JP6034413B2 - Metal gradient doped cathode material for lithium ion battery - Google Patents
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本発明は一種のリチウムイオン電池の金属勾配ドープ正極材料に係り、特に、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、ホウ素(B)、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、チタン(Ti)、ケイ素(Si)、及びスズ(Sn)のいずれか一種類の修飾元素を、連続濃度勾配分布方式で六方晶正極材料構造内にドープすることで、材料の電容量、使用寿命と安全性を改善し、それにより正極材料の高エネルギー化を増進するものに関する。 The present invention relates to a kind of metal gradient doped positive electrode material for lithium ion batteries, and in particular, magnesium (Mg), calcium (Ca), strontium (Sr), boron (B), aluminum (Al), gallium (Ga), indium. (in), titanium (Ti), silicon (Si), and any one type of modification elements of tin (Sn), by doping the hexagonal AkiraTadashikyoku material structure with a continuous gradient distribution scheme, conductive materials It relates to the one that improves the capacity, service life and safety, thereby increasing the energy of the positive electrode material.
近年、日増しに厳重になる地球温暖化現象及び石油の漸減するエネルギー資源危機に伴い、人類はより省エネで、炭素を減らせ、環境保護の電動車両を発展させる必要に迫られている。高い安全性と高いエネルギー密度を有して電動車両で使用できるリチウムイオン電池を研究開発することは、現在環境保護と省エネ領域において尤も重要な一環である。米国、欧州、日本、韓国、中国大陸と台湾は、いずれもすでに積極的に電動車と動力リチウムイオン電池の技術の研究開発、量産製造に積極的にとりくんでいる。また、3C消費性電子産業の勃興発展により、スマートホンとタブレットPCはすでに尤もホットな製品となっており、人々は随時随所で無線オンライン、オーディオビデオ放送、及びクラウドデータ受信等のモバイルスマート化機能を実行でき、これにより、3C電子製品の電源使用時間を延長する必要に迫られている。これにより、高エネルギー密度を具えたリチウムイオン電池を開発して、電動車と3C製品に応用できるようにする必要があるが、リチウムイオン電池のエネルギー密度は電池の採用する電極活性材料と関係があり、そのうち正極材料は尤も鍵となる。 In recent years, with the global warming phenomenon becoming increasingly severe and the energy resource crisis of petroleum gradually decreasing, mankind has been forced to develop more energy-saving, carbon-reduced, and environmentally-friendly electric vehicles. Researching and developing lithium-ion batteries that can be used in electric vehicles with high safety and high energy density is now an extremely important part of environmental protection and energy saving. The United States, Europe, Japan, South Korea, Mainland China and Taiwan have all been actively engaged in R & D and mass production of electric vehicle and power lithium-ion battery technologies. In addition, with the rise of 3C consumer electronics industry, smart phones and tablet PCs are already hot products, and people can use mobile smart functions such as wireless online, audio video broadcasting, and cloud data reception at any time. Therefore, it is necessary to extend the power usage time of the 3C electronic product. As a result, it is necessary to develop a lithium ion battery having a high energy density so that it can be applied to electric vehicles and 3C products. The energy density of a lithium ion battery is related to the electrode active material adopted by the battery. Yes, the positive electrode material is the key.
正極材料のリチウムイオン電池の性能に対する影響は甚だ大きく、これにより、正極材料の選択は、低コスト、高容量、高サイクル寿命、及び大電流充放電能力が良好であること等の要求のほか、より重要であることは、材料自身が良好な熱安定性を具えて電池の安全性を増加できることであり、数多くの正極材料中、六方晶正極材料は比較的高いエネルギー密度を具え、これにより広く研究、重視されている。リチウムイオン電池の正極材料中、リチウムコバルト酸化物(LiCoO2)の発展は最も長く、また現在市場で比較的常用されている六方晶正極材料(一元正極材料)である。ただし、Coは戦略物資で、価格は高く、取得が容易でなく且つ毒性を有することから、エネルギー密度が高く、コストが比較的低く、且つ比較的毒性のないリチウムニッケル酸化物(LiNiO2)がリチウムコバルト酸化物(LiCoO2)の代りに研究されるようになった。ただし、リチウムニッケル酸化物(LiNiO2)六方晶正極材料(一元性正極材料)はまた合成計量が困難で、熱安定性が低く且つ構造安定性が不良である等の問題を有しており、これらの問題を改善するために、Coを 添加してLiNiO2中の一部のNiと置換することで、LiNiO2の構造安定性を増加する。これにより、LiNixCo1-xO2六方晶正極材料(二元正極材料 )が出現し、それは、LiCoO2よりも高い電容量(実際の電容量>180mAhg-1)を有し、且つLiNiO2よりも良好な熱安定性を有し、次世代リチウムイオン電池の鍵となる正極材料である。二元正極材料は多くの長所を有するものの、市場の材料コストを考慮して、三元六方晶正極材料(LiNiXCoyMn1-X-yO2)が発展した。三元材料は二元材料に較べて電容量が低いものの、Mnを添加して置換することで材料コストを下げることができ、また材料構造の安定性と安全性を増加できる。
The influence of the positive electrode material on the performance of the lithium-ion battery is very large, and as a result, the selection of the positive electrode material has requirements such as low cost, high capacity, high cycle life, and high current charge / discharge capability, More importantly, the material itself has good thermal stability and can increase the safety of the battery. Among many positive electrode materials, the hexagonal positive electrode material has a relatively high energy density, which Research is emphasized. Among the positive electrode materials for lithium ion batteries, lithium cobalt oxide (LiCoO 2 ) has been the longest developed and is a hexagonal positive electrode material (single positive electrode material) that is relatively commonly used in the market today. However, Co is a strategic material, high in price, not easy to acquire and toxic. Therefore, lithium nickel oxide (LiNiO 2 ) having high energy density, relatively low cost, and relatively non-toxicity is used. It has been studied instead of lithium cobalt oxide (LiCoO 2 ). However, lithium nickel oxide (LiNiO 2 ) hexagonal positive electrode material (unitary positive electrode material) also has problems such as difficulty in synthesis measurement, low thermal stability and poor structural stability, to improve these problems, the addition of Co by replacing a part of Ni in LiNiO 2, to increase the structural stability of
現在業界は、高エネルギー密度の正極材料に対して主要な二つの開発方向を有しており、その一つは材料自身の高電容量をアップすることを前提に、ニッケル(Ni)を主要成分とする二元と三元正極材料を採用することで、もう一つは、正極材料作業電圧(4.2Vより大きい)をアップして材料の電容量を増加することである。 Industry currently has a two main development direction to the cathode material having a high energy density, on the assumption that the one which up high capacity of the material itself, the main nickel (Ni) component The other is to increase the electric capacity of the material by increasing the positive electrode material working voltage (greater than 4.2 V) by adopting the binary and ternary positive electrode materials.
