JP2016051503A - Positive electrode substance for lithium ion battery, and method for manufacturing the same - Google Patents
Positive electrode substance for lithium ion battery, and method for manufacturing the same Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 13
- 239000000126 substance Substances 0.000 title claims 2
- 239000007774 positive electrode material Substances 0.000 claims abstract description 82
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- -1 nickel lithium metal complex Chemical class 0.000 claims abstract description 5
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 56
- 239000002905 metal composite material Substances 0.000 claims description 56
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 24
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010304 firing Methods 0.000 description 9
- 238000010248 power generation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明はリチウムイオン電池用正極物質、該活物質を用いたリチウムイオン電池正極、この正極を有するリチウムイオン電池、及び上記リチウムイオン電池用正極物質の製造方法に関する。 The present invention relates to a positive electrode material for a lithium ion battery, a lithium ion battery positive electrode using the active material, a lithium ion battery having the positive electrode, and a method for producing the positive electrode material for the lithium ion battery.
スマートフォン、タブレット型パソコン等の小型電子機器の普及により、ユーザーが屋外で長時間これら小型電子機器を携帯し利用することは、もはや一般的になっている。そのため、これら小型電子機器の電源である電池には長時間の使用に耐える高容量の電池であることが求められており、そのような要求を満たすリチウムイオン二次電池が盛んに研究開発されている。同時に、スマートフォン、タブレット型パソコン等の小型電子機器の更なる高機能化、高性能化が図られており、そのような高機能・高性能小型電子機器では消費電力の増大が避けられない。したがって、電池の高容量化への要求がますます高まっている。 With the spread of small electronic devices such as smartphones and tablet computers, it is no longer common for users to carry and use these small electronic devices outdoors for a long time. For this reason, batteries that are the power sources of these small electronic devices are required to have a high capacity that can withstand long-term use, and lithium-ion secondary batteries that satisfy such requirements have been actively researched and developed. Yes. At the same time, small electronic devices such as smartphones and tablet computers are being further enhanced in function and performance, and such high-performance and high-performance small electronic devices cannot avoid increasing power consumption. Therefore, there is an increasing demand for higher battery capacity.
また、近年は、エネルギー受給に対する危機意識や環境志向の高まりよって、風力発電、メガソーラー発電、家庭用太陽光発電といった、従来型の集中型発電所とは異なる独立分散型発電設備の設置が増えている。しかしながら、風力発電、太陽光発電等の自然エネルギーを利用した発電設備が従来の発電施設に比べて電気供給の安定性に劣るという問題は、未だ解決されていない。２０１１年３月１１日に発生した東日本大震災、その後に引き起こされた原子力発電所停止にかかる給電状況の悪化以来、地震等の災害発生時における事業所や家庭単位での電力確保の重要性が、広く認識されるようになってきた。このため、消費地点単位で電源確保を確保する定置用蓄電池に注目が集まっている。しかしながら、現在の技術によれば、このような定置用蓄電池によって電気容量を確保するためには非常に大きな蓄電設備が必要とされる。このため、日本の住宅環境においてはそのような蓄電設備は、現時点では実用性を欠く。 Also, in recent years, with the growing awareness of energy crisis and environmental awareness, there has been an increase in the installation of independent decentralized power generation facilities such as wind power generation, mega solar power generation, and home solar power generation, which are different from conventional centralized power plants. ing. However, the problem that power generation facilities using natural energy such as wind power generation and solar power generation are inferior to the stability of electricity supply as compared with conventional power generation facilities has not yet been solved. Since the Great East Japan Earthquake that occurred on March 11, 2011, and the worsening of the power supply situation related to the nuclear power plant shutdown that was caused after that, the importance of securing power at business sites and households at the time of disasters such as earthquakes, It has become widely recognized. For this reason, attention has been focused on stationary storage batteries that ensure the supply of power on a consumption point basis. However, according to the current technology, a very large power storage facility is required to secure electric capacity with such a stationary storage battery. For this reason, in the Japanese residential environment, such power storage equipment lacks utility at present.
更に自動車産業においては、エネルギー効率のよい電気自動車、ハイブリッド自動車に注目が集まり、これらの自動車の開発が盛んに行われている。しかしながら、電池容量の不足による航続距離の不十分さ、加えて市中における充電設備の絶対的不足という問題は解決されていない。そのため、現時点では、電気エネルギーだけで動く電気自動車は、ハイブリッド自動車ほどには普及していない。電池容量の向上は、これら新型自動車の実用性を左右する課題である。 Further, in the automobile industry, attention is focused on energy efficient electric vehicles and hybrid vehicles, and development of these vehicles is actively performed. However, the problem of insufficient cruising distance due to insufficient battery capacity and the absolute shortage of charging facilities in the city has not been solved. Therefore, at present, electric vehicles that run only on electric energy are not as popular as hybrid vehicles. Improvement of battery capacity is an issue that affects the practicality of these new models.
