径Ｄ50は６．１３μｍであった。 The obtained powder was analyzed for each element of Si, O and Li. The contents of Si and Li were determined by ICP emission spectroscopy. The content of O was measured by an inert gas fusion infrared absorption method (GFA) using TC-436 manufactured by LECO. As a result, it was found that the composition of the deposited material was Li x Mg y SiO z (x = 0.2, y = 0.2, z = 1). The C coating amount was 1.0 wt% and the median diameter D 50 was 6.13 μm.
得られた粉末は、Ｌｉドープ及びＭｇドープを受け、且つＣコートを受けたＳｉＯ粉末である。この粉末に対して、ＢＩＢ法により粉末粒子の断面を露出させ、その断面を電界放射型ＳＥＭで観察した。また、露出した粒子断面に対して５ｋＶの電圧でＳｉ、Ｏ、Ｍｇの３元素についてＥＤＸマッピングを行った。Ｓｉ、Ｏ、ＭｇについてのＥＤＸマッピング結果を図１、図２、図３にそれぞれ示す。 The powder obtained is a SiO powder that is Li-doped and Mg-doped and C-coated. A cross section of powder particles was exposed to this powder by the BIB method, and the cross section was observed by a field emission SEM. In addition, EDX mapping was performed for the three elements of Si, O, and Mg at a voltage of 5 kV on the exposed particle cross section. The EDX mapping results for Si, O, and Mg are shown in FIGS. 1, 2, and 3, respectively.
ＥＤＸマッピングを行った粒子断面について、外接円の直径をＤOとしたとき、粒子表面からＤO／１００までの領域内におけるＳｉ、Ｏ、Ｍｇの組成比を１０点の平均で求めて、粒子表面でのＯに対するＭｇのモル比ｙｓ／ｚｓを求めた。また、粒子内部でのＯに対するＭｇのモル比ｙｉ／ｚｉを求めた。ｙｓ／ｚｓ＝０．２１、ｙｉ／ｚｉ＝０．２０であった。 For particle cross sections subjected to EDX mapping, when the diameter of the circumscribed circle and the D O, Si in the region from the particle surface to D O / 100, O, seeking the average of 10 points the composition ratio of Mg, particles The molar ratio ys / zs of Mg to O on the surface was determined. Further, the molar ratio yi / zi of Mg to O inside the particles was determined. It was ys / zs = 0.21 and yi / zi = 0.20.
ここで、粒子表面とは、粒子断面のＥＤＸマッピングにおいて、粒子内部とＳｉの信号が０となる部分の境界のうち、粒子内部側の面をいう。また、粒子内部の組成比は、粒子表面からＤO／５まで入ったところから、粒子表面からＤO／２まで入ったところまでの範囲内で且つ粒子内にある点の領域から１０点を無作為に選んで求めた。 Here, in the EDX mapping of the particle cross section, the particle surface refers to the surface on the particle inner side of the boundary between the inside of the particle and the portion where the Si signal is 0. The composition ratio inside the particle is within the range from the surface of the particle up to D O / 5 to the surface of the particle up to D O / 2, and 10 points from the area of the point inside the particle. Randomly selected and sought.
そして、Ｌｉドープ及びＭｇドープを受け、且つＣコートを受けたＳｉＯ粉末を用いてリチウムイオン二次電池用負極を作製し、その電池性能を評価した。 Then, a negative electrode for a lithium-ion secondary battery was produced using the SiO powder that had been subjected to Li-doping and Mg-doping and also had been subjected to C-coating, and the battery performance thereof was evaluated.
具体的には、ＳｉＯ粉末、ケッチェンブラック、及び非水溶剤系バインダーであるポリイミド前駆体を８５：５：１０の質量比で混合し、更にＮＭＰ（ｎメチルピロリドン）を加えて混練することでスラリーを作製した。そして、そのスラリーを厚さ４０μｍの銅箔上に塗布し、８０℃で１５分間予備乾燥し、直径１１ｍｍに打ち抜いた後、イミド化処理して負極とした。 Specifically, SiO powder, Ketjen black, and a polyimide precursor that is a non-aqueous solvent-based binder are mixed in a mass ratio of 85: 5: 10, and NMP (n-methylpyrrolidone) is further added and kneaded. A slurry was prepared. Then, the slurry was applied onto a copper foil having a thickness of 40 μm, pre-dried at 80 ° C. for 15 minutes, punched out to a diameter of 11 mm, and then imidized to obtain a negative electrode.