六方晶リチウムイオン電池正極材料は比較的高い電容量を有し、リチウムイオン電池正極材料の中で最も広く使用されているが、六方晶リチウムイオン電池正極材料の粉体表面は電解液と容易に反応を発生し、材料寿命が短くなり、且つ使用上、安全性の心配がある。 Hexagonal lithium ion battery positive electrode material has a relatively high capacitance, has been most widely used in the lithium ion battery positive electrode material, the powder surface of the hexagonal Li-ion battery cathode materials easily and electrolyte Reaction occurs, material life is shortened, and there are safety concerns in use.
周知の技術中、六方晶リチウムイオン電池正極材料の安定性をアップするため、多くの研究者は材料構造中に、比較的安定した修飾物質を添加し、それにより正極材料表面の安定性をアップし、そのうち、使用される修飾物質は六方晶正極材料主体を非構成のニッケル(Ni)、コバルト(Co)、マンガン(Mn)の三種類の活性金属元素である。 To improve the stability of hexagonal lithium-ion battery cathode materials in a well-known technology, many researchers add relatively stable modifiers in the material structure, thereby increasing the stability of the cathode material surface. Among them, the modifiers used are three kinds of active metal elements, nickel (Ni), cobalt (Co), and manganese (Mn), which are mainly composed of a hexagonal positive electrode material.
具体的には、常用される修飾方法には、材料表面修飾法と金属ドープ修飾法の二種類がある。 Specifically, there are two types of modification methods commonly used: a material surface modification method and a metal dope modification method.
材料表面修飾法に関しては、正極材料の外部を一層のナノサイズの非電気化学活性物質で被覆し、これにより正極材料表面の電解液との反応性を低減し、材料の使用寿命をアップする。しかし、材料全体を均一にナノサイズの保護層で被覆させる必要があり、技術上、一定の難度があり且つコントロールが容易でなく、このため大幅に産業上の利用性が低減する。 With respect to the material surface modification method, the outside of the positive electrode material is coated with a single nano-sized non-electrochemically active substance, thereby reducing the reactivity with the electrolyte on the surface of the positive electrode material and increasing the service life of the material. However, it is necessary to uniformly coat the entire material with a nano-sized protective layer, which is technically difficult and difficult to control, which greatly reduces industrial applicability.
金属ドープ法は、正極材料構造中に均一に非電気化学活性の金属をドープすることで、材料構造自身の安定性をアップするが、もし顕著に材料表面の電解液との反応を抑制しようとするなら、高剤量の修飾物質をドープする必要があり、これは材料の電容量の大幅な減少をもたらし得て、却って材料自身の高エネルギー密度の特徴を失わせてしまう。 The metal doping method improves the stability of the material structure itself by uniformly doping a non-electrochemically active metal in the positive electrode material structure, but if it attempts to significantly suppress the reaction with the electrolyte on the material surface to If, it is necessary to dope a high dosage amount of modulator, which is obtained resulted in a significant reduction in capacity of the material, resulting in rather to lose the characteristics of high energy density of the material itself.
このため、一種の、リチウムイオン電池の新規な金属勾配ドープ正極材料であって、材料修飾により材料の安定性と安全性をアップできると共に、材料のエネルギー密度上の性能も考慮し、高電容量と高い安全性を共に考慮したリチウムイオン電池の製作を達成でき、上述の周知の技術の問題を解決するものが必要とされている。 Thus, one, a novel metal gradient doped cathode material for lithium ion batteries, it is possible up stability and safety of the material by the material modification, also taking into account the performance of the energy density of the material, the high capacity Therefore, there is a need for a lithium ion battery that can be manufactured in consideration of both high safety and to solve the above-mentioned problems of the known technology.
本発明は一種のリチウムイオン電池の金属勾配ドープ正極材料を提供し、その材料粉体は、六方晶正極材料主体及び六方晶正極材料主体に濃度勾配ドープされる修飾金属で構成されて界面を有さず分層を有さない粉体構造であり、金属勾配ドープリチウムイオン電池正極材料全体剤量は、化学式 f mol% M doped LizNiaCobMncO2 を用いて表示でき、そのうち、LizNiaCobMncO2は六方晶正極材料主体を表示し、Mは修飾金属を表示し、且つ修飾金属のモル含有量は六方晶正極材料中のニッケル、コバルト及びマンガンの総モル含有量の0.5%以上であり、且つ六方晶正極材料中のニッケル、コバルト及びマンガンの総モル含有量の10%以下であり、並びに、0.5%(a+b+c)≦f≦10%(a+b+c)を用いて表示され得る。
The present invention provides a kind of metal gradient doped positive electrode material for lithium ion batteries, and the material powder is composed mainly of a hexagonal positive electrode material and a modified metal that is mainly doped with a concentration gradient of the hexagonal positive electrode material and has an interface. a powder structure without the layer separation without the metal gradient doped lithium ion battery positive electrode material total agent amount may be displayed by using the formula f mol% M doped Li z Ni a Co b
上述のリチウムイオン電池の金属勾配ドープ正極材料が含有する六方晶正極材料主体は、ニッケル、コバルト単一金属或いはニッケルとコバルト、ニッケルとマンガン、コバルトとマンガンの二種類の金属或いはニッケルとコバルトとマンガンの三種類の金属の、任意のいずれかの形式の酸化物で構成された正極材料活性ユニットとされ得て、並びに化学式LizNiaCobMncO2で表示され、その化学剤量範囲は、{0.9≦z≦1.2;a+b+c=1;0≦a≦1;0≦b≦1;0≦c≦0.6}を満足し、修飾金属はマグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、ホウ素(B)、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、チタン(Ti)、ケイ素(Si)、及びスズ(Sn)のうちの一種類の金属元素とされ、且つ修飾金属は正極材料粉体の表面に比較的集中し、並びにコアに向けて連続性の濃度逓減を現出し、連続濃度勾配ドープ分布を形成する。リチウムイオン電池の金属勾配ドープ正極材料粉体表面は濃度が比較的高い修飾金属を有し、材料の電解液に対する反応性が効果的に下げられ、これにより全体のリチウムイオン電池の操作安定性及び安全性が向上される。特に、低い剤量の修飾金属を使用するだけで効果を達成でき、周知の技術中の、過多の修飾金属をドープすることにより大幅に電容量が下がる問題を防止でき、ひいては全体のリチウムイオン電池のエネルギー密度を増加し、使用寿命を延長できる。 The hexagonal positive electrode material mainly contained in the metal gradient doped positive electrode material of the lithium ion battery described above is nickel, cobalt single metal or nickel and cobalt, nickel and manganese, cobalt and manganese, two kinds of metals or nickel, cobalt and manganese. A positive electrode material active unit composed of any type of oxides of the three types of metals, and represented by the chemical formula Li z Ni a Co b Mn c O 2 , and its chemical dosage range Satisfies {0.9 ≦ z ≦ 1.2; a + b + c = 1; 0 ≦ a ≦ 1; 0 ≦ b ≦ 1; 0 ≦ c ≦ 0.6}, and the modified metals are magnesium (Mg), calcium (Ca), strontium (Sr), boron (B), aluminum (Al), gallium (Ga), indium (In), titanium (Ti), silicon (Si), and tin (Sn) Is one type of metal elemental of out and modified metal are relatively concentrated in the surface of the positive electrode material powder, as well as current issues a concentration diminishing continuity towards the core, to form a continuous concentration gradient doping profile. The metal gradient doped positive electrode material powder surface of the lithium ion battery has a relatively high concentration of the modified metal, effectively reducing the reactivity of the material to the electrolyte, thereby improving the overall operational stability of the lithium ion battery and Safety is improved. In particular, it can be achieved only in effect using the modified metal low dosage amounts, in well-known techniques, by doping the modified metal excessive prevents significant capacitance problems to fall, thus the whole of the lithium ion battery The energy density can be increased and the service life can be extended.
