JP6243600B2 - Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery - Google Patents
Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 56
- 239000007774 positive electrode material Substances 0.000 title claims description 49
- 239000002245 particle Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- 238000010304 firing Methods 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910014211 My O Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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、リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池に関する。 The present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery.
リチウムイオン電池の正極活物質には、一般にリチウム含有遷移金属酸化物が用いられている。具体的には、コバルト酸リチウム（ＬｉＣｏＯ2）、ニッケル酸リチウム（ＬｉＮｉＯ2）、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）等であり、特性改善（高容量化、サイクル特性、保存特性、内部抵抗低減、レート特性）や安全性を高めるためにこれらを複合化することが進められている。車載用やロードレベリング用といった大型用途におけるリチウムイオン電池には、これまでの携帯電話用やパソコン用とは異なった特性が求められている。Lithium-containing transition metal oxides are generally used as positive electrode active materials for lithium ion batteries. Specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), etc., improved characteristics (higher capacity, cycle characteristics, storage characteristics, reduced internal resistance) In order to improve the rate characteristics and safety, it is underway to combine them. Lithium ion batteries for large-scale applications such as in-vehicle use and load leveling are required to have different characteristics from those of conventional mobile phones and personal computers.
電池特性の改善には、従来、種々の方法が用いられており、例えば特許文献１には、
ＬｉxＮｉ1-yＭyＯ2-δ
（０．８≦ｘ≦１．３、０＜ｙ≦０．５であり、Ｍは、Ｃｏ、Ｍｎ、Ｆｅ、Ｃｒ、Ｖ、Ｔｉ、Ｃｕ、Ａｌ、Ｇａ、Ｂｉ、Ｓｎ、Ｚｎ、Ｍｇ、Ｇｅ、Ｎｂ、Ｔａ、Ｂｅ、Ｂ、Ｃａ、Ｓｃ及びＺｒからなる群から選ばれる少なくとも一種の元素を示し、δは酸素欠損又は酸素過剰量に相当し、−０．１＜δ＜０．１を表す。）の組成で表されるリチウムニッケル複合酸化物を分級機に通し、粒子径の大きい物と小さい物とに平衡分離粒子径Ｄｈ＝１〜１０μｍで分離し、粒子径の大きい物と小さい物を、重量比で０：１００〜１００：０で配合することを特徴とするリチウム二次電池用正極材料の製造方法が開示されている。そして、これによれば、レート特性と容量のさまざまなバランスのリチウム二次電池用正極材料を容易に製造できる、と記載されている。Various methods have been conventionally used to improve battery characteristics. For example, Patent Document 1 discloses:
Li x Ni 1- y My O 2- δ
(0.8 ≦ x ≦ 1.3, 0 <y ≦ 0.5, and M is Co, Mn, Fe, Cr, V, Ti, Cu, Al, Ga, Bi, Sn, Zn, Mg, It represents at least one element selected from the group consisting of Ge, Nb, Ta, Be, B, Ca, Sc and Zr, δ corresponds to oxygen deficiency or oxygen excess, and −0.1 <δ <0.1 The lithium nickel composite oxide represented by the composition is passed through a classifier and separated into a large particle size and a small particle size with an equilibrium separation particle size Dh = 1 to 10 μm, and a large particle size A method for producing a positive electrode material for a lithium secondary battery, characterized in that small substances are blended at a weight ratio of 0: 100 to 100: 0. And according to this, it is described that the positive electrode material for lithium secondary batteries with various balance of rate characteristics and capacity can be easily manufactured.
特許文献１に記載のリチウムニッケル複合酸化物は、その組成式中の酸素量が過剰のものであるが、それでもなお高品質のリチウムイオン電池用正極活物質としては改善の余地がある。 Although the lithium nickel composite oxide described in Patent Document 1 has an excessive amount of oxygen in its composition formula, there is still room for improvement as a high-quality positive electrode active material for a lithium ion battery.
そこで、本発明は、良好な電池特性を有するリチウムイオン電池用正極活物質を提供することを課題とする。 Then, this invention makes it a subject to provide the positive electrode active material for lithium ion batteries which has a favorable battery characteristic.
