JP2008181830A - Nonaqueous electrolyte secondary battery - Google Patents
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Abstract
Description
本発明は、万が一過充電状態になった電池における安全性の向上及び高温サイクル特性の向上を目的とした非水電解質二次電池の改良に関する。 The present invention relates to an improvement in a non-aqueous electrolyte secondary battery for the purpose of improving safety and high-temperature cycle characteristics in a battery that is overcharged.
今日、携帯電話、ノートパソコン等の移動情報端末の高機能化・小型化および軽量化が急速に進展している。これらの端末の駆動電源として、高いエネルギー密度を有し、高容量であるリチウムイオン二次電池に代表される非水電解質二次電池が広く利用されている。 Today, mobile information terminals such as mobile phones and laptop computers are rapidly becoming more functional, smaller, and lighter. As a driving power source for these terminals, non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries having high energy density and high capacity are widely used.
近年では、リチウムイオン二次電池は、電動工具、電動アシスト自転車、ハイブリッド自動車等に使用することがなされており、これらの用途では、通常よりもハイレートで充放電を行うことが求められている。しかしながら、リチウムイオン二次電池をハイレートで充電する場合、通常の充電条件で充電する場合に比べて、過充電状態になりやすい。このため、ハイレート充電する際の安全性の向上が強く求められている。 In recent years, lithium ion secondary batteries have been used in electric tools, electric assist bicycles, hybrid vehicles, and the like. In these applications, it is required to charge and discharge at a higher rate than usual. However, when the lithium ion secondary battery is charged at a high rate, it is likely to be in an overcharged state as compared with the case of charging under normal charging conditions. For this reason, the improvement of the safety | security at the time of high rate charge is calculated | required strongly.
過充電の安全性を向上させるために、電池内圧の上昇により作動する電流遮断手段を組み込み、過充電の初期に分解してガスを発生させる炭酸リチウムを添加する技術が、特許文献１〜６に提案されている。 In order to improve the safety of overcharge, a technique that incorporates a current interrupting means that operates by increasing the battery internal pressure and adds lithium carbonate that decomposes and generates gas in the initial stage of overcharge is disclosed in Patent Documents 1 to 6. Proposed.
しかし、これらの技術によっても、万が一過充電となってしまった場合における電池の安全性（以下、過充電時安全性という）が未だ十分ではない。 However, even with these technologies, the safety of the battery in the event of overcharging (hereinafter referred to as overcharge safety) is still not sufficient.
本発明は、上記に鑑みなされたものであって、万が一過充電となってしまった場合でも安全性が高い非水電解質二次電池を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a non-aqueous electrolyte secondary battery with high safety even if it is overcharged.
上記課題を解決するための第１の本発明は、正極活物質を有する正極と、負極活物質を有する負極と、非水電解質と、を備えた非水電解質二次電池において、前記正極活物質としてニッケルコバルトマンガン酸リチウム（ＬｉａＮｉｘＣｏｙＭｎｚＯ２、０＜ａ≦１．１、０．１≦ｘ≦０．５、０＜ｙ、０．１≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）のみからなり、平均粒径５〜３０μｍの炭酸リチウムが、前記正極に対して０．５〜２．０質量％添加され、前記正極活物質と前記炭酸リチウムとが均一に混合されていることを特徴とする。 A first aspect of the present invention for solving the above problems is a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a nonaqueous electrolyte. As nickel cobalt lithium manganate (Li a Ni x Co y Mn z O 2 , 0 <a ≦ 1.1, 0.1 ≦ x ≦ 0.5, 0 <y, 0.1 ≦ z ≦ 0.5, x + y + z = 1), lithium carbonate having an average particle size of 5 to 30 μm is added to the positive electrode in an amount of 0.5 to 2.0 mass%, and the positive electrode active material and the lithium carbonate are uniformly mixed. It is characterized by.
ニッケルコバルトマンガン酸リチウムは、過充電時の化合物としての安定性が、従来より正極活物質として用いられているコバルト酸リチウムよりも極めて高い。また、理由は定かではないが、平均粒径５〜３０μｍの炭酸リチウムと正極活物質とが均一に混合されていることにより、過充電時の安全性が高まる。そして、これらの効果が相乗的に作用することにより、過充電時安全性が飛躍的に高まる。 Nickel cobalt lithium manganate has extremely higher stability as a compound during overcharge than lithium cobalt oxide conventionally used as a positive electrode active material. Moreover, although the reason is not certain, the safety | security at the time of an overcharge increases because lithium carbonate with an average particle diameter of 5-30 micrometers and a positive electrode active material are mixed uniformly. And these effects act synergistically, and the safety at the time of overcharge increases remarkably.
炭酸リチウムの添加量が０．５質量％未満であると十分な過充電時安全性向上効果が得られず、他方２．０質量％よりも多いと、炭酸リチウムが充放電サイクルのスムースな進行を阻害して、サイクル特性を低下させる。よって、炭酸リチウムの添加量は０．５〜２．０質量％であることが好ましい。 When the amount of lithium carbonate added is less than 0.5% by mass, a sufficient overcharge safety improvement effect cannot be obtained, while when it is more than 2.0% by mass, the lithium carbonate smoothly progresses in the charge / discharge cycle. To inhibit the cycle characteristics. Therefore, it is preferable that the addition amount of lithium carbonate is 0.5-2.0 mass%.
また、炭酸リチウムの平均粒径が５μｍ未満であると、炭酸リチウム粒子同士が凝集してしまい、炭酸リチウムと正極活物質とが均一に混合されなくなるので、炭酸リチウムによる過充電時安全性向上効果が十分に得られなくなるとともに、凝集した炭酸リチウムが充放電サイクルを阻害して、サイクル特性を低下させる。他方、３０μｍより大きい場合にも、炭酸リチウムと正極活物質とが均一に混合されなくなるので、炭酸リチウムによる過充電時安全性向上効果が十分に得られなくなるとともに、正極中に不均一に分散した炭酸リチウムが充放電サイクルを阻害して、サイクル特性を低下させる。よって、炭酸リチウムの平均粒径は５〜３０μｍであることが好ましい。 In addition, when the average particle size of lithium carbonate is less than 5 μm, the lithium carbonate particles are aggregated, and the lithium carbonate and the positive electrode active material are not uniformly mixed. Cannot be sufficiently obtained, and the agglomerated lithium carbonate hinders the charge / discharge cycle and deteriorates the cycle characteristics. On the other hand, even when the thickness is larger than 30 μm, the lithium carbonate and the positive electrode active material are not uniformly mixed, so that the lithium carbonate cannot sufficiently obtain the effect of improving the safety during overcharge and is unevenly dispersed in the positive electrode. Lithium carbonate inhibits the charge / discharge cycle and deteriorates the cycle characteristics. Therefore, the average particle size of lithium carbonate is preferably 5 to 30 μm.