具体的には、本発明の正極材料は比較的低い剤量の修飾金属を使用することで、電解液に対する反応性を低くする特徴のほか、良好な電気化学特性と熱安定性を共に有し、大幅にリチウムイオン電池の全体操作効率をアップし、使用寿命を延長し、並びに産業上の利用性をアップする。 Specifically, the positive electrode material of the present invention has both good electrochemical characteristics and thermal stability, in addition to the feature of reducing the reactivity to the electrolyte by using a relatively low amount of the modified metal. , Greatly increase the overall operation efficiency of the lithium ion battery, extend the service life, and improve the industrial utility.
以下に本発明の技術内容、構造特徴、達成する目的及び作用効果について、以下に例を挙げ並びに図面を組み合わせて詳細に説明する。 The technical contents, structural features, objects to be achieved, and operational effects of the present invention will be described in detail below with reference to examples and drawings.
図1を参照されたい。図1は本発明の実施例のリチウムイオン電池の金属勾配ドープ正極材料の構造表示図である。図1に示されるように、本発明のリチウムイオン電池の金属勾配ドープ正極材料1は粉体とされ、且つ全体上、六方晶正極材料主体及び六方晶正極材料に連続濃度勾配ドープされた修飾金属を含み、粉体内部は無界面で無分層であり、リチウムイオン電池の金属勾配ドープ正極材料剤量は、化学式 f mol% M doped LizNiaCobMncO2 を用いて表示でき、そのうち、LizNiaCobMncO2は六方晶正極材料主体を表示し、Mは修飾金属を表示し、且つ修飾金属のモル含有量は六方晶正極材料中のニッケル、コバルト及びマンガンの総モル含有量の0.5%以上であり、且つ六方晶正極材料中のニッケル、コバルト及びマンガンの総モル含有量の10%以下であり、0.5%(a+b+c)≦f≦10%(a+b+c)を用いて表示され得る。
Please refer to FIG. FIG. 1 is a structural display diagram of a metal gradient doped positive electrode material of a lithium ion battery according to an embodiment of the present invention. As shown in FIG. 1, the metal gradient-doped
上述のリチウムイオン電池の金属勾配ドープ正極材料が含有する六方晶正極材料主体は、ニッケル、コバルト単一金属或いはニッケルとコバルト、ニッケルとマンガン、コバルトとマンガンの二種類の金属或いはニッケルとコバルトとマンガンの三種類の金属の、任意のいずれかの形式の酸化物で構成された正極材料活性ユニットとされ得て、並びに化学式LizNiaCobMncO2で表示され、その化学剤量範囲は、{0.9≦z≦1.2;a+b+c=1;0≦a≦1;0≦b≦1;0≦c≦0.6}を満足し、その濃度勾配を以てドープされた修飾金属は連続逓減の分布方式で六方晶正極材料主体中にドープされ、特に、修飾金属はニッケル(Ni)、コバルト(Co)、マンガン(Mn)の三つの活性金属元素とは異なる金属元素であり且つ電解液に対して比較的不活性の金属である。 The hexagonal positive electrode material mainly contained in the metal gradient doped positive electrode material of the lithium ion battery described above is nickel, cobalt single metal or nickel and cobalt, nickel and manganese, cobalt and manganese, two kinds of metals or nickel, cobalt and manganese. A positive electrode material active unit composed of any type of oxides of the three types of metals, and represented by the chemical formula Li z Ni a Co b Mn c O 2 , and its chemical dosage range Satisfies the following conditions: {0.9 ≦ z ≦ 1.2; a + b + c = 1; 0 ≦ a ≦ 1; 0 ≦ b ≦ 1; 0 ≦ c ≦ 0.6} and is doped with the concentration gradient Is doped in the main material of hexagonal positive electrode in a continuously decreasing distribution system, and in particular, the modified metal is a metal element different from the three active metal elements of nickel (Ni), cobalt (Co), and manganese (Mn). It is a relatively inert metal with respect to the and and electrolyte.
比較的好ましい修飾金属は、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、ホウ素(B)、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、チタン(Ti)、ケイ素(Si)、及びスズ(Sn)のうちの一種類の金属或いはこれらに類する金属元素とされる。特に、修飾金属は六方晶正極材料粉体の表面Aに集中するようにドープされ、並びに六方晶正極材料粉体のコアBに向けて連続逓減し、修飾金属濃度逓減の方向は図中のCに示されるようであり、これにより必要な連続濃度勾配分布を形成する。 Relatively preferred modified metals are magnesium (Mg), calcium (Ca), strontium (Sr), boron (B), aluminum (Al), gallium (Ga), indium (In), titanium (Ti), silicon (Si ) And tin (Sn), or a metal element similar to these metals. In particular, the modified metal is doped so as to concentrate on the surface A of the hexagonal positive electrode material powder, and continuously decreases toward the core B of the hexagonal positive electrode material powder, and the direction of decreasing the concentration of the modified metal is C in the figure. This forms the required continuous concentration gradient distribution.
このほか、本発明のリチウムイオン電池の金属勾配ドープ正極材料の空間群はR−3mとされ、その粉体粒径D50は0.5〜25μmの間であり、金属勾配濃度は材料中で粉体粒径の半分で変化し、すなわち、約0.25〜12.5μmの変化区間とされる。特に、本発明の正極材料のタップ密度(tap−density)は、少なくとも1.5gcm-3以上とされ、且つその表面面積は0.1〜25m2g-1の間とされる。 In addition, the space group of the metal gradient doped positive electrode material of the lithium ion battery of the present invention is R-3m, the powder particle diameter D50 is between 0.5 and 25 μm, and the metal gradient concentration is powder in the material. It changes at half of the body particle size, that is, a change interval of about 0.25 to 12.5 μm. In particular, the tap density of the positive electrode material of the present invention is at least 1.5 gcm −3 or more, and the surface area is between 0.1 and 25 m 2 g −1 .