本発明者らは、鋭意検討した結果、正極活物質の酸素量と電池特性との間に密接な相関関係があることを見出した。すなわち、正極活物質の酸素量がある値以上であるとき、特に良好な電池特性が得られることを見出した。また、酸素量がある値以上である正極活物質において、粉体の平均粒径を制御することにより、より良好な電池特性が得られることを見出した。 As a result of intensive studies, the present inventors have found that there is a close correlation between the amount of oxygen of the positive electrode active material and the battery characteristics. That is, it has been found that particularly good battery characteristics can be obtained when the amount of oxygen in the positive electrode active material is greater than or equal to a certain value. Further, it has been found that better battery characteristics can be obtained by controlling the average particle diameter of the powder in the positive electrode active material having an oxygen amount of a certain value or more.
上記知見を基礎にして完成した本発明は一側面において、
組成式：Ｌｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+α
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表され、
平均粒径（Ｄ５０）が５〜１５μｍであり、粒度分布において、Ｄ９０が２０μｍ以下であるリチウムイオン電池用正極活物質である。
ここで、「Ｄ５０」とは、体積基準の積算分率で５０％に相当する粒子径のことをいい、「Ｄ９０」とは、体積基準の積算分率で９０％に相当する粒子径のことをいう。
In one aspect of the present invention completed based on the above knowledge,
Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge 2 , Bi, Sn, Mg, Ca, B and Zr. One or more types, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
Represented by
Average particle size (D50) of Ri is 5~15μm der, in particle size distribution, D90 is positive electrode active material for lithium ion batteries is 20μm or less.
Here, “D50” refers to a particle diameter corresponding to 50% in volume-based cumulative fraction, and “D90” refers to a particle diameter corresponding to 90% in volume-based cumulative fraction. the say.
本発明に係るリチウムイオン電池用正極活物質は一実施形態において、平均粒径（Ｄ５０）が７〜１３μｍである。 In one embodiment, the positive electrode active material for a lithium ion battery according to the present invention has an average particle size (D50) of 7 to 13 μm.
本発明に係るリチウムイオン電池用正極活物質は別の実施形態において、Ｍが、Ｍｎ及びＣｏから選択される１種以上である。 In another embodiment of the positive electrode active material for a lithium ion battery according to the present invention, M is at least one selected from Mn and Co.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、組成式において、α＞０．０５である。 In still another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has α> 0.05 in the composition formula.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、組成式において、α＞０．１である。 In still another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has α> 0.1 in the composition formula.
本発明は、別の側面において、本発明に係るリチウムイオン電池用正極活物質を用いたリチウムイオン電池用正極である。 In another aspect, the present invention is a positive electrode for a lithium ion battery using the positive electrode active material for a lithium ion battery according to the present invention.
本発明は、更に別の側面において、本発明に係るリチウムイオン電池用正極を用いたリチウムイオン電池である。 In still another aspect, the present invention is a lithium ion battery using the positive electrode for a lithium ion battery according to the present invention.
本発明によれば、良好な電池特性を有するリチウムイオン電池用正極活物質を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the positive electrode active material for lithium ion batteries which has a favorable battery characteristic can be provided.
（リチウムイオン電池用正極活物質の構成）
本発明のリチウムイオン電池用正極活物質の材料としては、一般的なリチウムイオン電池用正極用の正極活物質として有用な化合物を広く用いることができるが、特に、コバルト酸リチウム（ＬｉＣｏＯ2）、ニッケル酸リチウム（ＬｉＮｉＯ2）、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）等のリチウム含有遷移金属酸化物を用いるのが好ましい。このような材料を用いて作製される本発明のリチウムイオン電池用正極活物質は、
組成式：Ｌｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+α
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表される。
リチウムイオン電池用正極活物質における全金属に対するリチウムの比率が０．９〜１．２であるが、これは、０．９未満では、安定した結晶構造を保持し難く、１．２超では電池の高容量が確保できなくなるためである。(Configuration of positive electrode active material for lithium ion battery)
As a material of the positive electrode active material for lithium ion batteries of the present invention, compounds useful as a positive electrode active material for general positive electrodes for lithium ion batteries can be widely used. In particular, lithium cobaltate (LiCoO 2 ), It is preferable to use lithium-containing transition metal oxides such as lithium nickelate (LiNiO 2 ) and lithium manganate (LiMn 2 O 4 ). The positive electrode active material for a lithium ion battery of the present invention produced using such a material is
Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. 1 or more selected from the above, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
It is represented by
The ratio of lithium to all metals in the positive electrode active material for a lithium ion battery is 0.9 to 1.2. If the ratio is less than 0.9, it is difficult to maintain a stable crystal structure. This is because the high capacity cannot be secured.