作製された負極を用いてリチウムイオン二次電池を作製した。二次電池おける対極にはリチウム箔を用いた。電解質にはエチレンカーボネート、及びジエチルカーボネートを１：１の体積比で混合した溶液に、ＬｉＰＦ6（六フッ化リンリチウム）を１モル／リットルの割合になるように溶解させた溶液を用いた。そして、セパレータに厚さ３０μｍのポリエチレン製多孔質フィルムを用いて、コインセルを作製した。 A lithium ion secondary battery was produced using the produced negative electrode. Lithium foil was used as the counter electrode in the secondary battery. As the electrolyte, a solution in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 and LiPF 6 (lithium phosphorus hexafluoride) was dissolved at a ratio of 1 mol / liter was used. Then, a coin cell was produced by using a polyethylene porous film having a thickness of 30 μm as the separator.
作製されたリチウムイオン二次電池に対して、二次電池充放電試験装置（株式会社ナガノ製）を用いて充放電試験を行った。充放電の条件を表１に示す。 A charging / discharging test was performed on the manufactured lithium ion secondary battery using a secondary battery charging / discharging test device (manufactured by Nagano Co., Ltd.). Table 1 shows the charging / discharging conditions.
この充放電試験により、初回充電容量、初回充電容量に対する初回放電容量の比（初期効率）、初回の放電容量に対する３回目の放電容量の比（レート特性）、初回の放電容量に対する５０回目の放電容量の比（５０回目維持率）をそれぞれ求めた。 By this charge / discharge test, the initial charge capacity, the ratio of the initial discharge capacity to the initial charge capacity (initial efficiency), the ratio of the third discharge capacity to the initial discharge capacity (rate characteristic), the 50th discharge to the initial discharge capacity. The capacity ratios (50th retention rate) were determined.
（実施例２）
実施例１において、Ｓｉ粉末とＳｉＯ2粉末と粉末Ｌｉ源であるＬｉＯ2粉末と粉末Ｍｇ源であるＭｇＯ粉末との混合モル比で２５：１５：６：４とした。この比率が異なる以外は実施例１と同様の方法で、Ｌｉドープ・Ｍｇドープを受けたＣコートＳｉＯ粉末を作製した。
(Example 2)
In Example 1, the mixing molar ratio of Si powder, SiO 2 powder, LiO 2 powder as a powder Li source, and MgO powder as a powder Mg source was set to 25: 15: 6: 4. Li-doped / Mg-doped C-coated SiO powder was produced in the same manner as in Example 1 except that this ratio was different.
作製されたＳｉＯ粉末の組成はＬｉxＭｇyＳｉＯz（ｘ＝０．３、ｙ＝０．１、ｚ＝１）である。また、Ｃコート量は１．５ｗｔ％、メディアン径Ｄ50は６．０５μｍである。粒子表面でのＯに対するＭｇのモル比はｙｓ／ｚｓ＝０．１２、粒子内部でのＯに対するＭｇのモル比はｙｉ／ｚｉ＝０．１３である。 The composition of the produced SiO powder is Li x Mg y SiO z (x = 0.3, y = 0.1, z = 1). The C coating amount is 1.5 wt% and the median diameter D 50 is 6.05 μm. The molar ratio of Mg to O on the particle surface is ys / zs = 0.12, and the molar ratio of Mg to O inside the particle is yi / zi = 0.13.