以下に実施例と比較例を以て、並びに物理及び電気化学特性分析を以て、本発明の改善された性能を明らかにする。 The improved performance of the present invention will be elucidated below with examples and comparative examples, as well as with physical and electrochemical property analyses.
[実施例1]
1.アルミニウム勾配ドープのリチウムニッケルコバルト酸化物正極材料の合成:
化学共沈殿法を利用して球状ニッケルコバルト水酸化物(Ni0.82Co0.18(OH)2)を合成し、さらに水酸化リチウムを加えて混合し、リチウム塩とニッケルコバルト金属含有量の剤量比を1.02:1.00とし、この混合物を酸素ガス雰囲気下で、750℃で10時間焼成してLiNi0.82Co0.18O2正極材料(LNCO)を得る。さらにリチウムニッケルコバルト酸化物(LNCO)を反応タンク中に入れ、共沈殿法を使用し、適量の水酸化アルミニウムに均一にリチウムニッケルコバルト酸化物表面を被覆させた後、酸素ガス雰囲気中で750℃で3時間焼成しアルミニウム金属勾配ドープのリチウムニッケルコバルト酸化物正極材料(表示符号:Al(GD)−LNCO)を得る。
[Example 1]
1. Synthesis of aluminum gradient doped lithium nickel cobalt oxide cathode material:
Spherical nickel cobalt hydroxide (Ni 0.82 Co 0.18 (OH) 2 ) was synthesized using the chemical coprecipitation method, and lithium hydroxide was added and mixed. The dose ratio of lithium salt to nickel cobalt metal content 1.02: 1.00, and this mixture is fired at 750 ° C. for 10 hours in an oxygen gas atmosphere to obtain a LiNi 0.82 Co 0.18 O 2 positive electrode material (LNCO). Further, lithium nickel cobalt oxide (LNCO) was placed in the reaction tank, and the coprecipitation method was used to uniformly coat the surface of the lithium nickel cobalt oxide with an appropriate amount of aluminum hydroxide, followed by 750 ° C. in an oxygen gas atmosphere. To obtain an aluminum metal gradient-doped lithium nickel cobalt oxide positive electrode material (designated code: Al (GD) -LNCO).
2.ボタン型電池の製造と試験:
正極極板の製作:正極材料として、石墨:カーボンブラック:PVdF(polyvinylidene fluoride)=90:6:4の比例で計り取り、その後、一定比率のNMPを加えて均一に混合してスラリーとなし、150μmナイフを利用してスラリーをアルミ箔(18μm)上に塗布する。極板を先に加熱プラットフォームで加熱乾燥させ、さらに真空加熱乾燥し、NMP溶剤を除去する。電池組立前に、極板を先に圧延し、さらに極板を裁断して直径約12mmのコイン型極板となす。リチウム金属を負極とし、Al(GD)−LNCO極板を正極とし、電解質溶液は1M LiPF6を、ECとDMCの体積比1:1の混合溶剤に溶かしたものとする。充放電範囲をそれぞれ2.8−4.3Vと2.8−4.5Vとし、充放電電流を0.1Cとし、Al(GD)−LNCO正極材料の各種電気化学特性を測定する。さらに、充放電範囲をそれぞれ2.8−4.3Vと2.8−4.5Vとし、各種充放電電流(C−rate)で、Al(GD)−LNCO正極材料の各種電気化学特性を測定する。
2. Manufacturing and testing of button-type batteries:
Production of positive electrode plate: As a positive electrode material, graphite: carbon black: PVdF (polyvinylidene fluoride) = 90: 6: 4 is measured in proportion, and then a certain ratio of NMP is added and mixed uniformly to form a slurry. The slurry is applied on aluminum foil (18 μm) using a 150 μm knife. The electrode plate is first heat-dried on a heating platform, and further vacuum-heated to remove the NMP solvent. Before battery assembly, the electrode plate is first rolled, and the electrode plate is further cut into a coin-type electrode plate having a diameter of about 12 mm. Assume that lithium metal is used as a negative electrode, an Al (GD) -LNCO electrode plate is used as a positive electrode, and 1 M LiPF 6 is dissolved in a mixed solvent of EC and DMC in a volume ratio of 1: 1. The charge / discharge ranges are set to 2.8-4.3V and 2.8-4.5V, respectively, the charge / discharge current is set to 0.1C, and various electrochemical characteristics of the Al (GD) -LNCO positive electrode material are measured. Furthermore, charge / discharge ranges were set to 2.8-4.3V and 2.8-4.5V, respectively, and various electrochemical characteristics of Al (GD) -LNCO positive electrode materials were measured at various charge / discharge currents (C-rate). To do.
3.Al(GD)−LNCO正極材料の示差走査熱量計(DSC)測定:
ボタン型電池を構成し、4.3Vまで充電し、鉗子を用いてボタン型電池を分解し、正極極板を取り出し、並びに正極材料を削ぎ取り、3mgの正極材料を取ってアルミ坩堝に入れ、並びに3μL電解液を加え、さらにアルミ坩堝をかしめ接合しシールし、5℃ min-1の加熱速度とし、測定器の走査温度範囲は180−280℃とする。
3. Differential scanning calorimetry (DSC) measurement of Al (GD) -LNCO positive electrode material:
Configure the button type battery, charge to 4.3V, disassemble the button type battery with forceps, take out the positive electrode plate, scrape the positive electrode material, take 3 mg of the positive electrode material, put it in the aluminum crucible, In addition, 3 μL electrolytic solution is added, and an aluminum crucible is further caulked and bonded, and the heating rate is 5 ° C. min −1 , and the scanning temperature range of the measuring device is 180-280 ° C.