本発明のリチウムイオン電池用正極活物質は、酸素が組成式において上記のようにＯ2+α（α＞０）と示され、過剰に含まれており、リチウムイオン電池に用いた場合、容量、レート特性及び容量保持率等の電池特性が良好となる。また、酸素が過剰に含まれていることにより、製造工程における焼成を十分に行うことができるため、粒子形状や大きさが均一化する。ここで、αについて、好ましくはα＞０．０５であり、より好ましくはα＞０．１である。The positive electrode active material for a lithium ion battery according to the present invention has oxygen as O 2 + α (α> 0) as described above in the composition formula, and is contained excessively. Battery characteristics such as rate characteristics and capacity retention are improved. Moreover, since oxygen is contained excessively, firing in the manufacturing process can be sufficiently performed, so that the particle shape and size are made uniform. Here, α is preferably α> 0.05, and more preferably α> 0.1.
本発明のリチウムイオン電池用正極活物質は、一次粒子、一次粒子が凝集して形成された二次粒子、又は、一次粒子及び二次粒子の混合物で構成されている。これらの一次粒子、一次粒子が凝集して形成された二次粒子、又は、一次粒子及び二次粒子の混合物の平均粒径（Ｄ５０）は５〜１５μｍである。平均粒径（Ｄ５０）が５〜１５μｍであれば、ばらつきが抑制された粉体となり、リチウムイオン電池の電極作製時の活物質の均一な塗布が可能となり、さらに電極組成のばらつきを抑制することができる。このため、リチウムイオン電池に用いたときにレート特性及びサイクル特性が良好となる。平均粒径（Ｄ５０）は、好ましくは７〜１３μｍである。 The positive electrode active material for a lithium ion battery of the present invention is composed of primary particles, secondary particles formed by aggregation of primary particles, or a mixture of primary particles and secondary particles. The average particle diameter (D50) of these primary particles, secondary particles formed by aggregation of primary particles, or a mixture of primary particles and secondary particles is 5 to 15 μm. When the average particle diameter (D50) is 5 to 15 μm, the powder is suppressed in variation, and it is possible to uniformly apply the active material during the production of the electrode of the lithium ion battery, and further suppress variation in the electrode composition. Can do. For this reason, when it uses for a lithium ion battery, a rate characteristic and cycling characteristics become favorable. The average particle diameter (D50) is preferably 7 to 13 μm.
本発明のリチウムイオン電池用正極活物質は、粒度分布において、Ｄ９０が２０μｍ以下である。Ｄ９０が２０μｍ以下であれば、粒子間の反応のバラツキが小さくなりよりレート特性やサイクル特性が向上する効果を奏する。Ｄ９０は１３〜２０μｍであるのが好ましい。 The positive electrode active material for a lithium ion battery of the present invention has a D90 of 20 μm or less in the particle size distribution. If D90 is 20 μm or less, the variation in reaction between particles is reduced, and the effect of improving the rate characteristics and cycle characteristics is achieved. D90 is preferably 13 to 20 μm.
（リチウムイオン電池用正極及びそれを用いたリチウムイオン電池の構成）
本発明の実施形態に係るリチウムイオン電池用正極は、例えば、上述の構成のリチウムイオン電池用正極活物質と、導電助剤と、バインダーとを混合して調製した正極合剤をアルミニウム箔等からなる集電体の片面または両面に設けた構造を有している。また、本発明の実施形態に係るリチウムイオン電池は、このような構成のリチウムイオン電池用正極を備えている。(Configuration of positive electrode for lithium ion battery and lithium ion battery using the same)
The positive electrode for a lithium ion battery according to an embodiment of the present invention includes, for example, a positive electrode mixture prepared by mixing a positive electrode active material for a lithium ion battery having the above-described configuration, a conductive additive, and a binder from an aluminum foil or the like. The current collector has a structure provided on one side or both sides. Moreover, the lithium ion battery which concerns on embodiment of this invention is equipped with the positive electrode for lithium ion batteries of such a structure.