上記課題を解決するための第２の本発明は、正極活物質を有する正極と、負極活物質を有する負極と、非水電解質と、を備えた非水電解質二次電池において、前記正極活物質としてニッケルコバルトマンガン酸リチウム（ＬｉａＮｉｘＣｏｙＭｎｚＯ２、０＜ａ≦１．１、０．１≦ｘ≦０．５、０＜ｙ、０．１≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）と、スピネル型マンガン酸リチウム（ＬｉａＭｎ２Ｏ４、０＜ａ≦１．１）と、からなり、前記正極活物質に占める前記スピネル型マンガン酸リチウムの質量割合が、５０質量％以下であり、平均粒径５〜３０μｍの炭酸リチウムが、前記正極に対して０．５〜２．０質量％添加され、前記正極活物質と前記炭酸リチウムとが均一に混合されていることを特徴とする。 A second aspect of the present invention for solving the above problems is a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a nonaqueous electrolyte. As nickel cobalt lithium manganate (Li a Ni x Co y Mn z O 2 , 0 <a ≦ 1.1, 0.1 ≦ x ≦ 0.5, 0 <y, 0.1 ≦ z ≦ 0.5, x + y + z = 1) and spinel type lithium manganate (Li a Mn 2 O 4 , 0 <a ≦ 1.1), and the mass proportion of the spinel type lithium manganate in the positive electrode active material is 50 0.5% to 2.0% by mass of lithium carbonate having an average particle diameter of 5 to 30 μm is added to the positive electrode, and the positive electrode active material and the lithium carbonate are uniformly mixed. It is characterized by that.
スピネル型マンガン酸リチウムもまた、過充電時の化合物としての安定性が、従来より正極活物質として用いられているコバルト酸リチウムよりも極めて高い。このため、正極活物質を、ニッケルコバルトマンガン酸リチウムと、スピネル型マンガン酸リチウムと、の混合物とした場合にも、平均粒径が５〜３０μｍの炭酸リチウムを０．５〜２．０質量％正極に均一混合した状態で含ませることにより、過充電時安全性に優れた非水電解質二次電池が得られる。また、スピネル型マンガン酸リチウムは、ニッケルコバルトマンガン酸リチウムよりも低コストであるため、電池の低コスト化を図れる。 Spinel-type lithium manganate is also extremely higher in stability as a compound during overcharge than lithium cobaltate conventionally used as a positive electrode active material. For this reason, even when the positive electrode active material is a mixture of nickel cobalt lithium manganate and spinel type lithium manganate, 0.5 to 2.0 mass% of lithium carbonate having an average particle diameter of 5 to 30 μm is used. By including it in a state of being uniformly mixed in the positive electrode, a nonaqueous electrolyte secondary battery having excellent safety during overcharge can be obtained. Moreover, since spinel type lithium manganate is lower in cost than nickel cobalt lithium manganate, the cost of the battery can be reduced.
しかしながら、スピネル型マンガン酸リチウムは、ニッケルコバルトマンガン酸リチウムよりも放電容量が小さいというデメリットがあり、スピネル型マンガン酸リチウムを５０質量％よりも多くすると、非水電解質二次電池の放電容量が低下する。このため、正極活物質に占めるスピネル型マンガン酸リチウムの質量割合を、５０質量％以下とすることが好ましい。 However, the spinel type lithium manganate has a disadvantage that the discharge capacity is smaller than that of the nickel cobalt lithium manganate. If the spinel type lithium manganate is more than 50% by mass, the discharge capacity of the nonaqueous electrolyte secondary battery decreases. To do. For this reason, it is preferable that the mass ratio of the spinel type lithium manganate to the positive electrode active material is 50 mass% or less.
ここで、炭酸リチウムの添加量とは、正極材（正極集電体を除く正極の全構成要素）の合計質量を１００とした場合の炭酸リチウムの質量％を意味する。 Here, the addition amount of lithium carbonate means mass% of lithium carbonate when the total mass of the positive electrode material (all components of the positive electrode excluding the positive electrode current collector) is 100.
また、炭酸リチウムの平均粒径とは、レーザー回折式粒度分布測定装置(島津製作所製SALD-2000J)を用いて測定された、体積基準での積算粒子量が５０％となる粒子径を意味する。 The average particle size of lithium carbonate means a particle size at which the cumulative particle amount on a volume basis is 50%, measured using a laser diffraction particle size distribution analyzer (SALD-2000J manufactured by Shimadzu Corporation). .
以上説明したように、本発明によると、過充電時安全性に優れた非水電解質二次電池を実現することができる。 As described above, according to the present invention, it is possible to realize a nonaqueous electrolyte secondary battery excellent in safety during overcharge.
以下に、本発明を実施するための最良の形態を、実施例を用いて詳細に説明する。 Hereinafter, the best mode for carrying out the present invention will be described in detail using embodiments.
（実施例１）
（正極の作製）
炭酸リチウムと、Ｎｉ０．３３Ｃｏ０．３４Ｍｎ０．３３（ＯＨ）２で示される共沈水酸化物とを混合し、空気雰囲気中で１０００℃で２０時間焼成し、その後解砕して、平均粒径１１μｍのニッケルコバルトマンガン酸リチウム（ＬｉＮｉ０．０３Ｃｏ０．３４Ｍｎ０．３３Ｏ２）を得た。
(Example 1)
(Preparation of positive electrode)
Lithium carbonate and a coprecipitated hydroxide represented by Ni 0.33 Co 0.34 Mn 0.33 (OH) 2 were mixed, fired at 1000 ° C. for 20 hours in an air atmosphere, and then crushed, A nickel cobalt lithium manganate (LiNi 0.03 Co 0.34 Mn 0.33 O 2 ) having an average particle diameter of 11 μm was obtained.
上記ニッケルコバルトマンガン酸リチウムからなる正極活物質８９．５質量部と、平均粒径が１５μｍである炭酸リチウム０．５質量部と、炭素粉末からなる導電剤５質量部と、ポリビニリデンフルオライド（ＰＶｄＦ）からなる結着剤５質量部と、Ｎ−メチル−２−ピロリドン（ＮＭＰ）と、を均一に混合して正極活物質スラリーを調整した。この正極活物質スラリーを、厚み２０μｍのアルミニウム箔から成る正極集電体の両面にドクターブレード法により塗布し、その後乾燥して、スラリー調整時に用いた有機溶剤（ＮＭＰ）を除去した。この後、圧縮ローラーを用いて圧延し、５５×６００ｍｍの正極板を得た。 89.5 parts by mass of a positive electrode active material composed of the above-described nickel cobalt lithium manganate, 0.5 part by mass of lithium carbonate having an average particle size of 15 μm, 5 parts by mass of a conductive agent composed of carbon powder, and polyvinylidene fluoride ( A positive electrode active material slurry was prepared by uniformly mixing 5 parts by mass of a binder composed of PVdF) and N-methyl-2-pyrrolidone (NMP). This positive electrode active material slurry was applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm by a doctor blade method, and then dried to remove the organic solvent (NMP) used in preparing the slurry. Then, it rolled using the compression roller and obtained the positive electrode plate of 55x600mm.
（負極の作製）
天然黒鉛からなる負極活物質９５質量部と、ポリビニリデンフルオライド（ＰＶｄＦ）からなる結着剤５質量部と、Ｎ−メチル−２−ピロリドン（ＮＭＰ）と、を混合して負極活物質スラリーを調整した。この負極活物質スラリーを、厚み１０μｍの銅箔から成る負極集電体の両面にドクターブレード法により塗布し、その後乾燥して、スラリー調整時に用いた有機溶剤（ＮＭＰ）を除去した。この後、圧縮ローラーを用いて圧延し、５７×６５０ｍｍの負極板を得た。
(Preparation of negative electrode)
A negative electrode active material slurry is prepared by mixing 95 parts by mass of a negative electrode active material made of natural graphite, 5 parts by mass of a binder made of polyvinylidene fluoride (PVdF), and N-methyl-2-pyrrolidone (NMP). It was adjusted. This negative electrode active material slurry was applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 10 μm by a doctor blade method, and then dried to remove the organic solvent (NMP) used for slurry preparation. Then, it rolled using the compression roller and obtained the 57 * 650mm negative electrode plate.
（電極体の作製）
上記正極板と、負極板との間に、ポリプロピレン製微多孔膜からなるセパレータを介在させて巻回し、渦巻電極体を作製した。
(Production of electrode body)
A spiral electrode body was manufactured by interposing a separator made of a polypropylene microporous film between the positive electrode plate and the negative electrode plate.
（非水電解質の調整）
エチレンカーボネート５０体積部と、ジエチルカーボネート５０体積部と、を混合し（２５℃、１気圧における）、ＬｉＰＦ６を１モル／リットルとなるように溶解して、非水電解質となした。
(Nonaqueous electrolyte adjustment)
50 parts by volume of ethylene carbonate and 50 parts by volume of diethyl carbonate were mixed (at 25 ° C. and 1 atm), and LiPF 6 was dissolved at 1 mol / liter to obtain a non-aqueous electrolyte.
（電池の組み立て）
この上記渦巻電極体を電池外装缶内に挿入し、上記非水電解質を注液し、開口を封口することにより、理論容量が１８００ｍＡｈである円筒形の実施例１にかかるリチウムイオン二次電池を作製した。
(Battery assembly)
By inserting the spiral electrode body into a battery outer can, injecting the nonaqueous electrolyte, and sealing the opening, the lithium ion secondary battery according to the cylindrical example 1 having a theoretical capacity of 1800 mAh was obtained. Produced.
（実施例２）
正極活物質を８９質量部とし、炭酸リチウムを１．０質量部としたこと以外は、上記実施例１と同様にして、実施例２にかかるリチウムイオン二次電池を作製した。
(Example 2)
A lithium ion secondary battery according to Example 2 was produced in the same manner as in Example 1 except that the positive electrode active material was 89 parts by mass and lithium carbonate was 1.0 part by mass.
（実施例３）
正極活物質を８８質量部とし、炭酸リチウムを２．０質量部としたこと以外は、上記実施例１と同様にして、実施例３にかかるリチウムイオン二次電池を作製した。
(Example 3)
A lithium ion secondary battery according to Example 3 was manufactured in the same manner as in Example 1 except that the positive electrode active material was 88 parts by mass and lithium carbonate was 2.0 parts by mass.
（実施例４）
正極活物質を、平均粒径が１１μｍのニッケルコバルトマンガン酸リチウム（ＬｉＮｉ０．０３Ｃｏ０．３４Ｍｎ０．３３Ｏ２）と、公知の方法で作製した平均粒径が１１μｍのスピネル型マンガン酸リチウム（ＬｉＭｎ２Ｏ４）と、を質量比７：３で混合した混合物としたこと以外は、上記実施例１と同様にして、実施例４にかかるリチウムイオン二次電池を作製した。
Example 4
The positive electrode active material is made of nickel cobalt lithium manganate (LiNi 0.03 Co 0.34 Mn 0.33 O 2 ) having an average particle diameter of 11 μm and spinel manganic acid having an average particle diameter of 11 μm prepared by a known method. A lithium ion secondary battery according to Example 4 was produced in the same manner as in Example 1 except that lithium (LiMn 2 O 4 ) was mixed at a mass ratio of 7: 3.
（実施例５）
正極活物質を８９質量部とし、炭酸リチウムを１．０質量部としたこと以外は、上記実施例４と同様にして、実施例５にかかるリチウムイオン二次電池を作製した。
(Example 5)
A lithium ion secondary battery according to Example 5 was produced in the same manner as in Example 4 except that the positive electrode active material was 89 parts by mass and lithium carbonate was 1.0 part by mass.
（実施例６）
正極活物質を８８質量部とし、炭酸リチウムを２．０質量部としたこと以外は、上記実施例４と同様にして、実施例６にかかるリチウムイオン二次電池を作製した。
(Example 6)
A lithium ion secondary battery according to Example 6 was produced in the same manner as in Example 4 except that the positive electrode active material was 88 parts by mass and lithium carbonate was 2.0 parts by mass.
（実施例７）
正極活物質を、ニッケルコバルトマンガン酸リチウムとスピネル型マンガン酸リチウムを質量比５：５で混合した混合物としたこと以外は、上記実施例１と同様にして、実施例７にかかるリチウムイオン二次電池を作製した。
(Example 7)
The lithium ion secondary according to Example 7 was performed in the same manner as in Example 1 except that the positive electrode active material was a mixture in which nickel cobalt lithium manganate and spinel type lithium manganate were mixed at a mass ratio of 5: 5. A battery was produced.
（実施例８）
正極活物質を８９質量部とし、炭酸リチウムを１．０質量部としたこと以外は、上記実施例７と同様にして、実施例８にかかるリチウムイオン二次電池を作製した。
(Example 8)
A lithium ion secondary battery according to Example 8 was produced in the same manner as in Example 7 except that the positive electrode active material was 89 parts by mass and lithium carbonate was 1.0 part by mass.
（実施例９）
正極活物質を８８質量部とし、炭酸リチウムを２．０質量部としたこと以外は、上記実施例７と同様にして、実施例９にかかるリチウムイオン二次電池を作製した。
Example 9
A lithium ion secondary battery according to Example 9 was produced in the same manner as in Example 7 except that the positive electrode active material was 88 parts by mass and lithium carbonate was 2.0 parts by mass.
（実施例１０）
炭酸リチウムの平均粒径を５μｍとしたこと以外は、上記実施例１と同様にして、実施例１０にかかるリチウムイオン二次電池を作製した。
(Example 10)
A lithium ion secondary battery according to Example 10 was produced in the same manner as in Example 1 except that the average particle size of lithium carbonate was 5 μm.
（実施例１１）
炭酸リチウムの平均粒径を３０μｍとしたこと以外は、上記実施例１と同様にして、実施例１１にかかるリチウムイオン二次電池を作製した。
(Example 11)
A lithium ion secondary battery according to Example 11 was produced in the same manner as in Example 1 except that the average particle size of lithium carbonate was 30 μm.
（実施例１２）
ニッケルコバルトマンガン酸リチウムの平均粒径を５μｍとしたこと以外は、上記実施例１と同様にして、実施例１２にかかるリチウムイオン二次電池を作製した。
(Example 12)
A lithium ion secondary battery according to Example 12 was produced in the same manner as in Example 1 except that the average particle size of nickel cobalt lithium manganate was 5 μm.
（実施例１３）
ニッケルコバルトマンガン酸リチウムの平均粒径を２０μｍとしたこと以外は、上記実施例１と同様にして、実施例１３にかかるリチウムイオン二次電池を作製した。
(Example 13)
A lithium ion secondary battery according to Example 13 was produced in the same manner as in Example 1 except that the average particle diameter of nickel cobalt lithium manganate was 20 μm.
（比較例１）
炭酸リチウムを混合しなかったこと以外は、上記実施例１と同様にして、比較例１にかかるリチウムイオン二次電池を作製した。
(Comparative Example 1)
A lithium ion secondary battery according to Comparative Example 1 was produced in the same manner as in Example 1 except that lithium carbonate was not mixed.
（比較例２）
正極活物質を８９．９質量部とし、炭酸リチウムを０．１質量部としたこと以外は、上記実施例１と同様にして、比較例２にかかるリチウムイオン二次電池を作製した。
(Comparative Example 2)
A lithium ion secondary battery according to Comparative Example 2 was produced in the same manner as in Example 1 except that the positive electrode active material was 89.9 parts by mass and lithium carbonate was 0.1 parts by mass.
（比較例３）
正極活物質を８７．０質量部とし、炭酸リチウムを３．０質量部としたこと以外は、上記実施例１と同様にして、比較例３にかかるリチウムイオン二次電池を作製した。
(Comparative Example 3)
A lithium ion secondary battery according to Comparative Example 3 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to 87.0 parts by mass and lithium carbonate was changed to 3.0 parts by mass.
（比較例４）
正極活物質を８９．９質量部とし、炭酸リチウムを０．１質量部としたこと以外は、上記実施例４と同様にして、比較例４にかかるリチウムイオン二次電池を作製した。
(Comparative Example 4)
A lithium ion secondary battery according to Comparative Example 4 was produced in the same manner as in Example 4 except that the positive electrode active material was 89.9 parts by mass and lithium carbonate was 0.1 parts by mass.
（比較例５）
正極活物質を８７．０質量部とし、炭酸リチウムを３．０質量部としたこと以外は、上記実施例４と同様にして、比較例５にかかるリチウムイオン二次電池を作製した。
(Comparative Example 5)
A lithium ion secondary battery according to Comparative Example 5 was produced in the same manner as in Example 4 except that the positive electrode active material was changed to 87.0 parts by mass and lithium carbonate was changed to 3.0 parts by mass.
（比較例６）
正極活物質を８９．９質量部とし、炭酸リチウムを０．１質量部としたこと以外は、上記実施例７と同様にして、比較例６にかかるリチウムイオン二次電池を作製した。
(Comparative Example 6)
A lithium ion secondary battery according to Comparative Example 6 was produced in the same manner as in Example 7 except that the positive electrode active material was 89.9 parts by mass and lithium carbonate was 0.1 parts by mass.
（比較例７）
正極活物質を８７．０質量部とし、炭酸リチウムを３．０質量部としたこと以外は、上記実施例７と同様にして、比較例７にかかるリチウムイオン二次電池を作製した。
(Comparative Example 7)
A lithium ion secondary battery according to Comparative Example 7 was produced in the same manner as in Example 7 except that the positive electrode active material was changed to 87.0 parts by mass and lithium carbonate was changed to 3.0 parts by mass.
（比較例８）
正極活物質を、ニッケルコバルトマンガン酸リチウムとスピネル型マンガン酸リチウムを質量比４：６で混合した混合物としたこと以外は、上記実施例１と同様にして、比較例８にかかるリチウムイオン二次電池を作製した。
(Comparative Example 8)
The lithium ion secondary material according to Comparative Example 8 was the same as Example 1 except that the positive electrode active material was a mixture of nickel cobalt lithium manganate and spinel type lithium manganate mixed at a mass ratio of 4: 6. A battery was produced.
（比較例９）
正極活物質を８９質量部とし、炭酸リチウムを１．０質量部としたこと以外は、上記比較例８と同様にして、比較例９にかかるリチウムイオン二次電池を作製した。
(Comparative Example 9)
A lithium ion secondary battery according to Comparative Example 9 was produced in the same manner as in Comparative Example 8 except that the positive electrode active material was 89 parts by mass and lithium carbonate was 1.0 part by mass.
（比較例１０）
正極活物質を８８質量部とし、炭酸リチウムを２．０質量部としたこと以外は、上記比較例８と同様にして、比較例１０にかかるリチウムイオン二次電池を作製した。
(Comparative Example 10)
A lithium ion secondary battery according to Comparative Example 10 was produced in the same manner as Comparative Example 8 except that the positive electrode active material was 88 parts by mass and lithium carbonate was 2.0 parts by mass.
（比較例１１）
炭酸リチウムの平均粒径を３μｍとしたこと以外は、上記実施例１と同様にして、比較例１１にかかるリチウムイオン二次電池を作製した。
(Comparative Example 11)
A lithium ion secondary battery according to Comparative Example 11 was produced in the same manner as in Example 1 except that the average particle size of lithium carbonate was 3 μm.
（比較例１２）
炭酸リチウムの平均粒径を５０μｍとしたこと以外は、上記実施例１と同様にして、比較例１２にかかるリチウムイオン二次電池を作製した。
(Comparative Example 12)
A lithium ion secondary battery according to Comparative Example 12 was produced in the same manner as in Example 1 except that the average particle size of lithium carbonate was 50 μm.
（比較例１３）
正極活物質をコバルト酸リチウム（ＬｉＣｏＯ２）としたこと以外は、上記実施例１と同様にして、比較例１３にかかるリチウムイオン二次電池を作製した。
(Comparative Example 13)
A lithium ion secondary battery according to Comparative Example 13 was produced in the same manner as in Example 1 except that the positive electrode active material was lithium cobalt oxide (LiCoO 2 ).
〔平均粒径の測定〕
上記ニッケルコバルトマンガン酸リチウム、スピネル型マンガン酸リチウム、炭酸リチウムの平均粒径を、レーザー回折式粒度分布測定装置(島津製作所製SALD-2000J)を用いて測定した。この測定結果の体積基準での積算粒子量が５０％となる粒子径を、平均粒径とした。なお、この測定にあたり、ニッケルコバルトマンガン酸リチウム、スピネル型マンガン酸リチウムについては水を分散媒に用い、炭酸リチウムについてはエタノールを分散媒に用いた。
(Measurement of average particle size)
The average particle diameters of the nickel cobalt lithium manganate, spinel type lithium manganate, and lithium carbonate were measured using a laser diffraction particle size distribution analyzer (SALD-2000J manufactured by Shimadzu Corporation). The particle diameter at which the cumulative particle amount on the volume basis of this measurement result was 50% was taken as the average particle diameter. In this measurement, water was used as a dispersion medium for nickel cobalt lithium manganate and spinel type lithium manganate, and ethanol was used as a dispersion medium for lithium carbonate.
〔初期放電容量の測定〕
上記実施例１〜１３、比較例１〜１３にかかる電池を、２５℃において定電流１８００ｍＡで電圧が４．２Ｖとなるまで充電し、その後定電圧４．２Ｖで電流が３６ｍＡとなるまで充電した。この後、定電流１８００ｍＡで電圧が２．７５Ｖとなるまで放電し、その放電容量を測定した。この結果を下記表１に示す。
[Measurement of initial discharge capacity]
The batteries according to Examples 1 to 13 and Comparative Examples 1 to 13 were charged at a constant current of 1800 mA at 25 ° C. until the voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V until the current reached 36 mA. . Thereafter, the battery was discharged at a constant current of 1800 mA until the voltage reached 2.75 V, and the discharge capacity was measured. The results are shown in Table 1 below.
〔内部短絡試験〕
上記実施例１〜１３、比較例１〜７、比較例１１〜１３にかかる電池を各１０個用意し、それぞれ２５℃において定電流１８００ｍＡで電圧が４．４Ｖとなるまで充電し、その後定電圧４．４Ｖで電流が３６ｍＡとなるまで充電した。この充電状態の電池の中央付近に、直径３ｍｍの鉄製の釘を１００ｍｍ／秒で貫通させ、貫通させた。この試験において電池が燃焼したものをＮＧ、燃焼しなかったものをＯＫと判定した。この結果を下記表１に示す。なお、４．４Ｖという充電電圧は、電池が過充電された状態であり（通常の電池の使用電圧は４．２Ｖ以下）、実際の商品として市場に流通する電池には保護回路等の安全機構が設けられているため、このような過充電状態となることはない。また、通常の電池の使用環境においては、釘刺しのような極度の内部短絡が生じることもない。
[Internal short circuit test]
Ten batteries according to Examples 1 to 13, Comparative Examples 1 to 7, and Comparative Examples 11 to 13 were prepared, and each battery was charged at a constant current of 1800 mA at 25 ° C. until the voltage became 4.4 V, and then the constant voltage. The battery was charged at 4.4 V until the current reached 36 mA. An iron nail having a diameter of 3 mm was penetrated at 100 mm / second in the vicinity of the center of the charged battery. In this test, the battery burned was determined as NG, and the battery not burned was determined as OK. The results are shown in Table 1 below. The charging voltage of 4.4 V is a state in which the battery is overcharged (a normal battery operating voltage is 4.2 V or less), and a battery such as a protection circuit is provided for a battery distributed as an actual product in the market. Therefore, such an overcharge state is not caused. Further, in an ordinary battery usage environment, an extreme internal short circuit such as nail penetration does not occur.
〔サイクル特性試験〕
上記実施例１〜１３、比較例１〜７、比較例１１〜１３にかかる電池を、４０℃において定電流１８００ｍＡで電圧が４．２Ｖとなるまで充電し、その後定電圧４．２Ｖで電流が３６ｍＡとなるまで充電した。この後、４０℃において定電流１８００ｍＡで電圧が２．７５Ｖとなるまで放電した。この充放電サイクルを３００サイクル行い、下記の式によりサイクル特性を算出した。この結果を下記表１に示す。
サイクル特性（％）＝３００サイクル目放電容量÷１サイクル目放電容量×１００
[Cycle characteristic test]
The batteries according to Examples 1 to 13, Comparative Examples 1 to 7, and Comparative Examples 11 to 13 were charged at 40 ° C. with a constant current of 1800 mA until the voltage became 4.2 V, and then the current was constant with a constant voltage of 4.2 V. The battery was charged until it reached 36 mA. Thereafter, the battery was discharged at a constant current of 1800 mA at 40 ° C. until the voltage reached 2.75V. This charge / discharge cycle was performed 300 times, and the cycle characteristics were calculated by the following formula. The results are shown in Table 1 below.
Cycle characteristics (%) = 300th cycle discharge capacity / first cycle discharge capacity × 100
〔ＤＳＣ発熱開始温度の測定〕
上記実施例１〜１３、比較例１〜７、比較例１１〜１３にかかる電池を、２５℃において定電流１８００ｍＡで電圧が４．４Ｖとなるまで充電し、その後定電圧４．４Ｖで電流が３６ｍＡとなるまで充電した。この電池をドライボックス中で分解し、正極板を取り出し、正極板をジエチルカーボネートで洗浄した後、真空乾燥した。この正極板から正極材（正極集電体を除く正極の全構成要素を意味し、本実施例、比較例においては、正極活物質＋炭酸リチウム＋導電剤＋結着剤の合計）を５ｍｇ採取した。これを、エチレンカーボネート２ｍｇとともにアルゴン雰囲気下でステンレス製のセル中に封じ、示差走査熱量計（ＤＳＣ）にて５℃／分で昇温し、自己発熱が開始する温度を測定した。なお、４．４Ｖという電圧は、電池が過充電された状態である。この結果を下記表１に示す。
[Measurement of DSC heat generation start temperature]
The batteries according to Examples 1 to 13, Comparative Examples 1 to 7, and Comparative Examples 11 to 13 were charged at 25 ° C. at a constant current of 1800 mA until the voltage became 4.4 V, and then the current was constant at 4.4 V. The battery was charged until it reached 36 mA. This battery was disassembled in a dry box, the positive electrode plate was taken out, the positive electrode plate was washed with diethyl carbonate, and then vacuum-dried. From this positive electrode plate, 5 mg of positive electrode material (meaning all components of the positive electrode excluding the positive electrode current collector, in this example and comparative example, total of positive electrode active material + lithium carbonate + conductive agent + binder) was sampled. did. This was sealed in a stainless steel cell together with 2 mg of ethylene carbonate in an argon atmosphere, heated at 5 ° C./min with a differential scanning calorimeter (DSC), and the temperature at which self-heating was started was measured. The voltage of 4.4V is a state where the battery is overcharged. The results are shown in Table 1 below.
なお、比較例８〜１０にかかる電池について、内部短絡試験、サイクル特性試験、ＤＳＣ発熱開始温度の測定を行っていないのは、上記表１に示すように、初期放電容量が１６４４〜１６６２ｍＡｈと、理論容量の１８００ｍＡｈよりも大幅に低下しており、電池として不適であるためである。この初期放電容量の低下の理由は、スピネル型マンガン酸リチウム自体の放電容量がニッケルコバルトマンガン酸リチウムよりも低く、これを正極活物質中に６０質量％と多量に含ませているためによると考えられる。スピネル型マンガン酸リチウムの含有量が正極活物質全体の５０質量％以下である実施例１〜９では、初期放電容量の低下が見られないことから（表１参照）、スピネル型マンガン酸リチウムの含有量は、正極活物質全体の５０質量％以下であることが好ましい。 As for the batteries according to Comparative Examples 8 to 10, the internal short circuit test, the cycle characteristic test, and the DSC heat generation start temperature were not measured, as shown in Table 1 above, the initial discharge capacity was 1644 to 1662 mAh, This is because it is significantly lower than the theoretical capacity of 1800 mAh and is not suitable as a battery. The reason for the decrease in the initial discharge capacity is considered to be that the discharge capacity of the spinel type lithium manganate itself is lower than that of nickel cobalt lithium manganate and is contained in a large amount of 60% by mass in the positive electrode active material. It is done. In Examples 1 to 9 in which the content of the spinel type lithium manganate is 50% by mass or less of the whole positive electrode active material, since the initial discharge capacity is not reduced (see Table 1), the spinel type lithium manganate The content is preferably 50% by mass or less of the whole positive electrode active material.
上記表１から、正極活物質として従来より用いられているコバルト酸リチウムを用いた比較例１３は、内部短絡試験ＮＧ率が１００％、ＤＳＣ発熱開始温度が１７０℃と、正極活物質としてニッケルコバルトマンガン酸リチウムを用いた実施例１〜３、正極活物質としてニッケルコバルトマンガン酸リチウムとスピネル型マンガン酸リチウムとの混合物を用いた実施例４〜９の０％、２０４〜２１４℃よりも劣っていることがわかる。 From Table 1 above, Comparative Example 13 using lithium cobaltate conventionally used as the positive electrode active material has an internal short circuit test NG rate of 100%, a DSC heat generation start temperature of 170 ° C., and nickel cobalt as the positive electrode active material. Examples 1 to 3 using lithium manganate, 0% of Examples 4 to 9 using a mixture of nickel cobalt lithium manganate and spinel type lithium manganate as the positive electrode active material, inferior to 204 to 214 ° C I understand that.
このことは、コバルト酸リチウムは、化合物としての熱安定性や過充電時の安定性が、ニッケルコバルトマンガン酸リチウムやスピネル型マンガン酸リチウムよりも低いため、炭酸リチウムを含ませても過充電時安全性が向上しないことによると考えられる。 This is because lithium cobaltate has lower thermal stability as a compound and overcharge stability than nickel cobalt lithium manganate and spinel type lithium manganate. This is thought to be due to the fact that safety does not improve.
また、上記表１から、炭酸リチウムの添加量が０．１質量％以下である比較例１，比較例２，比較例４，比較例６は、内部短絡試験ＮＧ率が１００％と、炭酸リチウムの添加量が０．５質量％以上である実施例１〜９、比較例３，比較例５，比較例７の内部短絡試験ＮＧ率の０％よりも顕著に劣っていることがわかる。 Further, from Table 1 above, Comparative Example 1, Comparative Example 2, Comparative Example 4, and Comparative Example 6 in which the amount of lithium carbonate added is 0.1% by mass or less have an internal short circuit test NG ratio of 100%, and lithium carbonate. It can be seen that the amount of added is significantly inferior to 0% of the internal short-circuit test NG ratio of Examples 1 to 9, Comparative Example 3, Comparative Example 5, and Comparative Example 7 in which the amount of addition is 0.5 mass% or more.
この理由は定かではないが、正極に含まれる炭酸リチウム自体が過充電時の電池の安全性を高めるように作用して、釘刺しのような極度の内部短絡を生じさせても、電池を燃焼に至らせない。このため、炭酸リチウムを０．５質量％以上含む実施例１〜９、比較例３，比較例５，比較例７では、内部短絡試験ＮＧ率が０％となる。他方、炭酸リチウムの添加量が０．５質量％未満であると、炭酸リチウムによる過充電時安全性向上効果が十分に得られないため、比較例１，比較例２，比較例４，比較例６は、内部短絡試験ＮＧ率が１００％となる。よって、炭酸リチウムの添加量は、０．５質量％以上であることが好ましい。 The reason for this is not clear, but the lithium carbonate contained in the positive electrode itself works to enhance the safety of the battery when overcharged, causing the battery to burn even if it causes an extreme internal short circuit such as nail penetration. I will not lead to. For this reason, in Examples 1-9, Comparative Example 3, Comparative Example 5, and Comparative Example 7 containing 0.5 mass% or more of lithium carbonate, the internal short circuit test NG rate is 0%. On the other hand, if the amount of lithium carbonate added is less than 0.5% by mass, the effect of improving safety during overcharging with lithium carbonate cannot be sufficiently obtained, so Comparative Example 1, Comparative Example 2, Comparative Example 4, Comparative Example 6 has an internal short circuit test NG rate of 100%. Therefore, it is preferable that the addition amount of lithium carbonate is 0.5 mass% or more.
また、上記表１から、炭酸リチウムの添加量が３．０質量％である比較例３，比較例５，比較例７は、サイクル特性が５９〜６０％と、炭酸リチウムの添加量が０．５〜２．０質量％である実施例１〜９の７１〜８３％よりも大きく低下していることがわかる。 From Table 1 above, Comparative Example 3, Comparative Example 5, and Comparative Example 7 in which the amount of lithium carbonate added is 3.0% by mass has a cycle characteristic of 59 to 60% and the amount of lithium carbonate added is 0.00. It turns out that it has fallen largely from 71 to 83% of Examples 1-9 which are 5 to 2.0 mass%.
このことは、次のように考えられる。炭酸リチウムは充放電に寄与する物質ではなく、逆に充放電サイクルのスムースな進行を妨げるように作用する。よって、炭酸リチウムが３．０質量％以上含まれると、サイクル特性が大きく低下する。よって、正極中の炭酸リチウムの含有量は、２．０質量％以下であることが好ましい。 This is considered as follows. Lithium carbonate is not a substance that contributes to charge / discharge, but conversely acts to prevent the smooth progress of the charge / discharge cycle. Therefore, when lithium carbonate is contained in an amount of 3.0% by mass or more, the cycle characteristics are greatly degraded. Therefore, the lithium carbonate content in the positive electrode is preferably 2.0% by mass or less.
また、上記表１から、炭酸リチウムの平均粒径が３μｍである比較例１１では、内部短絡試験ＮＧ率が２０％、サイクル特性が６５％と、炭酸リチウムの平均粒径が５〜３０μｍである実施例２、実施例１０、実施例１１の０％、７７〜８３％よりも劣っていることがわかる。また、上記表１から、炭酸リチウムの平均粒径が５０μｍである比較例１２では、内部短絡試験ＮＧ率が５０％、サイクル特性が６６％と、炭酸リチウムの平均粒径が５〜３０μｍである実施例２、実施例１０、実施例１１の０％、７７〜８３％よりも劣っていることがわかる。 Moreover, from the said Table 1, in the comparative example 11 whose average particle diameter of lithium carbonate is 3 micrometers, internal short circuit test NG rate is 20%, cycling characteristics are 65%, and the average particle diameter of lithium carbonate is 5-30 micrometers. It turns out that it is inferior to 0% of Example 2, Example 10, and Example 11, 77 to 83%. Moreover, from the said Table 1, in the comparative example 12 whose average particle diameter of lithium carbonate is 50 micrometers, internal short circuit test NG rate is 50%, cycling characteristics are 66%, and the average particle diameter of lithium carbonate is 5-30 micrometers. It turns out that it is inferior to 0% of Example 2, Example 10, and Example 11, 77 to 83%.
このことは、次のように考えられる。炭酸リチウムの平均粒径が５μｍ未満であると、炭酸リチウム粒子同士が凝集してしまい、炭酸リチウムと正極活物質とが均一に混合されなくなるので、炭酸リチウムによる過充電時安全性向上効果が十分に得られなくなるとともに、凝集した炭酸リチウムが充放電サイクルのスムースな進行を阻害して、サイクル特性が低下する。他方、３０μｍより大きい場合にも、炭酸リチウムと正極活物質とが均一に混合されなくなるので、炭酸リチウムによる過充電時安全性向上効果が十分に得られなくなるとともに、正極中に不均一に分散した炭酸リチウムが、充放電サイクルのスムースな進行を阻害して、サイクル特性が低下する。よって、炭酸リチウムの平均粒径は５〜３０μｍであることが好ましい。 This is considered as follows. If the average particle size of the lithium carbonate is less than 5 μm, the lithium carbonate particles aggregate together, and the lithium carbonate and the positive electrode active material are not mixed uniformly. In addition, the agglomerated lithium carbonate inhibits the smooth progress of the charge / discharge cycle, and the cycle characteristics deteriorate. On the other hand, even when the thickness is larger than 30 μm, the lithium carbonate and the positive electrode active material are not uniformly mixed, so that the lithium carbonate cannot sufficiently obtain the effect of improving the safety during overcharge and is unevenly dispersed in the positive electrode. Lithium carbonate inhibits the smooth progress of the charge / discharge cycle, and the cycle characteristics deteriorate. Therefore, the average particle size of lithium carbonate is preferably 5 to 30 μm.
また、上記表１から、ニッケルコバルトマンガン酸リチウムの平均粒径が、５〜２０μｍである実施例２、実施例１２、実施例１３では、電池性能や内部短絡試験ＮＧ率に大きな差がないことがわかる。 Also, from Table 1 above, in Example 2, Example 12, and Example 13 in which the average particle size of nickel cobalt lithium manganate is 5 to 20 μm, there is no significant difference in battery performance and internal short circuit test NG rate. I understand.
（追加事項）
負極活物質としては、上記実施例で用いたもの以外に、炭素質物、リチウム合金、金属リチウム、リチウムを吸蔵・脱離できる金属酸化物等を単独で、あるいは複数種混合して用いることができる。
(extra content)
As the negative electrode active material, carbonaceous materials, lithium alloys, metal lithium, metal oxides capable of inserting and extracting lithium, etc. can be used alone or in combination of a plurality of types in addition to those used in the above examples. .
また、非水溶媒としては、上記実施例で用いたもの以外に、ブチレンカーボネート、γ−ブチロラクトン、γ−バレロラクトン、ジエチルカーボネート、スルホラン、酢酸エチル、テトラヒドロフラン、１，２−ジメトキシエタン、１，３−ジオキソラン、２−メトキシテトラヒドロフラン、ジエチルエーテル等を単独で、あるいは複数種混合して用いることができる。 In addition to those used in the above examples, non-aqueous solvents include butylene carbonate, γ-butyrolactone, γ-valerolactone, diethyl carbonate, sulfolane, ethyl acetate, tetrahydrofuran, 1,2-dimethoxyethane, 1,3. -Dioxolane, 2-methoxytetrahydrofuran, diethyl ether and the like can be used alone or in combination.
また、電解質塩としては、上記ＬｉＰＦ６以外に、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣｌＯ４、ＬｉＢＦ４を単独で、あるいは複数種混合して用いることができる。 In addition to LiPF 6 described above, LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiClO 4 , LiBF 4 may be used alone or in combination as an electrolyte salt. Can do.
以上説明したように、本発明によると、過充電時安全性に優れた非水電解質二次電池を実現できるので、産業上の意義は大きい。 As described above, according to the present invention, a nonaqueous electrolyte secondary battery excellent in safety at the time of overcharge can be realized.
Claims (2)
前記正極活物質としてニッケルコバルトマンガン酸リチウム（ＬｉａＮｉｘＣｏｙＭｎｚＯ２、０＜ａ≦１．１、０．１≦ｘ≦０．５、０＜ｙ、０．１≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）のみからなり、
平均粒径５〜３０μｍの炭酸リチウムが、前記正極に対して０．５〜２．０質量％添加され、
前記正極活物質と前記炭酸リチウムとが均一に混合されている、
ことを特徴とする非水電解質二次電池。 In a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a non-aqueous electrolyte,
As the positive electrode active material, lithium nickel cobalt manganate (Li a Ni x Co y Mn z O 2 , 0 <a ≦ 1.1, 0.1 ≦ x ≦ 0.5, 0 <y, 0.1 ≦ z ≦ 0.5, x + y + z = 1) only,
Lithium carbonate having an average particle size of 5 to 30 μm is added in an amount of 0.5 to 2.0 mass% with respect to the positive electrode.
The positive electrode active material and the lithium carbonate are uniformly mixed,
A non-aqueous electrolyte secondary battery.
前記正極活物質としてニッケルコバルトマンガン酸リチウム（ＬｉａＮｉｘＣｏｙＭｎｚＯ２、０＜ａ≦１．１、０．１≦ｘ≦０．５、０＜ｙ、０．１≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）と、スピネル型マンガン酸リチウム（ＬｉａＭｎ２Ｏ４、０＜ａ≦１．１）と、からなり、
前記正極活物質に占める前記スピネル型マンガン酸リチウムの質量割合が、５０質量％以下であり、
平均粒径５〜３０μｍの炭酸リチウムが、前記正極に対して０．５〜２．０質量％添加され、
前記正極活物質と前記炭酸リチウムとが均一に混合されている、
ことを特徴とする非水電解質二次電池。 In a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a non-aqueous electrolyte,
As the positive electrode active material, lithium nickel cobalt manganate (Li a Ni x Co y Mn z O 2 , 0 <a ≦ 1.1, 0.1 ≦ x ≦ 0.5, 0 <y, 0.1 ≦ z ≦ 0.5, x + y + z = 1) and spinel type lithium manganate (Li a Mn 2 O 4 , 0 <a ≦ 1.1),
The mass proportion of the spinel-type lithium manganate in the positive electrode active material is 50% by mass or less,
Lithium carbonate having an average particle size of 5 to 30 μm is added in an amount of 0.5 to 2.0 mass% with respect to the positive electrode.
The positive electrode active material and the lithium carbonate are uniformly mixed,
A non-aqueous electrolyte secondary battery.
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