[比較例1]
本実施例の比較に用いる比較例1、すなわち、未修飾のリチウムニッケルコバルト酸化物正極材料(符号LNCOで表示される)は、その合成方法が以下のとおりである。すなわち、化学共沈殿法を利用して球状ニッケルコバルト水酸化物(Ni0.82Co0.18(OH)2)を合成し、さらに水酸化リチウムを加えて混合し、リチウム塩とニッケルコバルト金属含有量の剤量比を1.02:1.00とし、この混合物を酸素ガス雰囲気下で、750℃で13時間焼成してLiNi0.82Co0.18O2正極材料(LNCO)を得る。後続のボタン型リチウム電池の製造と試験は実施例Al(GD)−LNCOと同じであり、LNCO正極材料の示差走査熱量計(DSC)測定も実施例Al(GD)−LNCOと同じである。
[Comparative Example 1]
The synthesis method of Comparative Example 1 used for the comparison of this example, that is, an unmodified lithium nickel cobalt oxide positive electrode material (indicated by the symbol LNCO) is as follows. That is, spherical nickel cobalt hydroxide (Ni 0.82 Co 0.18 (OH) 2 ) is synthesized using a chemical coprecipitation method, lithium hydroxide is added and mixed, and the lithium salt and nickel cobalt metal content agent are mixed. The quantity ratio is 1.02: 1.00, and this mixture is fired at 750 ° C. for 13 hours in an oxygen gas atmosphere to obtain a LiNi 0.82 Co 0.18 O 2 positive electrode material (LNCO). Subsequent button-type lithium batteries were manufactured and tested in the same manner as Example Al (GD) -LNCO, and differential scanning calorimetry (DSC) measurements of the LNCO positive electrode material were also the same as in Example Al (GD) -LNCO.
実施例1及び比較例1の試験結果はそれぞれ以下のようであり、試験結果は図2から図6に示されるとおりである。 The test results of Example 1 and Comparative Example 1 are as follows, and the test results are as shown in FIGS.
物理特性分析に関して、誘導結合プラズマ発光分光分析(ICP/OES)とエネルギー分散型X線分析(EDS)を使用して、実施例Al(GD)−LNCOの正極材料に対して全体、表面及び断面の元素定量分析を行う。ICP/OESでアルミニウム元素のリチウムニッケルコバルト酸化物全体へのドープのモル比率は2.55%である。図2(a)はAl(GD)−LNCO正極材料の表面形態とされ、図2(b)はAl(GD)−LNCO正極材料表面のアルミニウム元素分布図であり、Al(GD)−LNCO正極材料表面に確実に高剤量のアルミニウム元素が存在することを示す。このほか、図2(c)はAl(GD)−LNCO正極材料の断面形態を示し、Al(GD)−LNCO材料粉体中には界面がなく、且つ分層の構造がないことを示し、図2(d)は材料破断面のアルミニウム元素分布比率定量分析グラフであり、Al(GD)−LNCO材料表面のアルミニウム元素ドープ比率が8.48%とされ、Al(GD)−LNCO材料内部の表面からの距離が8.5μmの部分のアルミニウム元素ドープモル比率は0.83%に下がり、且つAl(GD)−LNCO正極材料のアルミニウム元素分布は表面からコアに向けて連続勾配逓減の分布を呈する。 For physical property analysis, the whole, surface and cross-section for the positive electrode material of Example Al (GD) -LNCO using inductively coupled plasma emission spectroscopy (ICP / OES) and energy dispersive X-ray analysis (EDS) Quantitative elemental analysis. In ICP / OES, the molar ratio of the doping of the aluminum element to the entire lithium nickel cobalt oxide is 2.55%. 2A is a surface form of the Al (GD) -LNCO positive electrode material, and FIG. 2B is an aluminum element distribution map on the surface of the Al (GD) -LNCO positive electrode material, and the Al (GD) -LNCO positive electrode. It shows that a high amount of aluminum element is surely present on the material surface. In addition, FIG. 2 (c) shows a cross-sectional form of the Al (GD) -LNCO positive electrode material, showing that there is no interface and no layered structure in the Al (GD) -LNCO material powder, FIG. 2D is a quantitative analysis graph of the aluminum element distribution ratio on the material fracture surface, where the aluminum element doping ratio on the surface of the Al (GD) -LNCO material is 8.48%, and the inside of the Al (GD) -LNCO material. The aluminum element doping molar ratio in the portion whose distance from the surface is 8.5 μm is reduced to 0.83%, and the aluminum element distribution of the Al (GD) -LNCO positive electrode material exhibits a continuously decreasing gradient from the surface toward the core. .
電気化学特性分析に関しては、本実施例のAl(GD)−LNCOと比較例1のLNCO材料の電気化学特性の差異は、図3中の材料充放電(0.1C)の充放電曲線特性を比較することで、明らかに見て取れる。電圧範囲2.8−4.3Vの間では、実施例のAl(GD)−LNCOの放電電容量は182.7mAhg-1であり、不可逆の電容量は33.2mAhg-1であり、もし、電圧範囲を2.8−4.5Vの間に引き上げると、実施例のAl(GD)−LNCOの放電電容量は197.8mAhg-1となり、不可逆の電容量は54.3mAhg-1とされる。 Regarding the electrochemical property analysis, the difference in the electrochemical property between the Al (GD) -LNCO of this example and the LNCO material of Comparative Example 1 is the charge / discharge curve property of the material charge / discharge (0.1C) in FIG. By comparing, it can be clearly seen. Between the voltage range 2.8-4.3V, the discharge capacity of the Al (GD) -LNCO examples are 182.7MAhg -1, capacitance irreversible is 33.2MAhg -1, if raising a voltage range between 2.8-4.5V, the discharge capacity of the Al (GD) -LNCO examples 197.8MAhg -1, and the the capacitance of irreversible are 54.3MAhg -1 .
このほか、図4は本発明の実施例1及び比較例1の異なる放電電流条件に変更したときの充放電曲線図である。そのうち、定電流充放電条件は、充電0.2C、放電0.5C〜7Cに設定され、作業電圧は2.8〜4.3Vの間である。図中、明らかに観察されることは、実施例のAl(GD)−LNCOは比較的高い放電電圧プラットフォームを有し、すなわち、7Cの放電電流下で、82.06%の高い電容量を保有し、比較例1のLNCOは僅かに71.10%の電容量が残るにすぎない。 In addition, FIG. 4 is a charge / discharge curve diagram when the discharge current conditions are changed to those in Example 1 and Comparative Example 1 of the present invention. Among them, the constant current charge / discharge conditions are set to charge 0.2C, discharge 0.5C to 7C, and the working voltage is between 2.8 to 4.3V. In the figure, clearly the observed thing, Al (GD) -LNCO embodiment has a relatively high discharge voltage platform, i.e., at a discharge current of a 7C, possess high capacitance 82.06% and, LNCO of Comparative example 1 is only slightly 71.10% of capacity remains.