（リチウムイオン電池用正極活物質の製造方法）
次に、本発明の実施形態に係るリチウムイオン電池用正極活物質の製造方法について詳細に説明する。
まず、金属塩溶液を作製する。当該金属は、Ｎｉ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上である。また、金属塩は硫酸塩、塩化物、硝酸塩、酢酸塩等であり、特に硝酸塩が好ましい。これは、焼成原料中に不純物として混入してもそのまま焼成できるため洗浄工程が省けることと、硝酸塩が酸化剤として機能し、焼成原料中の金属の酸化を促進する働きがあるためである。金属塩に含まれる各金属を所望のモル比率となるように調整しておく。これにより、正極活物質中の各金属のモル比率が決定する。(Method for producing positive electrode active material for lithium ion battery)
Next, the manufacturing method of the positive electrode active material for lithium ion batteries which concerns on embodiment of this invention is demonstrated in detail.
First, a metal salt solution is prepared. The metal is at least one selected from Ni and Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. It is. The metal salt is sulfate, chloride, nitrate, acetate, etc., and nitrate is particularly preferable. This is because even if it is mixed as an impurity in the firing raw material, it can be fired as it is, so that the washing step can be omitted, and nitrate functions as an oxidant, and promotes the oxidation of the metal in the firing raw material. Each metal contained in the metal salt is adjusted so as to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined.
次に、炭酸リチウムを純水に懸濁させ、その後、上記金属の金属塩溶液を投入して金属炭酸塩溶液スラリーを作製する。このとき、スラリー中に微小粒のリチウム含有炭酸塩が析出する。なお、金属塩として硫酸塩や塩化物等熱処理時にそのリチウム化合物が反応しない場合は飽和炭酸リチウム溶液で洗浄した後、濾別する。硝酸塩や酢酸塩のように、そのリチウム化合物が熱処理中にリチウム原料として反応する場合は洗浄せず、そのまま濾別し、乾燥することにより焼成前駆体として用いることができる。
次に、濾別したリチウム含有炭酸塩を乾燥することにより、リチウム塩の複合体（リチウムイオン電池正極材用前駆体）の粉末を得る。Next, lithium carbonate is suspended in pure water, and then the metal salt solution of the metal is added to prepare a metal carbonate solution slurry. At this time, fine particles of lithium-containing carbonate precipitate in the slurry. If the lithium compound does not react during heat treatment such as sulfate or chloride as a metal salt, it is washed with a saturated lithium carbonate solution and then filtered off. When the lithium compound reacts as a lithium raw material during the heat treatment, such as nitrate or acetate, it can be used as a calcined precursor by washing and drying as it is without washing.
Next, the lithium-containing carbonate separated by filtration is dried to obtain a lithium salt composite (precursor for lithium ion battery positive electrode material) powder.
次に、乾燥して得られたリチウムイオン電池正極材用前駆体の粉末を、篩、又は、市販の分級装置等を用いて分級し、１〜３０μｍの粒径の粉末のみを得る。 Next, the powder of the precursor for a lithium ion battery positive electrode material obtained by drying is classified using a sieve, a commercially available classifier, or the like to obtain only a powder having a particle diameter of 1 to 30 μm.
次に、所定の大きさの容量を有する焼成容器を準備し、この焼成容器に分級した１〜３０μｍの粒径のリチウムイオン電池正極材用前駆体の粉末を充填する。次に、リチウムイオン電池正極材用前駆体の粉末が充填された焼成容器を、焼成炉へ移設し、焼成を行う。焼成は、酸素雰囲気下で所定時間加熱保持することにより行う。また、１０１〜２０２ＫＰａでの加圧下で焼成を行うと、さらに組成中の酸素量が増加するため、好ましい。
その後、焼成容器から粉末を取り出し、市販の粉砕装置等を用いて解砕を行うことにより正極活物質の粉体を得る。このときの解砕は、所望の平均粒径が得られるように、適宜粉砕強度及び粉砕時間を調整して行う。Next, a firing container having a capacity of a predetermined size is prepared, and the powder of a precursor for a lithium ion battery positive electrode material having a particle diameter of 1 to 30 μm is filled in the firing container. Next, the firing container filled with the precursor powder for the lithium ion battery positive electrode material is transferred to a firing furnace and fired. Firing is performed by heating and holding in an oxygen atmosphere for a predetermined time. Further, it is preferable to perform baking under pressure of 101 to 202 KPa because the amount of oxygen in the composition further increases.