（実施例３）
本発明のＳｉＯx系粉末負極材を第１のドープ法により製造した。具体的にはＳｉＯx（ｘ＝１）を析出法で作製し、粉砕した。そのＳｉＯ粉末にアルゴンとプロパンの混合ガスを炭素源とする熱ＣＶＤにより８５０℃でＣコートを行った。そのＣコートＳｉＯ粉末に対して、粉末Ｌｉ源である水素化リチウムをＳｉＯとのモル比がＬｉ／Ｏ＝０．３５となるように混合した後、６００℃で２４時間焼成することによりＬｉドープを行った。
(Example 3)
The SiO x powder negative electrode material of the present invention was produced by the first doping method. Specifically, SiO x (x = 1) was prepared by a precipitation method and crushed. The SiO powder was C-coated at 850 ° C. by thermal CVD using a mixed gas of argon and propane as a carbon source. Lithium hydride, which is a powder Li source, was mixed with the C-coated SiO powder so that the molar ratio with SiO was Li / O = 0.35, and then the mixture was baked at 600 ° C. for 24 hours to perform Li doping. I went.
更に、ＬｉドープしたＣコートＳｉＯ粉末に、粉末Ｍｇ源である水素化マグネシウム粉末をモル比がＭｇ／Ｏ＝０．０５となるように混合し、６００℃で２４時間焼成することによりＭｇドープを行った。この際、６００℃へ昇温するときの昇温速度は３００℃／Ｈｒとした。この時点でのＣコート量は０．８ｗｔ％、メディアン径Ｄ50は６．２６μｍである。 Further, magnesium-hydride powder, which is a powder Mg source, is mixed with Li-doped C-coated SiO powder so that the molar ratio is Mg / O = 0.05, and the mixture is baked at 600 ° C. for 24 hours to add Mg-doped powder. went. At this time, the temperature rising rate when the temperature was raised to 600 ° C. was 300 ° C./Hr. At this point, the C coating amount is 0.8 wt% and the median diameter D 50 is 6.26 μm.
Ｓｉ、Ｏ、ＭｇについてのＥＤＸマッピング結果を図４、図５、図６にそれぞれ示す。これから求めた粒子表面でのＯに対するＭｇのモル比はｙｓ／ｚｓ＝０．３、粒子内部でのＯに対するＭｇのモル比はｙｉ／ｚｉ＝０．００１である。Ｍｇドープ層が粒子表面に限定的に形成されていることは図６からも明らかである。 The EDX mapping results for Si, O, and Mg are shown in FIGS. 4, 5, and 6, respectively. The molar ratio of Mg to O on the particle surface obtained from this is ys / zs = 0.3, and the molar ratio of Mg to O inside the particle is yi / zi = 0.001. It is clear from FIG. 6 that the Mg-doped layer is formed only on the surface of the particles.
（実施例４）
実施例３において、ＣコートＳｉＯ粉末に対して、粉末Ｌｉ源である水素化リチウムをＳｉＯとのモル比がＬｉ／Ｏ＝０．３７となるように混合した。また、ＬｉドープしたＳｉＯ粉末に対して、粉末Ｍｇ源である水素化マグネシウム粉末をモル比がＭｇ／Ｏ＝０．０３となるように混合した。Ｓｉ、Ｏ、ＭｇについてのＥＤＸマッピング結果から求めた粒子表面でのＯに対するＭｇのモル比はｙｓ／ｚｓ＝０．２２、粒子内部でのＯに対するＭｇのモル比はｙｉ／ｚｉ＝０．００１である。他は実施例３と同じである。
(Example 4)
In Example 3, lithium hydride as a powder Li source was mixed with the C-coated SiO powder so that the molar ratio with SiO was Li / O = 0.37. Further, magnesium hydride powder as a powder Mg source was mixed with Li-doped SiO powder so that the molar ratio was Mg / O = 0.03. The molar ratio of Mg to O on the particle surface was ys / zs = 0.22, and the molar ratio of Mg to O inside the particle was yi / zi = 0.001, which was obtained from the EDX mapping results of Si, O, and Mg. Is. Others are the same as in the third embodiment.
（実施例５）
実施例３において、ＣコートＳｉＯ粉末に対して、粉末Ｌｉ源である水素化リチウムをＳｉＯとのモル比がＬｉ／Ｏ＝０．３９となるように混合した。また、ＬｉドープしたＳｉＯ粉末に対して、粉末Ｍｇ源である水素化マグネシウム粉末をモル比がＭｇ／Ｏ＝０．０１となるように混合した。Ｓｉ、Ｏ、ＭｇについてのＥＤＸマッピング結果から求めた粒子表面でのＯに対するＭｇのモル比はｙｓ／ｚｓ＝０．０９、粒子内部でのＯに対するＭｇのモル比はｙｉ／ｚｉ＝０である。他は実施例３と同じである。
(Example 5)
In Example 3, lithium hydride as a powder Li source was mixed with the C-coated SiO powder so that the molar ratio with SiO was Li / O = 0.39. Further, magnesium hydride powder as a powder Mg source was mixed with Li-doped SiO powder so that the molar ratio was Mg / O = 0.01. The molar ratio of Mg to O on the particle surface obtained from the EDX mapping results for Si, O, and Mg is ys / zs = 0.09, and the molar ratio of Mg to O inside the particle is yi / zi = 0. . Others are the same as in the third embodiment.
（比較例１）
実施例３と同様の方法でＣコートＳｉＯ粉末を作製した。すなわち、ＳｉＯx（ｘ＝１）を析出法で作製し、粉砕した後、そのＳｉＯ粉末に、アルゴンとプロパンの混合ガスを炭素源とする熱ＣＶＤにより８５０℃でＣコートを行った。ＣコートＳｉＯ粉末におけるＣコート量は１ｗｔ％、メディアン径Ｄ50は６．１３μｍである。このＣコートＳｉＯ粉末の電池性能を実施例１と同じ方法で評価した。
(Comparative Example 1)
C-coated SiO powder was prepared in the same manner as in Example 3. That is, SiO x (x = 1) was prepared by a precipitation method, pulverized, and then the SiO powder was C-coated at 850 ° C. by thermal CVD using a mixed gas of argon and propane as a carbon source. The C coat amount in the C coat SiO powder is 1 wt%, and the median diameter D 50 is 6.13 μm. The battery performance of this C-coated SiO powder was evaluated by the same method as in Example 1.
（比較例２）
比較例１で作製したＣコートＳｉＯ粉末に対して、粉末Ｌｉ源である水素化リチウムをＳｉＯとのモル比がＬｉ／Ｏ＝０．４０となるように混合した後、６００℃で２４時間焼成することによりＬｉドープを行った。このＬｉドープＳｉＯ粉末の電池性能を実施例１と同じ方法で評価した。
(Comparative example 2)
Lithium hydride that is a powder Li source was mixed with the C-coated SiO powder produced in Comparative Example 1 so that the molar ratio with SiO was Li / O = 0.40, and then calcined at 600 ° C. for 24 hours. By doing so, Li doping was performed. The battery performance of this Li-doped SiO powder was evaluated by the same method as in Example 1.
（比較例３）
Ｓｉ粉末とＳｉＯ2粉末と粉末Ｍｇ源であるＭｇＯ粉末とをモル比で７：３：４の比率で混合して原料とした。これ以外は実施例１と同様の方法でＭｇドープＳｉＯ粉末を作製した。作製されたＳｉＯ粉末の組成はＬｉxＭｇyＳｉＯz（ｘ＝０、ｙ＝０．４、ｚ＝１）である。また、Ｃコート量は１．５ｗｔ％、メディアン径Ｄ50は６．０５μｍである。粒子表面でのＯに対するＭｇのモル比はｙｓ／ｚｓ＝０．４２、粒子内部でのＯに対するＭｇのモル比はｙｉ／ｚｉ＝０．３９である。このＭｇドープＳｉＯ粉末の電池性能を実施例１と同じ方法で評価した。
(Comparative example 3)
Si powder, SiO 2 powder, and MgO powder as a powder Mg source were mixed at a molar ratio of 7: 3: 4 to prepare a raw material. Except for this, the Mg-doped SiO powder was produced in the same manner as in Example 1. The composition of the produced SiO powder is Li x Mg y SiO z (x = 0, y = 0.4, z = 1). The C coating amount is 1.5 wt% and the median diameter D 50 is 6.05 μm. The molar ratio of Mg to O on the particle surface is ys / zs = 0.42, and the molar ratio of Mg to O inside the particle is yi / zi = 0.39. The battery performance of this Mg-doped SiO powder was evaluated by the same method as in Example 1.
実施例１〜５及び比較例１〜３において得られた各ＳｉＯ粉末の初回放電容量、初期効率、５０回目維持率及びレート特性を、各粉末の組成と共に表２に示す。 Table 2 shows the initial discharge capacity, initial efficiency, 50th maintenance rate and rate characteristics of each SiO powder obtained in Examples 1 to 5 and Comparative Examples 1 to 3, together with the composition of each powder.
比較例１で作製されたＳｉＯ粉末は、ＬｉドープもＭｇドープも受けていない通常のＣコートＳｉＯ負極材である。また、比較例２で作製されたＳｉＯ粉末は、Ｌｉドープのみを受けたＣコートＳｉＯ負極材であり、比較例３で作製されたＳｉＯ粉末は、Ｍｇドープのみを受けたＣコートＳｉＯ負極材である。 The SiO powder produced in Comparative Example 1 is a normal C-coated SiO negative electrode material that is neither Li-doped nor Mg-doped. In addition, the SiO powder prepared in Comparative Example 2 is a C-coated SiO negative electrode material that is only Li-doped, and the SiO powder prepared in Comparative Example 3 is a C-coated SiO negative electrode material that is only Mg-doped. is there.
比較例２のＬｉドープを受けたＳｉＯ負極材は、比較例１の通常のＳｉＯ負極材に比べると、不可逆容量キャンセル効果により初期効率に優れる。ただし、スラリー化工程での副反応により５０回目維持率、すなわちサイクル特性に著しく劣る。 The Li-doped SiO negative electrode material of Comparative Example 2 is superior in initial efficiency to the normal SiO negative electrode material of Comparative Example 1 due to the irreversible capacity canceling effect. However, due to a side reaction in the slurry forming step, the 50th maintenance rate, that is, the cycle characteristic is significantly deteriorated.
一方、比較例３のＭｇドープを受けたＳｉＯ負極材は、比較例２のＬｉドープを受けたＳｉＯ負極材に比べると、同等の初期効率を示しながら、スラリー化工程での安定性向上によりサイクル特性に優れ、しかも珪酸マグネシウムのＬｉイオン伝導度が高いことにより、急速充放電特性であるレート特性も優れる。しかしながら、Ｍｇの原子量が大きいことにより初回放電容量（重量あたりの容量）は大きく減少する。 On the other hand, the Mg-doped SiO negative electrode material of Comparative Example 3 showed the same initial efficiency as that of the Li-doped SiO negative electrode material of Comparative Example 2, while improving the stability in the slurrying process. Since the characteristics are excellent and the Li ion conductivity of magnesium silicate is high, the rate characteristics, which are rapid charge / discharge characteristics, are also excellent. However, since the atomic weight of Mg is large, the initial discharge capacity (capacity per weight) is greatly reduced.
これらに対し、実施例１及び２で作製されたＳｉＯ粉末は、ＬｉドープとＭｇドープを併用されたＳｉＯ負極材であり、合計ドープ量は同じであるものの、ＬｉドープとＭｇドープの併用により、高い初期効率及びレート特性を確保しつつ、初回放電容量を増加させる効果があり、特に注目すべきは５０回目維持率を大きく高める効果があることである。なかでも、実施例２のＳｉＯ負極材は、Ｍｇドープ量を控えたことにより初回放電容量を増加させる効果が大きい。 On the other hand, the SiO powders produced in Examples 1 and 2 are SiO negative electrode materials in which Li-doping and Mg-doping are used in combination, and although the total doping amount is the same, the combined use of Li-doping and Mg-doping results in There is an effect of increasing the initial discharge capacity while ensuring high initial efficiency and rate characteristics, and what is particularly noteworthy is the effect of greatly increasing the 50th maintenance rate. Among them, the SiO negative electrode material of Example 2 has a large effect of increasing the initial discharge capacity by reducing the Mg doping amount.
実施例３〜５で作製されたＳｉＯ粉末も、ＬｉドープとＭｇドープを併用されたＳｉＯ負極材であるが、Ｍｇが粒子表面に偏在してその表面をコートしている。このため、Ｍｇドープ量を更に控えてもなお同等以上の高い５０回目維持率を示し、なおかつ、そのＭｇドープ量の制限により、初回放電容量を更に増加させている。 The SiO powders produced in Examples 3 to 5 are also SiO negative electrode materials in which both Li doping and Mg doping are used, but Mg is unevenly distributed on the particle surface and coats the surface. Therefore, even if the Mg doping amount is further reduced, the same or higher high 50th maintenance rate is still exhibited, and the initial discharge capacity is further increased by the limitation of the Mg doping amount.
Claims (4)
０．５≦ｚ≦１．５
ｚ／５≦ｘ＋ｙ≦ｚ
ｚ／１００≦ｘ かつｚ／１００≦ｙ A silicon oxide-based powder negative electrode material used for forming a negative electrode of a lithium secondary battery, the composition of which is represented by Li x Mg y SiO z , where x, y, and z are positive real numbers and the following conditions are satisfied. A silicon oxide-based powder negative electrode material which is satisfied and has a median diameter (D 50 ) of 0.5 μm or more and 30 μm or less measured by a laser diffraction type particle size distribution measuring device.
0.5 ≦ z ≦ 1.5
z / 5 ≦ x + y ≦ z
z / 100≤x and z / 100≤y
ｙｓ／ｚｓは粒子表面でのＯに対するＭｇのモル比
ｙｉ／ｚｉは粒子内部でのＯに対するＭｇのモル比 The silicon oxide-based powder negative electrode material according to claim 1, wherein the composition satisfies ys / z s ≧ (yi / zi) · 5.
ys / zs is the molar ratio of Mg to O on the particle surface
yi / zi is the molar ratio of Mg to O inside the particle
The silicon oxide-based powder negative electrode material according to claim 1, wherein at least a part of the surface of the powder particles has a conductive carbon coating, and the amount of carbon in the conductive carbon coating is expressed as a ratio to the mass of the entire powder. 0.5-20 wt% silicon oxide powder negative electrode material.
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| WO2022059340A1 (en) * | 2020-09-18 | 2022-03-24 | 株式会社村田製作所 | Negative electrode active material for secondary batteries, negative electrode for secondary batteries, and secondary battery |
| CN112331854A (en) * | 2020-10-30 | 2021-02-05 | 浙江锂宸新材料科技有限公司 | Lithium magnesium silicate pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof |
| CN114497470B (en) * | 2020-11-13 | 2024-03-29 | 湖南中科星城石墨有限公司 | Composite material and preparation method and application thereof |
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| US7432015B2 (en) * | 2004-02-25 | 2008-10-07 | Samsung Sdi Co., Ltd. | Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery comprising the same |
| JP2007026983A (en) * | 2005-07-20 | 2007-02-01 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium ion secondary battery, its manufacturing method and lithium secondary battery using it |
| JP5369708B2 (en) * | 2009-01-26 | 2013-12-18 | 旭硝子株式会社 | Anode material for secondary battery and method for producing the same |
| JP5406799B2 (en) * | 2010-07-29 | 2014-02-05 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing the same, and lithium ion secondary battery |
| JP6013125B2 (en) * | 2012-10-16 | 2016-10-25 | 住友金属鉱山株式会社 | Method for producing lithium silicate compound and method for producing lithium ion battery |
| JP6079869B2 (en) * | 2013-03-22 | 2017-02-15 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP6407804B2 (en) * | 2015-06-17 | 2018-10-17 | 信越化学工業株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for producing negative electrode material for nonaqueous electrolyte secondary battery |
| JP6765984B2 (en) * | 2016-03-16 | 2020-10-07 | 信越化学工業株式会社 | Method for manufacturing negative electrode active material for non-aqueous electrolyte secondary battery and method for manufacturing negative electrode for non-aqueous electrolyte secondary battery |
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