図5の本発明の実施例1及び比較例1のサイクル寿命曲線図には、0.5Cの定電流で電圧範囲2.8−4.3Vの間で、材料に対して70回の充放電を行ない、計算して実施例Al(GD)−LNCOがなおも原電容量の91.11%を維持していることが分かり、比較例1のLNCOは僅かに原電容量の85.75%しか残っていない。もし電圧範囲を2.8−4.5Vに改め、並びに0.5C定電流で材料に対して充放電を行ない、40回の充放電試験を行うと、計算によれば実施例Al(GD)−LNCOはなおも原電容量の89.98%の電容量を維持し、比較例1のLNCOは原電容量の79.23%しか残っていないことが分かる。 The cycle life curves of Example 1 of the present invention and Comparative Example 1 in FIG. 5 show that the material is charged and discharged 70 times in a voltage range of 2.8-4.3 V at a constant current of 0.5 C. the performed calculations to find that in example Al (GD) -LNCO maintains still a 91.11% of the original capacity, LNCO of Comparative example 1 is 85.75% of the slightly original capacity Only remains. If the voltage range is changed to 2.8-4.5 V, the material is charged / discharged at a constant current of 0.5 C, and 40 charge / discharge tests are performed, the calculation results in Example Al (GD). -LNCO is still maintaining the 89.98% of the capacity of the original capacity, it can be seen that LNCO of Comparative example 1 has only remaining 79.23% of the original capacity.
これにより、以上の結果を総合すると、実施例Al(GD)−LNCOは確実に比較例1のLNCOに較べて優れた電気化学特性を有することが証明され得る。 Thus, when the above results are combined, it can be proved that the example Al (GD) -LNCO surely has superior electrochemical characteristics as compared with the LNCO of Comparative Example 1.
さらに図6を参照されたい。本実施例1及び比較例1の示差走査熱量計(DSC)測定図であり、図示されるように、比較例1の放熱分解温度は約214.3℃であり、しかし実施例Al(GD)−LNCOは明らかに引き上げられた分解温度を有し、その放熱分解温度は約229.9℃まで引き上げられ、且つ放熱量は855.06Jg-1より591.76Jg-1に下がり、これにより実施例Al(GD)−LNCOは比較的良好な熱安定性を有することが証明された。 See further FIG. FIG. 3 is a differential scanning calorimeter (DSC) measurement diagram of Example 1 and Comparative Example 1; as shown, the heat dissociation temperature of Comparative Example 1 is about 214.3 ° C., but Example Al (GD) -LNCO has a clearly increased decomposition temperature, its heat dissociation temperature is increased to about 229.9 ° C., and the heat dissipation is reduced from 855.06 Jg −1 to 591.76 Jg −1 , thereby Al (GD) -LNCO has proven to have a relatively good thermal stability.
[実施例2]
1.マグネシウム勾配ドープのリチウムニッケルコバルトマンガン酸化物正極材料の合成:
化学共沈殿法を利用して球状ニッケルコバルトマンガン水酸化物(Ni0.51Co0.29Mn0.20(OH)2)を合成した後、まず球状ニッケルコバルトマンガン水酸化物を酸素ガス雰囲気下で600℃で10時間焼結し、球状ニッケルコバルトマンガン酸化物を得た後、さらに水酸化リチウムを加えて混合し、リチウム塩とニッケルコバルトマンガン金属含有量の剤量比を1.02:1.00とし、この混合物を酸素ガス雰囲気下で、850℃で18時間焼成してLiNi0.51Co0.29Mn0.20O2正極材料(LNCMO)を得る。さらにリチウムニッケルコバルトマンガン酸化物(LNCMO)を反応タンク中に入れ、共沈殿法を使用し、適量の水酸化マグネシウムに均一にリチウムニッケルコバルトマンガン酸化物表面を被覆させた後、酸素ガス雰囲気中で850℃で2時間焼成しマグネシウム勾配ドープのリチウムニッケルコバルトマンガン酸化物正極材料(表示符号はMg(GD)−LNCMO)を得る。
[Example 2]
1. Synthesis of magnesium gradient doped lithium nickel cobalt manganese oxide cathode material:
After synthesizing spherical nickel cobalt manganese hydroxide (Ni 0.51 Co 0.29 Mn 0.20 (OH) 2 ) using a chemical coprecipitation method, first, spherical nickel cobalt manganese hydroxide is synthesized at 600 ° C. under an oxygen gas atmosphere. After sintering for a while to obtain spherical nickel cobalt manganese oxide, lithium hydroxide was further added and mixed, and the dose ratio of lithium salt to nickel cobalt manganese metal content was set to 1.02: 1.00. The mixture is calcined at 850 ° C. for 18 hours under an oxygen gas atmosphere to obtain a LiNi 0.51 Co 0.29 Mn 0.20 O 2 positive electrode material (LNCMO). Further, lithium nickel cobalt manganese oxide (LNCMO) is put in a reaction tank, and after coprecipitation is used, the lithium nickel cobalt manganese oxide surface is uniformly coated on a suitable amount of magnesium hydroxide, and then in an oxygen gas atmosphere. Calcination is performed at 850 ° C. for 2 hours to obtain a magnesium gradient-doped lithium nickel cobalt manganese oxide positive electrode material (indicated by Mg (GD) -LNCMO).
2.ボタン型電池の製造と試験:
正極極板の製作:正極材料として、石墨:カーボンブラック:PVdF(polyvinylidene fluoride)=91:6:3の比例で計り取り、その後、一定比率のNMPを加えて均一に混合してスラリーとなし、150μmナイフを利用してスラリーをアルミ箔(18μm)上に塗布する。極板を先に加熱プラットフォームで加熱乾燥させ、さらに真空加熱乾燥し、NMP溶剤を除去する。電池組立前に、極板を先に圧延し、さらに極板を裁断して直径約12mmのコイン型極板となす。リチウム金属を負極とし、Mg(GD)−LNCMO極板を正極とし、電解質溶液は1M LiPF6をECとDMCの体積比1:1の混合溶剤に溶したものとする。充放電範囲をそれぞれ2.8−4.3Vと2.8−4.5Vとし、各種充放電電流(C−rate)で、Mg(GD)−LNCMO正極材料の各種電気化学特性を測定する。
2. Manufacturing and testing of button-type batteries:
Production of positive electrode plate: As a positive electrode material, graphite: carbon black: PVdF (polyvinylidene fluoride) = 91: 6: 3 is measured in proportion, and then a certain ratio of NMP is added and mixed uniformly to form a slurry. The slurry is applied on aluminum foil (18 μm) using a 150 μm knife. The electrode plate is first heat-dried on a heating platform, and further vacuum-heated to remove the NMP solvent. Before battery assembly, the electrode plate is first rolled, and the electrode plate is further cut into a coin-type electrode plate having a diameter of about 12 mm. The lithium metal is used as the negative electrode, the Mg (GD) -LNCMO electrode plate is used as the positive electrode, and the electrolyte solution is prepared by dissolving 1M LiPF 6 in a mixed solvent of EC and DMC in a volume ratio of 1: 1. The charge / discharge ranges are 2.8-4.3V and 2.8-4.5V, respectively, and various electrochemical characteristics of the Mg (GD) -LNCMO positive electrode material are measured at various charge / discharge currents (C-rate).