Thereafter, the powder is taken out from the firing container and pulverized using a commercially available pulverizer or the like to obtain a positive electrode active material powder. The crushing at this time is performed by appropriately adjusting the crushing strength and the crushing time so that a desired average particle diameter can be obtained.
以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。 Examples for better understanding of the present invention and its advantages are provided below, but the present invention is not limited to these examples.
（実施例１〜３、参考例４、実施例５〜８、参考例９、実施例１０〜１４、参考例１５）
まず、表１に記載の投入量の炭酸リチウムを純水３．２リットルに懸濁させた後、金属塩溶液を４．８リットル投入した。ここで、金属塩溶液は、各金属の硝酸塩の水和物を、各金属が表１に記載の組成比になるように調整し、また全金属モル数が１４モルになるように調整した。
なお、炭酸リチウムの懸濁量は、製品（リチウムイオン二次電池正極材料、すなわち正極活物質）をＬｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+αでｘが表１の値となる量であって、それぞれ次式で算出されたものである。
Ｗ（ｇ）＝７３．９×１４×（１＋０．５{（１＋Ｘ）/（１−Ｘ）}×Ａ
上記式において、「Ａ」は、析出反応として必要な量の他に、ろ過後の原料に残留する炭酸リチウム以外のリチウム化合物によるリチウムの量をあらかじめ懸濁量から引いておくために掛ける数値である。「Ａ」は、硝酸塩や酢酸塩のように、リチウム塩が焼成原料として反応する場合は０．９であり、硫酸塩や塩化物のように、リチウム塩が焼成原料として反応しない場合は１．０である。
この処理により溶液中に微小粒のリチウム含有炭酸塩が析出したが、この析出物を、フィルタープレスを使用して濾別した。
続いて、析出物を乾燥してリチウム含有炭酸塩（リチウムイオン電池正極材用前駆体）を得た。
次に、乾燥して得たリチウム含有炭酸塩を篩にかけて、１〜３０μｍの粒径のものに分級した。
次に、焼成容器を準備し、この焼成容器内にリチウム含有炭酸塩を充填した。次に、焼成容器を、大気圧下、酸素雰囲気炉に入れて、表１に記載の焼成温度で１０時間加熱保持した後冷却して酸化物を得た。
次に、得られた酸化物を小型粉砕機（ホソカワミクロンＡＣＭ-2ＥＣ）を用いて平均粒径５〜１５μｍに解砕し、リチウムイオン二次電池正極材の粉末を得た。
(Examples 1 to 3, Reference Example 4, Examples 5 to 8, Reference Example 9, Examples 10 to 14, Reference Example 15)
First, after suspending lithium carbonate of the input amount shown in Table 1 in 3.2 liters of pure water, 4.8 liter of metal salt solution was charged. Here, the nitrate hydrate of each metal was adjusted so that each metal might become the composition ratio of Table 1, and the total metal mole number might be set to 14 mol.
Incidentally, a suspension of lithium carbonate, the product (lithium ion secondary battery positive electrode material, i.e. a cathode active material) x with Li (Li x Ni 1-xy M y) O 2 + α becomes a value shown in Table 1 Each of which is calculated by the following equation.
W (g) = 73.9 × 14 × (1 + 0.5 {(1 + X) / (1-X)} × A
In the above formula, “A” is a numerical value to be multiplied in order to subtract the amount of lithium from the lithium compound other than lithium carbonate remaining in the raw material after filtration from the amount of suspension in addition to the amount necessary for the precipitation reaction. is there. “A” is 0.9 when lithium salt reacts as a firing raw material such as nitrate or acetate, and “1” when lithium salt does not react as a firing raw material such as sulfate or chloride. 0.
By this treatment, fine particles of lithium-containing carbonate were precipitated in the solution, and this precipitate was filtered off using a filter press.
Subsequently, the precipitate was dried to obtain a lithium-containing carbonate (a precursor for a lithium ion battery positive electrode material).
Next, the lithium-containing carbonate obtained by drying was sieved and classified into particles having a particle size of 1 to 30 μm.
Next, a firing container was prepared, and this firing container was filled with a lithium-containing carbonate. Next, the firing container was placed in an oxygen atmosphere furnace under atmospheric pressure, heated and held at the firing temperature shown in Table 1 for 10 hours, and then cooled to obtain an oxide.