上述のような、電子機器、電力確保、自動車などの産業を支える共通の製品の一つがリチウムイオン電池である。上述のような問題点に共通する原因が、リチウムイオン電池の体積当たりの容量が足りないことにある。リチウムイオン電池の体積当たりの容量が足りないという問題を引き起こす大きな要因は、リチウムイオン二次電池に用いられる正極活物質の単位体積当たりの放電容量が小さいことである。 One of the common products that support industries such as electronic devices, power securing, and automobiles as described above is a lithium ion battery. A common cause of the above problems is that the capacity per volume of the lithium ion battery is insufficient. A major factor causing the problem that the capacity per volume of the lithium ion battery is insufficient is that the discharge capacity per unit volume of the positive electrode active material used in the lithium ion secondary battery is small.
その一方で、リチウムイオン電池の用途拡大に伴って、リチウムイオン電池には、過酷な環境下でも電池特性が維持されること、安全性が高く長期使用に耐えることが求められている。このため、リチウムイオン電池用正極活物質には、充放電を繰り返しても充放電特性が低下しないこと、例え酸素や水分に接したとしてもその表面が酸化されにくいこと、充放電に伴う発熱量が小さいことなどが求められている。 On the other hand, along with the expansion of the use of lithium ion batteries, lithium ion batteries are required to maintain battery characteristics even in harsh environments and to have high safety and endure long-term use. For this reason, the positive electrode active material for lithium ion batteries does not deteriorate the charge / discharge characteristics even after repeated charge / discharge, the surface is not easily oxidized even if it comes into contact with oxygen or moisture, and the calorific value associated with charge / discharge Is required to be small.
リチウムイオン電池用正極活物質としては、ＬＣＯ型正極活物質（Ｌｉ、Ｃｏの複合酸化物）が挙げられるが、放電容量が低く、改質が必要とされる。これに対して、ＬＮＣＯ型正極活物質（Ｌｉ、Ｎｉ、Ｃｏの複合酸化物）、特にＬＮＣＡＯ正極活物質（Ｌｉ、Ｎｉ、Ｃｏ、Ａｌの複合酸化物）は、ＬＣＯ型正極活物質に比べて安価で放電容量が高いことが利点とされる。 Examples of the positive electrode active material for a lithium ion battery include an LCO positive electrode active material (a composite oxide of Li and Co). However, the discharge capacity is low and modification is required. On the other hand, the LNCO type positive electrode active material (Li, Ni, Co composite oxide), in particular, the LNCAO positive electrode active material (Li, Ni, Co, Al composite oxide) is compared with the LCO type positive electrode active material. The advantage is that it is inexpensive and has a high discharge capacity.
正極活物質の耐久性や安全性を高めるために、正極活物質粒子の表面改質が従来から行われてきた。例えば、特許文献１、２には、ＬＮＣＯ型正極活物質の表面を様々な金属酸化物で被覆することが記載されている。しかし、これらの表面改質された正極活物質が、良好な充放電特性と耐久性、安全性を兼ね備えるものであることは確認できていない。ＬＮＣＯ型、特にＬＮＣＡＯ型正極活物質を様々な特性で改質できる表面改質剤は、未だ見出されていない。 In order to improve the durability and safety of the positive electrode active material, surface modification of the positive electrode active material particles has been conventionally performed. For example, Patent Documents 1 and 2 describe that the surface of an LNCO-type positive electrode active material is coated with various metal oxides. However, it has not been confirmed that these surface-modified positive electrode active materials have good charge / discharge characteristics, durability, and safety. No surface modifier has yet been found that can modify LNCO type, particularly LNCAO type positive electrode active materials with various properties.
そこで本発明は、電気特性だけでなく、安全性、耐久性などの様々な要求をバランスよく達成できるＬＮＣＯ型正極活物質の表面改質剤を探索した。 Therefore, the present invention searched for a surface modifier for an LNCO-type positive electrode active material that can achieve not only electrical characteristics but also various requirements such as safety and durability in a balanced manner.
その結果、そのような表面改質剤として硝酸コバルトを新たに見出した。 As a result, cobalt nitrate was newly found as such a surface modifier.
すなわち本発明は以下のものである。
（発明１）以下の一般式（１）で表されるニッケルリチウム金属複合酸化物の表面にコバルト化合物が被覆されたものである、リチウムイオン電池用正極活物質。
That is, the present invention is as follows.
(Invention 1) A positive electrode active material for a lithium ion battery, wherein the surface of a nickel lithium metal composite oxide represented by the following general formula (1) is coated with a cobalt compound.
（ただし式（１）中、Ｍは、Ｃｏ，Ｍｎ，Ｆｅ、Ｃｕから選ばれる１つ以上の金属元素であり、ＮはＡｌ、Ｗ、Ｔａ、Ｂから選ばれる１つ以上の金属元素であり、０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。）
（発明２）一般式（１）におけるＭがＣｏである、発明１のリチウムイオン電池用正極活物質。
(In the formula (1), M is one or more metal elements selected from Co, Mn, Fe, and Cu, and N is one or more metal elements selected from Al, W, Ta, and B) 0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10.)
(Invention 2) The positive electrode active material for a lithium ion battery according to Invention 1, wherein M in the general formula (1) is Co.
（発明３）一般式（１）におけるＮがＡｌであることを特徴とする、発明１または２のいずれかに記載のリチウムイオン電池用正極活物質。 (Invention 3) The positive electrode active material for a lithium ion battery according to any one of Invention 1 or 2, characterized in that N in the general formula (1) is Al.
（発明４）一般式（１）におけるＭがＣｏであり、かつ、ＮがＡｌであることを特徴とする、発明１〜３のいずれかに記載のリチウムイオン電池用正極活物質。 (Invention 4) The positive electrode active material for a lithium ion battery according to any one of Inventions 1 to 3, wherein M in the general formula (1) is Co and N is Al.
（発明５）ニッケルリチウム金属複合酸化物に対して０．１〜１０．０モル％のコバルト化合物で表面が被覆されていることを特徴とする、発明１〜４のいずれかに記載のリチウムイオン電池用正極活物質。 (Invention 5) The lithium ion according to any one of Inventions 1 to 4, wherein the surface is coated with 0.1 to 10.0 mol% of a cobalt compound with respect to the nickel lithium metal composite oxide. Positive electrode active material for batteries.
（発明６）コバルト化合物が硝酸コバルト由来であることを特徴とする、発明１〜５のいずれかに記載のリチウムイオン電池用正極活物質。 (Invention 6) The positive electrode active material for a lithium ion battery according to any one of Inventions 1 to 5, wherein the cobalt compound is derived from cobalt nitrate.
（発明７）発明１〜６のいずれかに記載のリチウムイオン電池用正極活物質を用いることを特徴とする、リチウムイオン電池用正極。 (Invention 7) A positive electrode for a lithium ion battery, characterized by using the positive electrode active material for a lithium ion battery according to any one of Inventions 1 to 6.
（発明８）発明７に記載のリチウムイオン電池用正極を備えることを特徴とする、リチリウムイオン電池。 (Invention 8) A lithium ion battery comprising the positive electrode for a lithium ion battery according to Invention 7.
（発明９）以下の一般式（１）で表されるニッケルリチウム金属複合酸化物の表面にコバルト化合物を被覆する工程を含む、リチウムイオン電池用正極活物質の製造方法。 (Invention 9) A method for producing a positive electrode active material for a lithium ion battery, comprising a step of coating a cobalt compound on the surface of a nickel lithium metal composite oxide represented by the following general formula (1).
（ただし式（１）中、Ｍは、Ｃｏ，Ｍｎ，Ｆｅ、Ｃｕから選ばれる１つ以上の金属元素であり、ＮはＡｌ、Ｗ、Ｔａ、Ｂから選ばれる１つ以上の金属元素であり、０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。）
（発明１０）一般式（１）におけるＭがＣｏであることを特徴とする、発明９に記載のリチウムイオン電池用正極活物質の製造方法。
(In the formula (1), M is one or more metal elements selected from Co, Mn, Fe, and Cu, and N is one or more metal elements selected from Al, W, Ta, and B) 0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10.)
(Invention 10) The method for producing a positive electrode active material for a lithium ion battery according to Invention 9, wherein M in the general formula (1) is Co.
（発明１１）一般式（１）におけるＮがＡｌであることを特徴とする、発明９または１０に記載のリチウムイオン電池用正極活物質の製造方法。 (Invention 11) The method for producing a positive electrode active material for a lithium ion battery according to Invention 9 or 10, wherein N in the general formula (1) is Al.
（発明１２）一般式（１）における一般式（１）におけるＭがＣｏであり、かつ、ＮがＡｌであることを特徴とする、発明９〜１１のいずれかに記載のリチウムイオン電池用正極活物質の製造方法。 (Invention 12) The positive electrode for a lithium ion battery according to any one of Inventions 9 to 11, wherein M in the general formula (1) in the general formula (1) is Co and N is Al. A method for producing an active material.
（発明１３）ニッケルリチウム金属複合酸化物に対して０．１〜１０．０モル％のコバルト化合物で表面を被覆することを特徴とする、発明９〜１２のいずれかに記載のリチウムイオン電池用正極活物質の製造方法。 (Invention 13) The lithium ion battery according to any one of Inventions 9 to 12, wherein the surface is coated with 0.1 to 10.0 mol% of a cobalt compound with respect to the nickel lithium metal composite oxide. A method for producing a positive electrode active material.
（発明１４）ニッケルリチウム金属複合酸化物の表面にコバルト化合物を被覆する工程において、硝酸コバルトとニッケルリチウム金属複合酸化物とを接触させることを特徴とする、発明９〜１３のいずれかに記載のリチウムイオン電池用正極活物質の製造方法。 (Invention 14) In the process of coating the surface of the nickel lithium metal composite oxide with a cobalt compound, cobalt nitrate and nickel lithium metal composite oxide are brought into contact with each other. A method for producing a positive electrode active material for a lithium ion battery.
（発明１５）ニッケルリチウム金属複合酸化物の表面にコバルト化合物を被覆する工程において、硝酸コバルトのエタノール溶液にニッケルリチウム金属複合酸化物を混合し、得られた混合物を乾燥、次いで焼成することを特徴とする、発明９〜１４のいずれかに記載のリチウムイオン電池用正極活物質の製造方法。 (Invention 15) In the step of coating the surface of the nickel lithium metal composite oxide with a cobalt compound, the nickel lithium metal composite oxide is mixed with an ethanol solution of cobalt nitrate, and the resulting mixture is dried and then fired. The manufacturing method of the positive electrode active material for lithium ion batteries in any one of invention 9-14.
本発明のリチウムイオン電池用正極活物質は、水分や炭酸ガスによる性能劣化が起こりにくく、高い充放電効率を示し、発熱量が低減できる。 The positive electrode active material for a lithium ion battery of the present invention is less susceptible to performance deterioration due to moisture and carbon dioxide gas, exhibits high charge / discharge efficiency, and can reduce the amount of heat generated.
本発明のリチウムイオン電池用正極活物質を構成するニッケルリチウム金属複合酸化物は、以下の一般式（１）で表される化合物である。 The nickel lithium metal composite oxide constituting the positive electrode active material for a lithium ion battery of the present invention is a compound represented by the following general formula (1).
（ただし式（１）中、Ｍは、Ｃｏ，Ｍｎ，Ｆｅ、Ｃｕから選ばれる１つ以上の金属元素であり、ＮはＡｌ、Ｗ、Ｔａ、Ｂから選ばれる１つ以上の金属元素であり、０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。）
本発明のリチウムイオン電池用正極活物質を構成するニッケルリチウム金属複合酸化物は、好ましくは、上記一般式（１）においてMがCo、NがAlである、以下の一般式（２）で表される化合物である。（ただし式（２）中、０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。）
(In the formula (1), M is one or more metal elements selected from Co, Mn, Fe, and Cu, and N is one or more metal elements selected from Al, W, Ta, and B) 0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10.)
The nickel lithium metal composite oxide constituting the positive electrode active material for a lithium ion battery of the present invention is preferably represented by the following general formula (2), wherein M is Co and N is Al in the general formula (1). It is a compound. (In the formula (2), 0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10.)
上記ニッケルリチウム金属複合酸化物は、以下の方法により製造することができる。 The nickel lithium metal composite oxide can be produced by the following method.
（１．原料の溶解）原料としては、一般式（１）を構成する金属の、硫酸塩、硝酸塩などの可溶性金属塩を用いることができる。硝酸塩を用いた場合、硝酸性窒素を含む廃液処理にコストがかかるため、硝酸塩の使用は工業的には好ましくない。通常は一般式（１）を構成する金属の硫酸塩が用いられる。本発明の低アルカリ性ＬＮＣＡＯ系正極活物質の製造方法では、まず、原料である硫酸ニッケル、硫酸コバルトのそれぞれを水に溶解する。 (1. Dissolution of raw materials) As raw materials, soluble metal salts such as sulfates and nitrates of metals constituting the general formula (1) can be used. When nitrate is used, it is costly to treat waste liquid containing nitrate nitrogen, so use of nitrate is not industrially preferable. Usually, a metal sulfate constituting the general formula (1) is used. In the method for producing a low alkaline LNCAO positive electrode active material of the present invention, first, each of nickel sulfate and cobalt sulfate as raw materials is dissolved in water.
（２．沈殿）硫酸ニッケル水溶液、硫酸コバルト水溶液、沈殿剤としての水酸化ナトリウムとアンモニア水を沈殿槽内で混合する。水酸化ニッケルと水酸化コバルトの共沈殿物が生成する。 (2. Precipitation) A nickel sulfate aqueous solution, a cobalt sulfate aqueous solution, sodium hydroxide as a precipitating agent and aqueous ammonia are mixed in a precipitation tank. A coprecipitate of nickel hydroxide and cobalt hydroxide is formed.
（３．濾過・洗浄）沈殿物を濾過し、水分を除去して水酸化物ケーキを分離する。水酸化物ケーキを水酸化ナトリウム水溶液で洗浄し、硫酸イオンを除去する。さらに水酸化物ケーキを純粋で洗浄して水酸化ナトリウムを除去する。こうして水酸化ニッケルと水酸化コバルトからなる前駆体ケーキが得られる。 (3. Filtration / Washing) The precipitate is filtered to remove moisture and separate the hydroxide cake. The hydroxide cake is washed with an aqueous sodium hydroxide solution to remove sulfate ions. Further, the hydroxide cake is washed with pure to remove sodium hydroxide. Thus, a precursor cake composed of nickel hydroxide and cobalt hydroxide is obtained.
（４．乾燥）前駆体ケーキを乾燥する。乾燥方法は、大気圧下での熱風乾燥、赤外線乾燥、真空乾燥などのいずれでもよい。真空乾燥を行うことにより短時間で乾燥することができる。前駆体中の水分が１重量％程度になるまで乾燥する。 (4. Drying) The precursor cake is dried. The drying method may be any of hot air drying under atmospheric pressure, infrared drying, vacuum drying, and the like. It can dry in a short time by performing vacuum drying. Dry until the water content in the precursor is about 1% by weight.
（５．粉体混合）乾燥後の前駆体粉末に、水酸化アルミニウムと水酸化リチウム粉末を加え、剪断力をかけて混合する。 (5. Powder mixing) Aluminum hydroxide and lithium hydroxide powder are added to the dried precursor powder and mixed by applying a shearing force.
（６．焼成）混合物を酸素存在下で焼成する。焼成により、以下の反応が起こる。 (6. Firing) The mixture is fired in the presence of oxygen. The following reaction occurs by firing.
本発明のリチウムイオン電池用正極活物質は、上述の工程を経て得られたニッケルリチウム金属複合酸化物の表面を以下の方法によりコバルト化合物で被覆することによって、得られる。 The positive electrode active material for a lithium ion battery of the present invention is obtained by coating the surface of the nickel lithium metal composite oxide obtained through the above-described steps with a cobalt compound by the following method.
（被覆用コバルト原料）本発明では、最終的にニッケルリチウム金属複合酸化物の表面を覆うコバルト化合物を供給するための原料として、硝酸コバルトを用いる。硝酸コバルトとして、硝酸コバルト六水和物：Ｃｏ（ＮＯ３）２・６Ｈ２Ｏを用いる。 (Cobalt raw material for coating) In the present invention, cobalt nitrate is used as a raw material for supplying a cobalt compound that finally covers the surface of the nickel lithium metal composite oxide. As the cobalt nitrate, cobalt nitrate hexahydrate: Co (NO 3 ) 2 .6H 2 O is used.
（被覆用コバルト化合物の混合）ニッケルリチウム金属複合酸化物と硝酸コバルト六水和物のエタノール溶液を混合し、６０〜９０℃で加熱する。その後、混合物を乾燥する。 (Mixing of Cobalt Compound for Coating) A nickel lithium metal composite oxide and an ethanol solution of cobalt nitrate hexahydrate are mixed and heated at 60 to 90 ° C. Thereafter, the mixture is dried.
（混合物の焼成）乾燥された上記混合物を酸素存在下で焼成する。焼成温度は５００〜８００℃の範囲である。焼成の過程で硝酸イオンが分解し、ニッケルリチウム金属複合酸化物の表面とコバルト成分が反応し、コバルト化合物からなる被覆層が形成される。こうして、コバルト化合物で表面が被覆されたニッケルリチウム金属複合酸化物からなる、本発明の正極活物質が得られる。 (Baking of mixture) The dried mixture is fired in the presence of oxygen. The firing temperature is in the range of 500 to 800 ° C. During the firing process, nitrate ions are decomposed, the surface of the nickel lithium metal composite oxide reacts with the cobalt component, and a coating layer made of a cobalt compound is formed. In this way, the positive electrode active material of this invention which consists of nickel lithium metal complex oxide by which the surface was coat | covered with the cobalt compound is obtained.
コバルト化合物で表面が被覆されたニッケルリチウム金属複合酸化物の充放電容量、充放電効率は、コバルト化合物で被覆していないニッケルリチウム金属複合酸化物の充放電容量、充放電効率と同等か、これより高い。したがって、本発明の正極活物質は初期電気特性が改善している。 The charge / discharge capacity and charge / discharge efficiency of the nickel lithium metal composite oxide whose surface is coated with a cobalt compound are the same as or equal to the charge / discharge capacity and charge / discharge efficiency of the nickel lithium metal composite oxide not coated with the cobalt compound. taller than. Therefore, the positive electrode active material of the present invention has improved initial electrical characteristics.
コバルト化合物で表面が被覆されたニッケルリチウム金属複合酸化物の水分吸収量、炭酸ガス吸収量は、コバルト化合物で被覆していないニッケルリチウム金属複合酸化物の水分吸収量、炭酸ガス吸収量よりも極めて低い。したがって、本発明の正極活物質は、水分や空気に対する暴露耐性が向上している。 The water absorption and carbon dioxide absorption of the nickel lithium metal composite oxide whose surface is coated with the cobalt compound is much higher than the water absorption and carbon dioxide absorption of the nickel lithium metal composite oxide not coated with the cobalt compound. Low. Therefore, the positive electrode active material of the present invention has improved exposure resistance to moisture and air.
水分や炭酸ガスを吸収した後は、コバルト化合物で被覆していないニッケルリチウム金属複合酸化物の放電容量、充放電効率は大きく低下する。これに対して、水分や炭酸ガスを吸収した後でも、コバルト化合物で表面が被覆されたニッケルリチウム金属複合酸化物の放電容量、充放電効率の低下はごくわずかである。したがって、本発明の正極活物質では、水分や空気への暴露による電池特性の低下が抑制されている。 After absorbing moisture and carbon dioxide, the discharge capacity and charge / discharge efficiency of the nickel-lithium metal composite oxide not coated with the cobalt compound are greatly reduced. On the other hand, even after absorbing moisture and carbon dioxide gas, the decrease in discharge capacity and charge / discharge efficiency of the nickel lithium metal composite oxide whose surface is coated with a cobalt compound is negligible. Therefore, in the positive electrode active material of the present invention, deterioration of battery characteristics due to exposure to moisture and air is suppressed.
コバルト化合物で表面が被覆されたニッケルリチウム金属複合酸化物の示差走査熱量計によって測定された発熱量は、コバルト化合物で被覆していないニッケルリチウム金属複合酸化物の発熱量に比べて格段に低い。したがって、本発明の正極活物質は安全性が改善している。 The calorific value measured by a differential scanning calorimeter of the nickel lithium metal composite oxide whose surface is coated with a cobalt compound is much lower than the calorific value of the nickel lithium metal composite oxide not coated with the cobalt compound. Therefore, the safety of the positive electrode active material of the present invention is improved.
本発明のリチウムイオン電池の正極活物質のみでリチウムイオン電池の正極活物質を構成してもよいし、本発明の正極活物質に、その長所が発現する程度の量で他の正極活物質を混合してもよい。例えば、本発明の正極活物質５０重量部と、本発明以外のリチウムイオン電池二次電池用正極活物質５０重量部とを混合したものを、正極活物質として用いることができる。リチウムイオン電池の正極を製造する場合には、上述の本発明の正極活物質、導電助剤、バインダー、分散用有機溶媒を加えて正極用合剤スラリーを調製し、電極に塗布する。 The positive electrode active material of the lithium ion battery may be composed of only the positive electrode active material of the lithium ion battery of the present invention, or other positive electrode active materials may be added to the positive electrode active material of the present invention in such an amount that the advantages are expressed. You may mix. For example, a mixture of 50 parts by weight of the positive electrode active material of the present invention and 50 parts by weight of a positive electrode active material for a lithium ion battery secondary battery other than the present invention can be used as the positive electrode active material. When manufacturing the positive electrode of a lithium ion battery, the positive electrode active material of the above-mentioned this invention, a conductive support agent, a binder, and the organic solvent for dispersion are added, the positive mix slurry is prepared, and it applies to an electrode.
以下の方法で、本発明のリチウムイオン電池用正極活物質を構成するニッケルリチウム金属複合酸化物を製造した。 The nickel lithium metal composite oxide which comprises the positive electrode active material for lithium ion batteries of this invention was manufactured with the following method.
（ニッケルリチウム金属複合酸化物の調製）硫酸ニッケル及び硫酸コバルトを溶解させた水溶液に水酸化ナトリウム水溶液を加え、生じた沈殿を濾過、洗浄、乾燥した。水酸化ニッケル−水酸化コバルト共沈物が得た。得られた水酸化ニッケル−水酸化コバルト共沈物に水酸化リチウムと水酸化アルミニウムを粉体で混合し焼成原料を得た。この焼成原料を酸素気流中、７８０℃で焼成した。ＬｉＮｉ０．８２５、Ｃｏ０．１５５、Ａｌ０．０２Ｏ２で表されるニッケルリチウム金属複合酸化物が得られた。
［実施例１］
焼成後のニッケルリチウム金属複合酸化物１５０ｇを秤量した。これに対して０．２５モル％に相当する硝酸コバルトを含む硝酸コバルト六水和物を、５０ｍｌエタノール溶液に溶解し、硝酸コバルトのエタノール溶液を調整した。ニッケルリチウム金属複合酸化物と上記硝酸コバルトのエタノール溶液を混合し、８０℃で１時間加熱した。液状成分が揮発して混合物が粉状になってから、温度８０℃において混合物を２時間乾燥した。乾燥された混合物を酸素ガス中、７５０℃で４時間焼成した。本発明の正極活物質を得た。
［実施例２］
焼成後のニッケルリチウム金属複合酸化物に対して１モル％に相当する硝酸コバルトを含む硝酸コバルト六水和物を用いた点以外は実施例と同じ条件で、本発明の正極活物質を得た。
［実施例３］
焼成後のニッケルリチウム金属複合酸化物に対して４モル％に相当する硝酸コバルトを含む硝酸コバルト六水和物を用いた点以外は実施例と同じ条件で、本発明の正極活物質を得た。
［比較例１］
被覆前のニッケルリチウム金属複合酸化物を比較用の正極活物質とした。
［比較例２］
（酸化ジルコニウム被覆正極活物質の製造）焼成後のニッケルリチウム金属複合酸化物１５０ｇと、これに対して４モル％に相当する酸化ジルコニウムを含む酸化ジルコニウム水ゾル１５０ｇを混合した。混合物をろ過し、得られた固形物を９０℃に保ち、８時間乾燥した。乾燥された混合物を酸素ガス中、７５０℃で４時間焼成した。酸化ジルコニウムで表面が被覆されたニッケルリチウム金属複合酸化物が得られた。
［比較例３］
（アルミナ被覆正極活物質の製造）焼成後のニッケルリチウム金属複合酸化物１５０ｇと、これに対して５モル％に相当するアルミナを混合した。混合物を酸素ガス中、７００℃で４時間焼成した。アルミナで表面が被覆されたニッケルリチウム金属複合酸化物が得られた。
実施例、比較例で得られた正極活物質の環境暴露に対する耐性を以下の方法で評価した。
(Preparation of nickel lithium metal composite oxide) A sodium hydroxide aqueous solution was added to an aqueous solution in which nickel sulfate and cobalt sulfate were dissolved, and the resulting precipitate was filtered, washed and dried. A nickel hydroxide-cobalt hydroxide coprecipitate was obtained. The obtained nickel hydroxide-cobalt hydroxide coprecipitate was mixed with lithium hydroxide and aluminum hydroxide in powder form to obtain a calcined raw material. The fired raw material was fired at 780 ° C. in an oxygen stream. A nickel lithium metal composite oxide represented by LiNi 0.825, Co 0.155, and Al 0.02 O 2 was obtained.
[Example 1]
150 g of the nickel-lithium metal composite oxide after firing was weighed. On the other hand, cobalt nitrate hexahydrate containing cobalt nitrate corresponding to 0.25 mol% was dissolved in 50 ml ethanol solution to prepare an ethanol solution of cobalt nitrate. The nickel lithium metal composite oxide and the ethanol solution of cobalt nitrate were mixed and heated at 80 ° C. for 1 hour. After the liquid component volatilized and the mixture became powdery, the mixture was dried at a temperature of 80 ° C. for 2 hours. The dried mixture was calcined at 750 ° C. for 4 hours in oxygen gas. A positive electrode active material of the present invention was obtained.
[Example 2]
A positive electrode active material of the present invention was obtained under the same conditions as in Examples, except that cobalt nitrate hexahydrate containing cobalt nitrate corresponding to 1 mol% with respect to the nickel-lithium metal composite oxide after firing was used. .
[Example 3]
A positive electrode active material of the present invention was obtained under the same conditions as in Examples, except that cobalt nitrate hexahydrate containing cobalt nitrate corresponding to 4 mol% with respect to the nickel-lithium metal composite oxide after firing was used. .
[Comparative Example 1]
The nickel lithium metal composite oxide before coating was used as a positive electrode active material for comparison.
[Comparative Example 2]
(Production of zirconium oxide-coated positive electrode active material) 150 g of the nickel-lithium metal composite oxide after firing and 150 g of a zirconium oxide water sol containing zirconium oxide corresponding to 4 mol% were mixed. The mixture was filtered and the resulting solid was kept at 90 ° C. and dried for 8 hours. The dried mixture was calcined at 750 ° C. for 4 hours in oxygen gas. A nickel lithium metal composite oxide whose surface was coated with zirconium oxide was obtained.
[Comparative Example 3]
(Production of Alumina-Coated Positive Electrode Active Material) After firing, 150 g of nickel-lithium metal composite oxide was mixed with alumina corresponding to 5 mol%. The mixture was calcined in oxygen gas at 700 ° C. for 4 hours. A nickel lithium metal composite oxide whose surface was coated with alumina was obtained.
The resistance to environmental exposure of the positive electrode active materials obtained in the examples and comparative examples was evaluated by the following methods.
（暴露試験）正極活物質を、相対湿度５８％、３０℃に保たれた空気恒温槽内に７２時間暴露した。暴露前後の、正極活物質の総水分量と炭酸イオン含有量の変化を測定した。暴露前後の正極活物質の総水分量の変化を表１に示す。暴露前後の正極活物質の炭酸イオン含有量の変化を表２に示す。 (Exposure Test) The positive electrode active material was exposed for 72 hours in an air thermostat kept at 30 ° C. and a relative humidity of 58%. Changes in the total water content and carbonate ion content of the positive electrode active material before and after exposure were measured. Table 1 shows changes in the total water content of the positive electrode active material before and after exposure. Table 2 shows changes in the carbonate ion content of the positive electrode active material before and after the exposure.
表１に示すように、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されている実施例１，２，３は、比較例１，２，３に比べ総水分量の変化が少ない。すなわち、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されることにより、外気中の水分によるニッケルリチウム金属複合酸化物を含む正極活物質の性能劣化が起こりにくい。
As shown in Table 1, in Examples 1, 2, and 3 in which the surface of the nickel-lithium metal composite oxide was coated with a cobalt compound derived from cobalt nitrate, the change in the total water content was compared with Comparative Examples 1, 2, and 3. Less is. That is, when the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, performance deterioration of the positive electrode active material containing the nickel lithium metal composite oxide due to moisture in the outside air hardly occurs.
表２に示すように、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されている実施例１，２，３は、比較例１，２，３に比べ炭酸イオン量の変化が少ない。すなわち、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されることにより、外気中の炭酸ガスによるニッケルリチウム金属複合酸化物を含む正極活物の性能劣化が起こりにくい。
As shown in Table 2, in Examples 1, 2, and 3 in which the surface of the nickel lithium metal composite oxide was coated with a cobalt compound derived from cobalt nitrate, the amount of carbonate ions was changed as compared with Comparative Examples 1, 2, and 3. Less is. That is, when the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, performance deterioration of the positive electrode active material containing the nickel lithium metal composite oxide due to carbon dioxide gas in the outside air hardly occurs.
実施例、比較例で得られた正極活物質の初期電気特性を以下の方法で評価した。 The initial electrical characteristics of the positive electrode active materials obtained in Examples and Comparative Examples were evaluated by the following methods.
（初期電気特性）実施例、比較例の正極活物質を、上記暴露条件に置かず、ただちにそれらの充電容量、放電容量、充放電効率を測定した。結果を表３に示す。 (Initial electrical characteristics) The positive electrode active materials of Examples and Comparative Examples were not subjected to the above exposure conditions, and their charge capacity, discharge capacity, and charge / discharge efficiency were immediately measured. The results are shown in Table 3.
表３に示すように、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されている実施例１，２，３は、比較例１，２と同等かあるいはそれを上回る充放電効率を示す。すなわち、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されても、ニッケルリチウム金属複合酸化物を含む正極活物質の初期電気特性は損なわれないか、あるいは向上する。
As shown in Table 3, Examples 1, 2, and 3 in which the surface of nickel-lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate are equivalent to or higher than those of Comparative Examples 1 and 2. Shows efficiency. That is, even if the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, the initial electrical characteristics of the positive electrode active material containing the nickel lithium metal composite oxide are not impaired or improved.
実施例、比較例で得られた正極活物質の環境暴露による電気特性の変化を以下の方法で評価した。 Changes in electrical characteristics due to environmental exposure of the positive electrode active materials obtained in Examples and Comparative Examples were evaluated by the following methods.
（環境暴露を経た電気特性）正極活物質を相対湿度５０％、２５℃に保たれた空気恒温槽内に７日間暴露した。暴露前後の充電容量、放電容量、充放電効率を測定し、比較した。評価結果を表４に示す。 (Electrical characteristics after environmental exposure) The positive electrode active material was exposed for 7 days in an air thermostat kept at 25% relative humidity and 50%. The charge capacity, discharge capacity, and charge / discharge efficiency before and after exposure were measured and compared. The evaluation results are shown in Table 4.
表４に示すように、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されている実施例１では、環境暴露後にも関わらず充放電効率が向上している。これに対して被覆していない比較例１では、環境暴露後の充放電効率は低下している。すなわち、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆すると、ニッケルリチウム金属複合酸化物を含む電気特性は環境暴露により損なわれることはない。 As shown in Table 4, in Example 1 in which the surface of the nickel lithium metal composite oxide was coated with a cobalt compound derived from cobalt nitrate, the charge / discharge efficiency was improved despite exposure to the environment. On the other hand, in the comparative example 1 which is not coat | covered, the charge / discharge efficiency after environmental exposure is falling. That is, when the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, the electrical characteristics including the nickel lithium metal composite oxide are not impaired by environmental exposure.
さらに、実施例、比較例について、以下の方法で熱安定性を評価した。評価結果を表５に示す。 Furthermore, thermal stability was evaluated by the following methods for the examples and comparative examples. The evaluation results are shown in Table 5.
（熱安定性）前述の初期電気特性の評価で用いた方法に準じた方法で正極活物質を充電し、その示差走査熱量分析を行った。示差走査熱量の測定には日立ハイテクサイエンス社製 ＤＳＣ−７０２０ 示差走査熱量計を用いた。 (Thermal stability) The positive electrode active material was charged by the method according to the method used in the evaluation of the initial electrical characteristics described above, and the differential scanning calorimetry was performed. A differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd. was used for measurement of the differential scanning calorific value.
表５に示すように、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆されている実施例１，２，３では、被覆していない比較例１に比べて発熱量は小さい。すなわち、ニッケルリチウム金属複合酸化物の表面が硝酸コバルト由来のコバルト化合物で被覆すると、ニッケルリチウム金属複合酸化物を含む正極活物質の発熱量が低減される。 As shown in Table 5, in Examples 1, 2, and 3 in which the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, the calorific value is smaller than that in Comparative Example 1 that is not coated. . That is, when the surface of the nickel lithium metal composite oxide is coated with a cobalt compound derived from cobalt nitrate, the calorific value of the positive electrode active material containing the nickel lithium metal composite oxide is reduced.
本発明は、初期電気特性、安全性、耐久性に優れるリチウムイオン電池の製造に貢献する。本発明の正極活物質を用いて、より小型の電子機器や、蓄電設備や車両などのより高い安全性と耐久性が求められる工業製品に用いられるリチウムイオン電池が提供されることが、期待される。 The present invention contributes to the manufacture of a lithium ion battery excellent in initial electrical characteristics, safety, and durability. The positive electrode active material of the present invention is expected to provide a lithium ion battery for use in industrial products that require higher safety and durability, such as smaller electronic devices, power storage facilities, and vehicles. The
Claims (15)
（ただし式（１）中、Ｍは、Ｃｏ，Ｍｎ，Ｆｅ、Ｃｕから選ばれる１つ以上の金属元素であり、
ＮはＡｌ、Ｗ、Ｔａ、Ｂから選ばれる１つ以上の金属元素であり、
０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。） The positive electrode active material for lithium ion batteries by which the cobalt compound is coat | covered on the surface of the nickel lithium metal complex oxide represented by the following general formula (1).
(In the formula (1), M is one or more metal elements selected from Co, Mn, Fe, and Cu;
N is one or more metal elements selected from Al, W, Ta, and B,
0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10. )
（ただし式（１）中、Ｍは、Ｃｏ，Ｍｎ，Ｆｅ、Ｃｕから選ばれる１つ以上の金属元素であり、
ＮはＡｌ、Ｗ、Ｔａ、Ｂから選ばれる１つ以上の金属元素であり、
０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．０１＜ｚ＜０．１０である。） The manufacturing method of the positive electrode active material for lithium ion batteries including the process of coat | covering the cobalt compound on the surface of the nickel lithium metal complex oxide represented by the following General formula (1).
(In the formula (1), M is one or more metal elements selected from Co, Mn, Fe, and Cu;
N is one or more metal elements selected from Al, W, Ta, and B,
0.90 <x <1.10, 0.01 <y <0.15, 0.01 <z <0.10. )
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| JP2020181638A (en) * | 2019-04-23 | 2020-11-05 | トヨタ自動車株式会社 | Coating positive electrode active material |
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| EP4095949A1 (en) * | 2021-05-28 | 2022-11-30 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery including the same |
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| JP2020525993A (en) * | 2017-10-12 | 2020-08-27 | エルジー・ケム・リミテッド | Positive electrode active material for lithium secondary battery, method for producing the same, positive electrode for lithium secondary battery including the same, and lithium secondary battery |
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| US11682755B2 (en) | 2017-12-04 | 2023-06-20 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material |
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