3.Mg(GD)−LNCMO正極材料の示差走査熱量計(DSC)測定:
ボタン型電池を構成し、4.5Vまで充電し、鉗子を用いてボタン型電池を分解し、正極極板を取り出し、並びに正極材料を削ぎ取り、3mgの正極材料を取ってアルミ坩堝に入れ、並びに3μL電解液を加え、さらにアルミ坩堝をかしめ接合しシールし、5℃ min-1の加熱速度とし、測定器の走査温度範囲は220−300℃とする。
3. Differential scanning calorimetry (DSC) measurement of Mg (GD) -LNCMO positive electrode material:
Configure the button type battery, charge to 4.5V, disassemble the button type battery with forceps, take out the positive electrode plate, scrape the positive electrode material, take 3 mg of the positive electrode material, put it in the aluminum crucible, In addition, 3 μL electrolyte is added, and an aluminum crucible is caulked and sealed, and the heating rate is 5 ° C. min −1 , and the scanning temperature range of the measuring device is 220-300 ° C.
[比較例2]
比較例2は、すなわち、未修飾のリチウムニッケルコバルトマンガン酸化物正極材料(符号LNCMOで表示される)は、その合成方法が以下のとおりである。すなわち、化学共沈殿法を利用して球状ニッケルコバルトマンガン水酸化物(Ni0.51Co0.29Mn0.20(OH)2)を合成し、球状ニッケルコバルトマンガン水酸化物を酸素雰囲気下で600℃の温度で10時間焼成し、球状ニッケルコバルトマンガン酸化物を得る。さらに水酸化リチウムを加えて混合し、リチウム塩とニッケルコバルトマンガン含有量の剤量比を1.02:1.00とし、この混合物を酸素ガス雰囲気下で、850℃で20時間焼成してLiNi0.51Co0.29Mn0.20O2正極材料(LNCMO)を得る。後続のボタン型リチウム電池の製造と試験は実施例Mg(GD)−LNCMOと同じであり、LNCMO正極材料の示差走査熱量計(DSC)測定も実施例Mg(GD)−LNCMOと同じである。
[Comparative Example 2]
In Comparative Example 2, that is, an unmodified lithium nickel cobalt manganese oxide positive electrode material (indicated by symbol LNCMO), the synthesis method is as follows. That is, spherical nickel cobalt manganese hydroxide (Ni 0.51 Co 0.29 Mn 0.20 (OH) 2 ) was synthesized using a chemical coprecipitation method, and the spherical nickel cobalt manganese hydroxide was synthesized at a temperature of 600 ° C. in an oxygen atmosphere. Sinter for 10 hours to obtain spherical nickel cobalt manganese oxide. Further, lithium hydroxide was added and mixed, and the dose ratio of lithium salt to nickel cobalt manganese content was set to 1.02: 1.00. This mixture was calcined at 850 ° C. for 20 hours in an oxygen gas atmosphere, and LiNi. 0.51 Co 0.29 Mn 0.20 O 2 cathode material (LNCMO) is obtained. Subsequent button-type lithium batteries are manufactured and tested in the same manner as Example Mg (GD) -LNCMO, and differential scanning calorimetry (DSC) measurements of the LNCMO cathode material are also the same as Example Mg (GD) -LNCMO.
実施例2及び比較例2の試験結果はそれぞれ以下のようであり、試験結果は図7から図11に示されるとおりである。 The test results of Example 2 and Comparative Example 2 are as follows, and the test results are as shown in FIGS.
物理特性分析に関して、誘導結合プラズマ発光分光分析(ICP/OES)とエネルギー分散型X線分析(EDS)を使用して、実施例Mg(GD)−LNCMOの正極材料に対して全体、表面及び断面の元素定量分析を行う。ICP/OESで測定したマグネシウム元素のリチウムニッケルコバルトマンガン酸化物全体へのドープのモル比率は1.7%である。図7(a)はMg(GD)−LNCMO正極材料の表面形態とされ、図7(b)はMg(GD)−LNCMO正極材料表面のマグネシウム元素分布図であり、Mg(GD)−LNCMO正極材料表面に確実に高剤量のマグネシウム元素が存在することを示す。このほか、図7(c)はMg(GD)−LNCMO正極材料の断面形態を示し、Mg(GD)−LNCMO材料粉体中には界面がなく、且つ分層の構造がないことを示し、図7(d)は材料破断面のマグネシウム元素分布比率定量分析グラフであり、Mg(GD)−LNCMO材料表面のマグネシウム元素ドープ比率が2.5%とされ、Mg(GD)−LNCMO材料内部の表面からの距離が6.5μmの部分のマグネシウム元素ドープモル比率は0.5%に下がり、且つMg(GD)−LNCMO正極材料のマグネシウム元素分布は表面からコアに向けて連続勾配逓減の分布を呈する。 For physical property analysis, inductively coupled plasma emission spectroscopy (ICP / OES) and energy dispersive X-ray analysis (EDS) are used for the cathode material of Example Mg (GD) -LNCMO as a whole, surface and cross section. Quantitative elemental analysis. The molar ratio of the magnesium element to the entire lithium nickel cobalt manganese oxide measured by ICP / OES is 1.7%. 7A is a surface form of the Mg (GD) -LNCMO positive electrode material, and FIG. 7B is a magnesium element distribution diagram on the surface of the Mg (GD) -LNCMO positive electrode material. Mg (GD) -LNCMO positive electrode It shows that a high amount of magnesium element is surely present on the material surface. In addition, FIG. 7C shows a cross-sectional form of the Mg (GD) -LNCMO positive electrode material, showing that there is no interface and no layered structure in the Mg (GD) -LNCMO material powder, FIG. 7 (d) is a quantitative analysis graph of the magnesium element distribution ratio on the material fracture surface, where the magnesium element doping ratio on the surface of the Mg (GD) -LNCMO material is 2.5%, and the Mg (GD) -LNCMO material inside The magnesium element doping molar ratio of the portion whose distance from the surface is 6.5 μm is reduced to 0.5%, and the magnesium element distribution of the Mg (GD) -LNCMO positive electrode material exhibits a decreasing gradient from the surface toward the core. .