Next, the obtained oxide was pulverized to a mean particle size of 5 to 15 μm using a small pulverizer (Hosokawa Micron ACM-2EC) to obtain a powder of a lithium ion secondary battery positive electrode material.
（実施例１６）
実施例１６として、原料の各金属を表１に示すような組成とし、金属塩を塩化物とし、リチウム含有炭酸塩を析出させた後、飽和炭酸リチウム溶液で洗浄し、濾過する以外は、実施例１〜３、参考例４、実施例５〜８、参考例９、実施例１０〜１４、参考例１５と同様の処理を行った。
(Example 16)
Example 16 was carried out except that each raw material had a composition as shown in Table 1, the metal salt was chloride, lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 3, Reference Example 4, Examples 5 to 8, Reference Example 9, Examples 10 to 14, and Reference Example 15 was performed.
（参考例１７）
参考例１７として、原料の各金属を表１に示すような組成とし、金属塩を硫酸塩とし、リチウム含有炭酸塩を析出させた後、飽和炭酸リチウム溶液で洗浄し、濾過する以外は、実施例１〜３、参考例４、実施例５〜８、参考例９、実施例１０〜１４、参考例１５と同様の処理を行った。
( Reference Example 17)
As Reference Example 17, each metal of the raw material had a composition as shown in Table 1, the metal salt was sulfate, lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 3, Reference Example 4, Examples 5 to 8, Reference Example 9, Examples 10 to 14, and Reference Example 15 was performed.
（実施例１８）
実施例１８として、原料の各金属を表１に示すような組成とし、焼成を大気圧下ではなく１２０ＫＰａの加圧下で行った以外は、実施例１〜３、参考例４、実施例５〜８、参考例９、実施例１０〜１４、参考例１５と同様の処理を行った。
(Example 18)
As Example 18, each metal of the raw material had a composition shown in Table 1, and Examples 1 to 3, Reference Example 4, and Example 5 were used except that firing was performed under a pressure of 120 KPa instead of atmospheric pressure. 8. The same treatment as in Reference Example 9, Examples 10 to 14, and Reference Example 15 was performed.
（比較例１〜３）
比較例１〜３として、原料の各金属を表１に示すような組成とし、前駆体乾燥後の分級を行わず、且つ、最後の酸化物の解砕を平均粒径が５μｍ以下もしくは２０μｍ以上になるように行った点以外は、実施例１〜３、参考例４、実施例５〜８、参考例９、実施例１０〜１４、参考例１５と同様の処理を行った。
(Comparative Examples 1-3)
As Comparative Examples 1 to 3, the raw materials have the compositions shown in Table 1, the classification after drying the precursor is not performed, and the final oxide is crushed by an average particle size of 5 μm or less or 20 μm or more The same treatment as in Examples 1 to 3, Reference Example 4, Examples 5 to 8, Reference Example 9, Examples 10 to 14, and Reference Example 15 was performed, except that the process was performed.
（比較例４〜７）
比較例４〜７として、原料の各金属を表１に示すような組成とし、酸素雰囲気炉ではなく空気雰囲気炉で焼成工程を行った点以外は、比較例１と同様の処理を行った。(Comparative Examples 4-7)
As Comparative Examples 4 to 7, the same processing as in Comparative Example 1 was performed, except that each metal of the raw material had a composition as shown in Table 1 and the firing step was performed in an air atmosphere furnace instead of an oxygen atmosphere furnace.
（評価）
−正極材組成の評価−
各正極材中の金属含有量は、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）で測定し、各金属の組成比（モル比）を算出し、表１の通りとなったことを確認した。また、酸素含有量はＬＥＣＯ法で測定しαを算出した。(Evaluation)
-Evaluation of composition of positive electrode material-
The metal content in each positive electrode material was measured with an inductively coupled plasma optical emission spectrometer (ICP-OES), and the composition ratio (molar ratio) of each metal was calculated to confirm that it was as shown in Table 1. . The oxygen content was measured by the LECO method and α was calculated.
−平均粒径（Ｄ５０）及びＤ９０の評価−
各正極材の粉末を採取し、Ｄ５０及びＤ９０をレーザー回折型粒度分布測定装置（島津製作所 ＳＡＬＤ−３０００）によって測定した。-Evaluation of average particle diameter (D50) and D90-
The powder of each positive electrode material was extract | collected and D50 and D90 were measured with the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation SALD-3000).
−電池特性の評価−
各正極材と、導電材と、バインダーとを８５：８：７の割合で秤量し、バインダーを有機溶媒（Ｎ−メチルピロリドン）に溶解したものに、正極材料と導電材とを混合してスラリー化し、Ａｌ箔上に塗布して乾燥後にプレスして正極とした。続いて、対極をＬｉとした評価用の２０３２型コインセルを作製し、電解液に１Ｍ−ＬｉＰＦ6をＥＣ−ＤＭＣ（１：１）に溶解したものを用いて、電流密度０．２Ｃの際の放電容量を測定した。また電流密度０．２Ｃのときの電池容量に対する電流密度２Ｃのときの、放電容量の比を算出してレート特性を得た。さらに、容量保持率は、室温で１Ｃの放電電流で得られた初期放電容量と１００サイクル後の放電容量を比較することによって測定した。
これらの結果を表１に示す。-Evaluation of battery characteristics-
Each positive electrode material, conductive material, and binder are weighed in a ratio of 85: 8: 7, and the positive electrode material and the conductive material are mixed into a slurry in which the binder is dissolved in an organic solvent (N-methylpyrrolidone). And coated on an Al foil, dried and pressed to obtain a positive electrode. Subsequently, a 2032 type coin cell for evaluation with Li as the counter electrode was prepared, and 1M-LiPF 6 dissolved in EC-DMC (1: 1) was used as the electrolyte, and the current density was 0.2C. The discharge capacity was measured. Further, a rate characteristic was obtained by calculating a ratio of the discharge capacity when the current density was 2C to the battery capacity when the current density was 0.2C. Furthermore, the capacity retention was measured by comparing the initial discharge capacity obtained with a 1 C discharge current at room temperature with the discharge capacity after 100 cycles.
These results are shown in Table 1.
Claims (9)
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表され、
平均粒径（Ｄ５０）が５〜１５μｍであり、粒度分布において、Ｄ９０が１８．５μｍ以下であるリチウムイオン電池用正極活物質。 Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B, and Zr. 1 or more types, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
Represented by
A positive electrode active material for a lithium ion battery having an average particle size (D50) of 5 to 15 μm and a particle size distribution of D90 of 18.5 μm or less.
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B, and Zr. 1 or more types, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
で表され、Represented by
平均粒径（Ｄ５０）が５〜１２μｍであり、粒度分布において、Ｄ９０が２０μｍ以下であるリチウムイオン電池用正極活物質。A positive electrode active material for a lithium ion battery having an average particle size (D50) of 5 to 12 μm and a particle size distribution of D90 of 20 μm or less.
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| PCT/JP2011/066718 WO2012073548A1 (en) | 2010-12-03 | 2011-07-22 | Positive electrode active material for lithium-ion battery, a positive electrode for lithium-ion battery, and lithium-ion battery |
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| JP2012546712A Active JP6243600B2 (en) | 2010-12-03 | 2011-07-22 | Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery |
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| JP2006054159A (en) * | 2004-07-15 | 2006-02-23 | Sumitomo Metal Mining Co Ltd | Anode active material for non-aqueous secondary battery, and its manufacturing method |
| JP2006127955A (en) * | 2004-10-29 | 2006-05-18 | Sumitomo Metal Mining Co Ltd | Positive electrode active substance for nonaqueous secondary cell and its manufacturing method |
| CN101151748B (en) * | 2005-02-08 | 2010-10-06 | 三菱化学株式会社 | Lithium secondary battery and its anode material |
| JP2007257890A (en) * | 2006-03-20 | 2007-10-04 | Nissan Motor Co Ltd | Positive electrode material for nonaqueous lithium ion battery and battery using this |
| WO2007142275A1 (en) * | 2006-06-09 | 2007-12-13 | Agc Seimi Chemical Co., Ltd. | Positive electrode active material for rechargeable battery with nonaqueous electrolyte, and method for manufacturing the same |
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| TWI453984B (en) | 2014-09-21 |
| JPWO2012073548A1 (en) | 2014-05-19 |
| WO2012073548A1 (en) | 2012-06-07 |
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