電気化学特性分析に関しては、本実施例のMg(GD)−LNCMOと比較例2のLNCMO材料の電気化学特性の差異は、図8中の材料充放電(0.1C)の充放電曲線特性を比較することで、明らかに見て取れる。電圧範囲2.8−4.3Vの間では、実施例のMg(GD)−LNCMOの放電電容量は160.3mAhg-1であり、不可逆の電容量は30.2mAhg-1であり、もし、電圧範囲が2.8−4.5Vの間であると、実施例のMg(GD)−LNCMOの放電電容量は189.9mAhg-1となり、不可逆の電容量は29.2mAhg-1とされる。さらに、図9の各種充放電曲線図から分かるように、定電流条件が充電0.2C及び放電0.5C−7Cであると、作業電圧が2.8−4.3Vの間のとき、実施例のMg(GD)−LNCMOは比較的高い放電電圧プラットフォームを有し、すなわち、7Cの放電電流下で、すなわち78.4%の高い電容量を保有できるが、比較例2のLNCMOは72.5%の電容量しか残っていない。 Regarding the electrochemical property analysis, the difference between the electrochemical properties of the Mg (GD) -LNCMO of this example and the LNCMO material of Comparative Example 2 is the charge / discharge curve property of the material charge / discharge (0.1C) in FIG. By comparing, it can be clearly seen. Between the voltage range 2.8-4.3V, the discharge capacity of the Mg (GD) -LNCMO examples are 160.3MAhg -1, capacitance irreversible is 30.2MAhg -1, if If the voltage range is between 2.8-4.5V, the discharge capacity of the Mg (GD) -LNCMO examples 189.9MAhg -1, and the the capacitance of irreversible are 29.2MAhg -1 . Further, as can be seen from the various charge / discharge curve diagrams of FIG. 9, when the constant current condition is charge 0.2C and discharge 0.5C-7C, the operation is performed when the working voltage is between 2.8-4.3V. examples of Mg (GD) -LNCMO has a relatively high discharge voltage platform, i.e., at a discharge current of a 7C, i.e. can retain high capacity of 78.4%, LNCMO of Comparative example 2 72. 5% of capacity only does not remain.
さらに図10のサイクル寿命曲線図に示されるように、0.5Cの定電流で電圧範囲2.8−4.3Vの間で、材料に対して70回の充放電を行なったところ、計算により実施例Mg(GD)−LNCMOがなおも原電容量の91.7%を維持していることが分かり、比較例2のLNCMOは僅かに原電容量の83.6%しか残っていない。もし電圧範囲を2.8−4.5Vに改め、並びに0.5Cの定電流で材料に対して充放電を行ない、70回の充放電試験を行うと、計算によれば実施例Mg(GD)−LNCMOはなおも原電容量の86.7%の電容量を維持し、比較例2のLNCMOは原電容量の71.3%しか残っていないことが分かる。 Further, as shown in the cycle life curve diagram of FIG. 10, the material was charged and discharged 70 times in the voltage range of 2.8 to 4.3 V at a constant current of 0.5 C. We see that the example Mg (GD) -LNCMO maintains still 91.7% of the original capacity, LNCMO of Comparative example 2 only remaining 83.6% of the slightly original capacity. If the voltage range is changed to 2.8-4.5V, the material is charged / discharged at a constant current of 0.5C, and the charge / discharge test is performed 70 times, the calculation results in the example Mg (GD ) -LNCMO is still maintained 86.7% of the capacity of the original capacity, it can be seen that LNCMO of Comparative example 2 only remaining 71.3% of the original capacity.
以上の結果を総合すると、実施例Mg(GD)−LNCMOは確実に比較例2のLNCMOに較べて優れた電気化学特性を有することが証明され得る。 Taking the above results together, it can be proved that the example Mg (GD) -LNCMO surely has superior electrochemical properties as compared with the LNCMO of Comparative Example 2.
さらに図11を参照されたい。それは本実施例2及び比較例2の示差走査熱量計(DSC)測定図であり、図示されるように、比較例2のLNCMOの放熱分解温度は約254℃であるが、実施例Mg(GD)−LNCMOは明らかに引き上げられた分解温度を有し、その放熱分解温度は約266℃まで引き上げられ、且つ放熱量は227.3Jg-1より115.9Jg-1に下がり、これにより実施例Mg(GD)−LNCMOは比較的良好な熱安定性を有することが証明された。 See further FIG. It is a differential scanning calorimeter (DSC) measurement diagram of the present Example 2 and Comparative Example 2. As shown in the figure, the heat dissipation decomposition temperature of LNCMO of Comparative Example 2 is about 254 ° C., but Example Mg (GD ) -LNCMO has an apparently increased decomposition temperature, its heat dissociation decomposition temperature is increased to about 266 ° C., and the heat dissipation amount is reduced from 227.3 Jg −1 to 115.9 Jg −1 , thus (GD) -LNCMO has been shown to have relatively good thermal stability.
全体的には、本発明の正極材料を利用して製造されたリチウム二次電池は任意の円形及び方形のステンレス、アルミ及びアルミ合金缶外装のリチウム電池を含み得て、また、任意のアルミ箔パウチ熱圧シール方式で包装された高分子リチウム電池及び関係外装設計のリチウム電池に適用され、これにより電池の安全性と電容量をアップできる。 In general, the lithium secondary battery manufactured using the positive electrode material of the present invention can include any circular and square stainless steel, aluminum and aluminum alloy can-covered lithium batteries, and any aluminum foil. It is applied to the lithium battery of the packaged polymer lithium battery and related exterior design pouch heat pressure sealing method, thereby up safety and capacity of the battery.
以上をまとめると、本発明の特徴は、濃度勾配を有するよう金属がドープされた六方晶正極材料を提供し、粉体表面上の比較的高い金属ドープ濃度を利用して材料の電解液に対する反応性を低減し、またコアに向けて連続して漸次低減する金属ドープ濃度により、ドープ金属の総含有量を減らし、高電圧下で材料の高い電容量、使用寿命を共に考慮し、並びに使用上の安全性を改善し、正極材料の高エネルギー化による実用性と産業上の利用性を増し、リチウム電池製作に必要な正極極板への応用に非常に適合する。 In summary, the features of the present invention provide a hexagonal positive electrode material doped with metal to have a concentration gradient, and the reaction of the material to the electrolyte using a relatively high metal doping concentration on the powder surface. reduced sex, and by metal doping concentration of reducing gradually continuously toward the core, reducing the total content of doping metal, high capacity of the material at high voltages, considering both the service life and the use on Therefore, it is very suitable for application to the positive electrode plate necessary for lithium battery fabrication.
以上は本発明の好ましい実施例の説明に過ぎず、並びに本発明を限定するものではなく、本発明に提示の精神より逸脱せずに完成されるその他の同等の効果の修飾或いは置換は、いずれも本発明の権利請求範囲内に属する。 The foregoing is only a description of the preferred embodiment of the present invention, and is not intended to limit the present invention. Other equivalent effect modifications or substitutions that may be accomplished without departing from the spirit of the present invention are not Are also within the scope of the claims of the present invention.
1 リチウムイオン電池の金属勾配ドープ正極材料
A 表面
B コア
C 修飾金属濃度低減方向
1 Lithium-ion battery metal gradient doped cathode material A Surface B Core C Modified metal concentration reduction direction
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |