JP6449593B2 - Low alkali nickel lithium metal composite oxide powder and method for producing the same - Google Patents
Low alkali nickel lithium metal composite oxide powder and method for producing the same Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims description 69
- 239000002905 metal composite material Substances 0.000 title claims description 63
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 title claims description 58
- 239000000843 powder Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000003513 alkali Substances 0.000 title description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 29
- 239000001569 carbon dioxide Substances 0.000 claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- 239000007774 positive electrode material Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 10
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- -1 nickel lithium metal complex Chemical class 0.000 claims description 3
- 238000010304 firing Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010248 power generation Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent 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
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003756 stirring Methods 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は低アルカリニッケルリチウム金属複合酸化物、これを含むリチウムイオン電池正極物質、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、及び上記低アルカリニッケルリチウム金属複合酸化物の製造方法に関する。 The present invention relates to a low alkali nickel lithium metal composite oxide, a lithium ion battery positive electrode material including the same, a lithium ion battery positive electrode using the active material, a lithium ion battery having the positive electrode, and the low alkali nickel lithium metal composite oxide It relates to the manufacturing method.
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言った、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、未だ解決されておいない。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事業所や家庭単位の電力確保が重要であることが認識されに関する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, due to the growing awareness of energy crisis and environmental awareness, the installation of independent and 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. Is increasing. However, the problem that power generation equipment using natural energy such as wind power generation and solar power generation is 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 caused by the subsequent stoppage of nuclear power plants, it has been recognized that it is important to secure electric power for business units and households when disasters such as earthquakes occur The importance of this has been 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。 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.
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.
リチウムイオン電池の正極活物質としては、コバルト酸リチウム（ＬＣＯ）に代表されるコバルト系正極活物質が用いられてきた。コバルト酸リチウムを用いて電極を作成すると、電極密度は１立方センチメートル当たり３．９ｇを超える大密度を達成できる。しかしその一方、コバルト酸リチウム自身の放電容量は実質１５０ｍＡｈ／ｇ程度と低い。 As a positive electrode active material of a lithium ion battery, a cobalt-based positive electrode active material typified by lithium cobaltate (LCO) has been used. When an electrode is made using lithium cobaltate, an electrode density of greater than 3.9 g per cubic centimeter can be achieved. However, on the other hand, the discharge capacity of lithium cobalt oxide itself is as low as about 150 mAh / g.
リチウムイオン電池の正極活物質としては、ＬＮＣＯ（Ｌｉ、Ｎｉ、Ｃｏの複合酸化物），特にＬＮＣＡＯ（Ｌｉ、Ｎｉ、Ｃｏ、Ａｌの複合酸化物）に代表されるニッケル系正極活物質も検討されている。ＬＮＣＡＯの単位重量当たりの放電容量はコバルト系正極活物質よりも大きく、１９０ｍＡｈｇ−１を超える。しかしながら、これらの活物質自身の密度が低く電極密度を増大させることが困難であることから、単位体積当たりの放電容量を向上させることが出来なかった。しかもＬＮＣＡＯには共アルカリ性のＬｉ化合物が残留しているために、正極剤スラリーのゲル化を引き起こるという、電極製造上の問題点も指摘されてきた。 As a positive electrode active material of a lithium ion battery, a nickel-based positive electrode active material represented by LNCO (Li, Ni, Co composite oxide), particularly LNCAO (Li, Ni, Co, Al composite oxide) has been studied. ing. The discharge capacity per unit weight of LNCAO is larger than that of the cobalt-based positive electrode active material and exceeds 190 mAhg-1. However, since the density of these active materials themselves is low and it is difficult to increase the electrode density, the discharge capacity per unit volume cannot be improved. Moreover, since a co-alkaline Li compound remains in LNCAO, it has been pointed out that there is a problem in electrode production that causes gelation of the positive electrode slurry.
リチウムイオン電池の体積当たりの放電容量と、放電容量保持性を改善するための、リチウムイオン正極活物質の製造方法は、種々のものが提案されている。例えば、特許文献１，２には、炭酸ガスを用いた熱処理工程を含む方法が記載されている。しかしながら、これらの先行技術ではＬＮＣＡＯ系のニッケル系正極活物質について検討されていない。また、特許文献３に記載されているように、ＬＮＣＡＯを含む正極剤スラリーのゲル化を防止するために従来から水洗が提案されてきたが、水洗によって放電容量が低下するという問題があった。 Various methods for producing a lithium ion positive electrode active material for improving the discharge capacity per volume of a lithium ion battery and the discharge capacity retention have been proposed. For example, Patent Documents 1 and 2 describe a method including a heat treatment step using carbon dioxide gas. However, these prior arts have not studied LNCAO-based nickel-based positive electrode active materials. In addition, as described in Patent Document 3, water washing has been conventionally proposed in order to prevent gelation of the positive electrode agent slurry containing LNCAO, but there is a problem that the discharge capacity is reduced by water washing.
このように、高容量のリチウムイオンに適しており、しかも、正極剤製造時に問題のないＬＮＣＡＯ型正極活物質としては、未だ満足できるものが得られていない。 Thus, a satisfactory LNCAO-type positive electrode active material that is suitable for high-capacity lithium ions and that does not have a problem during the production of the positive electrode agent has not yet been obtained.
本発明は、電極製造や電池性能に有利なＬＮＣＡＯ型正極活物質正極活物質を提供することを課題とする。 This invention makes it a subject to provide the LNCAO type positive electrode active material positive electrode active material advantageous to electrode manufacture and battery performance.
本発明の発明者は、ＬＮＣＡＯに代表される正極活物質の製造について鋭意検討した。その結果、原料混合物の焼成工程に引き続き、焼成物を高温で炭酸ガスで処理することにより所望の正極活物質用のニッケルリチウム金属複合酸化物粉体を得ることに成功した。 The inventor of the present invention diligently studied the production of a positive electrode active material represented by LNCAO. As a result, succeeding in obtaining the desired nickel-lithium metal composite oxide powder for the positive electrode active material by treating the fired product with carbon dioxide gas at a high temperature following the firing step of the raw material mixture.
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（２）で表されるニッケルリチウム金属複合酸化物からなり、
その２ｇを１００ｇの水に分散させた際の上澄の水素イオン濃度がｐＨで１１．４未満であり、余剰の水酸化リチウムの量が０．４重量％未満であり、
以下の工程をこの順で行うことを特徴とする、低アルカリ性ニッケルリチウム金属複合酸化物粉体。
工程１：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。
工程２：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。
工程３：上記共沈殿物を濾過、洗浄して、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。
工程４：上記前駆体ケーキを乾燥する。
工程５：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。
工程６：混合物を酸素存在下で焼成する。
工程７：焼成して得られたニッケルリチウム金属複合酸化物を、炭酸ガスを含む気体と接 触させる。この時の接触時間は２００以上６００℃以下、接触時間は１０時間以上３０時 間以下である。
That is, the present invention is as follows.
(Invention 1) A nickel-lithium metal composite oxide represented by the following general formula (2) :
Its 2g hydrogen ion concentration of supernatant when dispersed in 100g water is less than 11.4 in pH, the amount of excess lithium hydroxide Ri der less than 0.4 wt%,
A low alkaline nickel lithium metal composite oxide powder characterized by performing the following steps in this order .
Step 1: The raw materials nickel sulfate and cobalt sulfate are dissolved in water.
Step 2: A coprecipitate of nickel hydroxide and cobalt hydroxide is formed.
Process 3: The said coprecipitate is filtered and wash | cleaned, and the precursor cake which consists of nickel hydroxide and cobalt hydroxide is obtained.
Step 4: The precursor cake is dried.
Step 5: Add aluminum hydroxide and lithium hydroxide powder to the dried precursor powder, and mix by applying a shearing force.
Step 6: The mixture is fired in the presence of oxygen.
Step 7: The calcined nickel lithium-metal composite oxide obtained by, let come in contact with the gas containing carbon dioxide gas. The contact time when more than 200 600 ° C. or less, the contact time is less between at least 30 10 hours.
（発明２）充電・放電性能が、０．１Ｃ充電における容量が２１０−２３０ｍＡｈ／ｇの範囲であり、０．１Ｃ放電における容量が１７５−１９０ｍＡｈ／ｇの範囲である、発明１の低アルカリ性ニッケルリチウム金属複合酸化物粉体。
(Invention 2 ) Low alkaline nickel according to Invention 1 , wherein the charge / discharge performance is in the range of 210-230 mAh / g at 0.1 C charge and the capacity in the range of 175-190 mAh / g at 0.1 C discharge. Lithium metal composite oxide powder.
（発明３）発明１又は２の低アルカリ性ニッケルリチウム金属複合酸化物粉体を含むことを特徴とする、リチウムイオン電池用正極活物質。
(Invention 3 ) A positive electrode active material for a lithium ion battery, comprising the low alkaline nickel lithium metal composite oxide powder of Invention 1 or 2 .
（発明４）発明３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 4 ) A positive electrode for a lithium ion battery, characterized in that the positive electrode active material for a lithium ion battery of Invention 3 is used.
（発明５）発明４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 5 ) A lithium ion battery comprising the positive electrode for a lithium ion battery according to Invention 4 .
（発明６）以下の一般式（２）で表されるニッケルリチウム金属複合酸化物からなり、
その２ｇを１００ｇの水に分散させた際の上澄の水素イオン濃度がｐＨで１１．４未満であり、余剰の水酸化リチウムの量が０．４重量％未満であり、
以下の工程をこの順で行うことを特徴とする、低アルカリ性ニッケルリチウム金属複合酸化物粉体の製造方法。
工程１：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。
工程２：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。
工程３：上記共沈殿物を濾過、洗浄して、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。
工程４：上記前駆体ケーキを乾燥する。
工程５：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。
工程６：混合物を酸素存在下で焼成する。
工程７：焼成して得られたニッケルリチウム金属複合酸化物を、炭酸ガスを含む気体と接 触させる。この時の接触時間は２００以上６００℃以下、接触時間は１０時間以上３０時 間以下である。
(Invention 6 ) A nickel-lithium metal composite oxide represented by the following general formula (2) :
Its 2g hydrogen ion concentration of supernatant when dispersed in 100g water is less than 11.4 in pH, the amount of excess lithium hydroxide Ri der less than 0.4 wt%,
The manufacturing method of the low alkaline nickel lithium metal complex oxide powder characterized by performing the following processes in this order .
Step 1: The raw materials nickel sulfate and cobalt sulfate are dissolved in water.
Step 2: A coprecipitate of nickel hydroxide and cobalt hydroxide is formed.
Process 3: The said coprecipitate is filtered and wash | cleaned, and the precursor cake which consists of nickel hydroxide and cobalt hydroxide is obtained.
Step 4: The precursor cake is dried.
Step 5: Add aluminum hydroxide and lithium hydroxide powder to the dried precursor powder, and mix by applying a shearing force.
Step 6: The mixture is fired in the presence of oxygen.
Step 7: The calcined nickel lithium-metal composite oxide obtained by, let come in contact with the gas containing carbon dioxide gas. The contact time when more than 200 600 ° C. or less, the contact time is less between at least 30 10 hours.
（発明７）低アルカリ性ニッケルリチウム金属複合酸化物粉体の０．１Ｃ放電における初期放電容量が、１９０ｍＡｈ／ｇ以上である、発明６のリチウムイオン電池用正極活物質の製造方法。
(Invention 7 ) The method for producing a positive electrode active material for a lithium ion battery according to Invention 6 , wherein the initial discharge capacity of the low alkaline nickel lithium metal composite oxide powder at 0.1 C discharge is 190 mAh / g or more.
本発明のニッケルリチウム金属複合酸化物粉体は、低アルカリ性であり、電池特性が優れている。 The nickel lithium metal composite oxide powder of the present invention is low alkaline and has excellent battery characteristics.
本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体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。
The nickel lithium metal composite oxide constituting the low alkaline nickel lithium metal composite oxide powder of the present invention is 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。）
本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体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。
(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 low alkaline nickel lithium metal composite oxide powder of the present invention preferably has the following general formula (2) wherein M is Co and N is Al in the general formula (1). ).
（ただし式（２）中、０．９０＜ｘ＜１．１０、０．０１＜ｙ＜０．１５、０．００５＜ｚ＜０．１０である。）
本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体は、以下の方法により製造することができる。
(In the formula (2), 0.90 <x <1.10, 0.01 <y <0.15, 0.005 <z <0.10.)
The low alkaline nickel lithium metal composite oxide powder of the present invention 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ニッケルリチウム金属複合酸化物粉体の製造方法では、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 nickel lithium metal composite oxide powder 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 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.
焼成後に、微細粒状のニッケルリチウム金属複合酸化物が得られる。その粒子のメジアン径は概ね２０μｍ以下、通常は５〜１０μｍの範囲にある。 After firing, a finely divided nickel-lithium metal composite oxide is obtained. The median diameter of the particles is approximately 20 μm or less, usually in the range of 5 to 10 μm.
（７．高温炭酸ガス処理）本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体の製造では、焼成工程に続き、高温下で、ニッケルリチウム金属複合酸化物を炭酸ガスを含む気体と接触させる。炭酸ガスを含む気体には制限がないが、通常は、空気、あるいは酸素ガスと炭酸ガスとの混合気体が用いられる。接触温度は ２００〜６００℃、好ましくは、３００〜５００℃である。接触時間は１０〜３０時間、好ましくは１０〜２０時間である。この処理は、焼成工程の直後に焼成設備内で行うことができる。処理に新たな設備は必要でない。焼成炉の温度を制御し、炭酸ガスを含む気体を一定時間焼成炉内に通すことで、焼成工程から高温炭酸ガス処理を連続して行うことが出来る。 (7. High-temperature carbon dioxide treatment) In the production of the low alkaline nickel lithium metal composite oxide powder of the present invention, the nickel lithium metal composite oxide is brought into contact with a gas containing carbon dioxide gas at a high temperature following the firing step. Although there is no restriction | limiting in the gas containing a carbon dioxide gas, Usually, the mixed gas of air or oxygen gas and a carbon dioxide gas is used. The contact temperature is 200 to 600 ° C, preferably 300 to 500 ° C. The contact time is 10 to 30 hours, preferably 10 to 20 hours. This treatment can be performed in the firing facility immediately after the firing step. No new equipment is required for processing. By controlling the temperature of the firing furnace and passing a gas containing carbon dioxide through the firing furnace for a certain period of time, high-temperature carbon dioxide treatment can be continuously performed from the firing step.
（８．解砕）本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体の製造方法では、高温炭酸ガス処理の後に、必要に応じて、さらに解砕工程を設けることができる。解砕工程では、ジェットミルなどの破砕機を用いて、焼成後の低アルカリ性ニッケルリチウム金属複合酸化物粉体の凝集した粒子を破壊する。適度に細粒化されたニッケルリチウム金属複合酸化物を用いると、均一で塗布性に優れる正極剤スラリーが得られる。このような正極剤スラリーにより、正極電極の生産効率を向上させることができる。しかも、正極活物質のイオン放出性も安定化され、電池性能も向上する。 (8. Crushing) In the method for producing the low alkaline nickel lithium metal composite oxide powder of the present invention, a crushing step can be further provided as needed after the high-temperature carbon dioxide treatment. In the crushing step, the agglomerated particles of the low alkaline nickel lithium metal composite oxide powder after firing are broken using a crusher such as a jet mill. When a nickel-lithium metal composite oxide finely grained is used, a uniform positive electrode slurry having excellent coating properties can be obtained. The positive electrode slurry can improve the production efficiency of the positive electrode. In addition, the ion release property of the positive electrode active material is stabilized, and the battery performance is improved.
こうして、本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体が得られる。本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体は、上記高温炭酸ガス処理によって、ｐＨが１１．４以下に低減されており、余剰の水酸化リチウムの含有量が０．４重量％以下に低減されている。低アルカリ性を示す本発明のニッケルリチウム金属複合酸化物は、リチウムイオン電池正極剤スラリーにバインダーとして含まれるＰＶＤＦとの反応性が低い。このため、本発明のニッケルリチウム金属複合酸化物を正極活物質として使用した場合、正極製造時の正極剤スラリーのゲル化が起こりにくく、正極剤スラリーと電極との密着性が損なわれない。 Thus, the low alkaline nickel lithium metal composite oxide powder of the present invention is obtained. In the low alkaline nickel lithium metal composite oxide powder of the present invention, the pH is reduced to 11.4 or less by the high temperature carbon dioxide treatment, and the excess lithium hydroxide content is 0.4 wt% or less. Has been reduced. The nickel lithium metal composite oxide of the present invention exhibiting low alkalinity has low reactivity with PVDF contained as a binder in the lithium ion battery positive electrode slurry. For this reason, when the nickel lithium metal composite oxide of the present invention is used as a positive electrode active material, gelation of the positive electrode agent slurry during the production of the positive electrode hardly occurs, and the adhesion between the positive electrode agent slurry and the electrode is not impaired.
しかも、本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体は、初期放電容量の劣化が小さい。 Moreover, the low alkaline nickel lithium metal composite oxide powder of the present invention has little deterioration in initial discharge capacity.
本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体は、リチウムイオン電池の正極活物質として利用できる。本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体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、本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体に、その長所が発現する程度の量で他のニッケルリチウム金属複合酸化物を混合してもよい。例えば、本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体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を５０重量部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、上述の本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体を含む正極活物質、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 low alkaline nickel lithium metal composite oxide powder of the present invention can be used as a positive electrode active material of a lithium ion battery. The positive electrode active material of the lithium ion battery may be composed only of the low alkaline nickel lithium metal composite oxide powder of the present invention, and the advantages are manifested in the low alkaline nickel lithium metal composite oxide powder of the present invention. Other nickel lithium metal composite oxides may be mixed in a certain amount. For example, a mixture of 50 parts by weight of the low alkaline nickel lithium metal composite oxide powder 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 may be used as the positive electrode active material. it can. When producing a positive electrode of a lithium ion battery, a positive electrode active material containing the above-mentioned low alkaline nickel lithium metal composite oxide powder of the present invention, a conductive additive, a binder, and an organic solvent for dispersion are added to mix the positive electrode. A slurry is prepared and applied to the electrode.
本発明の低アルカリ性ニッケルリチウム金属複合酸化物粉体の製造に用いるニッケルリチウム金属複合酸化物を以下の２通りの手順（手順Ａ，手順Ｂ）で製造した。 The nickel lithium metal composite oxide used for the production of the low alkaline nickel lithium metal composite oxide powder of the present invention was produced by the following two procedures (procedure A and procedure B).
（手順Ａ）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、攪拌速度毎分６００回転で攪拌し、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のための原料を得た。この原料を酸素気流中、７８０℃で焼成した。その結果、５０％粒径（いわゆるメジアン径）が７．２９μｍのニッケルリチウム金属複合酸化物が得られた。これを、ニッケルリチウム金属複合酸化物（A）と呼ぶ。このニッケルリチウム金属複合酸化物（A）を後述の実施例１〜３、比較例１、３に用いた。 (Procedure A) A sodium hydroxide aqueous solution was added to an aqueous solution in which nickel sulfate and cobalt sulfate were dissolved, and the mixture was stirred at a stirring speed of 600 rpm, 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 raw material for firing. This raw material was fired at 780 ° C. in an oxygen stream. As a result, a nickel lithium metal composite oxide having a 50% particle size (so-called median diameter) of 7.29 μm was obtained. This is called a nickel lithium metal composite oxide (A). This nickel lithium metal composite oxide (A) was used in Examples 1 to 3 and Comparative Examples 1 and 3 described later.
（手順Ｂ）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、攪拌速度毎分５００回転で攪拌し、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のための原料を得た。この原料を酸素気流中、７８０℃で焼成した。その結果、５０％粒径（いわゆるメジアン径）が７．５μｍのニッケルリチウム金属複合酸化物が得られた。これを、ニッケルリチウム金属複合酸化物（B）と呼ぶ。このニッケルリチウム金属複合酸化物（B）を後述の実施例４〜７、比較例２に用いた。 (Procedure B) An aqueous sodium hydroxide solution was added to an aqueous solution in which nickel sulfate and cobalt sulfate were dissolved, and the mixture was stirred at a stirring speed of 500 revolutions per minute, 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 raw material for firing. This raw material was fired at 780 ° C. in an oxygen stream. As a result, a nickel lithium metal composite oxide having a 50% particle size (so-called median diameter) of 7.5 μm was obtained. This is referred to as nickel lithium metal composite oxide (B). This nickel lithium metal composite oxide (B) was used in Examples 4 to 7 and Comparative Example 2 described later.
後述の実施例、比較例の条件で、上記焼成されたニッケルリチウム金属複合酸化物を処理し、あるいは処理しなかったものについて、以下の分析を行った。 The following analysis was performed on the case where the calcined nickel lithium metal composite oxide was treated or not treated under the conditions of Examples and Comparative Examples described later.
（ｐH測定）処理後のニッケルリチウム金属複合酸化物２ｇを２５℃の純水１００ｍｌに加え、マグネチックスターラーで３分間攪拌し、その後吸引濾過した。得られた濾液のｐＨを堀場製作所製ｐＨメーターで測定した。 (Measurement of pH) 2 g of the nickel-lithium metal composite oxide after treatment was added to 100 ml of pure water at 25 ° C., stirred for 3 minutes with a magnetic stirrer, and then suction filtered. The pH of the obtained filtrate was measured with a pH meter manufactured by Horiba.
（水酸化リチウムの滴定）処理後のニッケルリチウム金属複合酸化物２ｇを２５℃の純水１００ｍｌに加え、マグネチックスターラーで３分間攪拌し、その後吸引濾過した。得られた濾液の１０ｍｌをピペットで分取し、０．１Ｎ塩酸で滴定することによって水酸化リチウムの含有量を定量した。
［実施例１］
上述の焼成後のニッケルリチウム金属複合酸化物を、出入りの無い空気中、３００℃で、２０時間、処理した。空気中の炭酸ガス濃度は０．０５体積％であった。
［実施例２］
処理温度を５００℃に変えた点以外は実施例１と同じ条件で処理を行った。
［実施例３］
処理時間を１０時間に変えた点以外は実施例１と同じ条件で処理を行った。
［実施例４］
焼成後のニッケルリチウム金属複合酸化物を、酸素と炭酸ガスとの混合気体中、３００℃で、２０時間、処理した。上記混合気体中は、流量４．９７５L／ｍｉｎの酸素と、流量０．０２５L／ｍｉｎの炭酸ガスからなる、総流量５L／ｍｉｎの混合気流であり、炭酸ガス濃度は ０．５体積％であった。
［実施例５］
混合気流として、流量４．７５L／ｍｉｎの酸素と、流量０．２５L／ｍｉｎの炭酸ガスからなる、総流量５L／ｍｉｎの混合気流を用い、混合気体中の炭酸ガス濃度が５体積％である点以外は実施例４と同じ条件で処理を行った。
［実施例６］
空気として、流量５L／ｍｉｎ、炭酸ガス濃度が０．０５体積％の空気を用いた点以外は実施例１と同じ条件で処理を行った。
［実施例７］
空気として、流量５L／ｍｉｎ、炭酸ガス濃度が０．０５体積％の空気を用い、処理温度を４００℃とした点以外は実施例1と同じ条件で処理を行った。
［比較例１］
実施例１〜３で用いたニッケルリチウム金属複合酸化物について炭酸ガスによる処理をせず、そのまま、そのｐH及び残存水酸化リチウムの定量を行った。結果を表１に示す。表１では、処理をしなかったことを「- - -」で表示する。
［比較例２］
実施例４〜７で用いたニッケルリチウム金属複合酸化物について炭酸ガスによる処理をせず、そのまま、ｐH及び残存水酸化リチウムの定量を行った。
［比較例３］
処理温度を７５０℃に変えた点以外は実施例１と同じ条件で処理を行った。
(Titration of lithium hydroxide) 2 g of the nickel-lithium metal composite oxide after treatment was added to 100 ml of pure water at 25 ° C., stirred for 3 minutes with a magnetic stirrer, and then suction filtered. 10 ml of the obtained filtrate was pipetted and titrated with 0.1N hydrochloric acid to quantify the lithium hydroxide content.
[Example 1]
The above-mentioned nickel-lithium metal composite oxide after firing was treated at 300 ° C. for 20 hours in air without entering and exiting. The carbon dioxide gas concentration in the air was 0.05% by volume.
[Example 2]
The treatment was performed under the same conditions as in Example 1 except that the treatment temperature was changed to 500 ° C.
[Example 3]
Processing was performed under the same conditions as in Example 1 except that the processing time was changed to 10 hours.
[Example 4]
The nickel lithium metal composite oxide after firing was treated in a mixed gas of oxygen and carbon dioxide at 300 ° C. for 20 hours. The above mixed gas is a mixed airflow of oxygen at a flow rate of 4.975 L / min and carbon dioxide gas at a flow rate of 0.025 L / min, with a total flow rate of 5 L / min, and the carbon dioxide concentration is 0.5% by volume. It was.
[Example 5]
As the mixed gas stream, a mixed gas stream consisting of oxygen at a flow rate of 4.75 L / min and carbon dioxide gas at a flow rate of 0.25 L / min is used, and the concentration of carbon dioxide in the mixed gas is 5% by volume. Processing was performed under the same conditions as in Example 4 except for the points.
[Example 6]
The treatment was performed under the same conditions as in Example 1 except that air having a flow rate of 5 L / min and carbon dioxide concentration of 0.05% by volume was used.
[Example 7]
The treatment was performed under the same conditions as in Example 1 except that air having a flow rate of 5 L / min and carbon dioxide concentration of 0.05% by volume was used and the treatment temperature was 400 ° C.
[Comparative Example 1]
The nickel lithium metal composite oxide used in Examples 1 to 3 was not treated with carbon dioxide gas, and the pH and residual lithium hydroxide were quantified as they were. The results are shown in Table 1. In Table 1, “---” indicates that no processing has been performed.
[Comparative Example 2]
The nickel lithium metal composite oxides used in Examples 4 to 7 were not treated with carbon dioxide gas, and the pH and residual lithium hydroxide were quantified as they were.
[Comparative Example 3]
The treatment was performed under the same conditions as in Example 1 except that the treatment temperature was changed to 750 ° C.
上記実施例、比較例で用いたニッケルリチウム金属複合酸化物、これらの炭酸ガスによる処理の条件を表１に示す。 Table 1 shows the nickel lithium metal composite oxides used in the above Examples and Comparative Examples, and the conditions for treatment with these carbon dioxide gases.
上記実施例で得られた本発明のニッケルリチウム金属複合酸化物粉体と、比較例で得られた対照品の評価結果を、表２に示す。 Table 2 shows the evaluation results of the nickel lithium metal composite oxide powder of the present invention obtained in the above Examples and the control product obtained in the Comparative Example.
表２に示されるように、所定の条件でニッケルリチウム金属複合酸化物を炭酸ガス含有気体で処理した実施例では、ｐＨが低減され、電池特性にも優れる低アルカリ性ニッケルリチウム金属複合酸化物粉体が得られた。 As shown in Table 2, in an example in which nickel lithium metal composite oxide was treated with a carbon dioxide-containing gas under predetermined conditions, low alkaline nickel lithium metal composite oxide powder with reduced pH and excellent battery characteristics was gotten.
本発明では、焼成工程に引き続き、簡単な操作で高温炭酸ガス処理を行うことによって、電池性能や正極製造にとって望ましい低アルカリ性ニッケルリチウム金属複合酸化物粉体を製造することに成功した。本発明は、高容量のリチウムイオン電池の低コストでの製造に貢献すると期待される。 In the present invention, the low-alkaline nickel-lithium metal composite oxide powder, which is desirable for battery performance and positive electrode production, has been successfully produced by performing high-temperature carbon dioxide treatment with a simple operation following the firing step. The present invention is expected to contribute to low-cost production of high capacity lithium ion batteries.
Claims (7)
その２ｇを１００ｇの水に分散させた際の上澄の水素イオン濃度がｐＨで１１．４未満であり、余剰の水酸化リチウムの量が０．４重量％未満であり、
以下の工程をこの順で行って製造されることを特徴とする、低アルカリ性ニッケルリチウム金属複合酸化物粉体。
工程１：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。
工程２：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。
工程３：上記共沈殿物を濾過、洗浄して、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。
工程４：上記前駆体ケーキを乾燥する。
工程５：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。
工程６：混合物を酸素存在下で焼成する。
工程７：焼成して得られたニッケルリチウム金属複合酸化物を、炭酸ガスを含む気体と接 触させる。この時の接触温度は２００以上６００℃以下、接触時間は１０時間以上３０時 間以下である。 It consists of nickel lithium metal composite oxide represented by the following general formula (2) ,
Its 2g hydrogen ion concentration of supernatant when dispersed in 100g water is less than 11.4 in pH, the amount of excess lithium hydroxide Ri der less than 0.4 wt%,
A low alkaline nickel-lithium metal composite oxide powder produced by performing the following steps in this order .
Step 1: The raw materials nickel sulfate and cobalt sulfate are dissolved in water.
Step 2: A coprecipitate of nickel hydroxide and cobalt hydroxide is formed.
Process 3: The said coprecipitate is filtered and wash | cleaned, and the precursor cake which consists of nickel hydroxide and cobalt hydroxide is obtained.
Step 4: The precursor cake is dried.
Step 5: Add aluminum hydroxide and lithium hydroxide powder to the dried precursor powder, and mix by applying a shearing force.
Step 6: The mixture is fired in the presence of oxygen.
Step 7: The calcined nickel lithium-metal composite oxide obtained by, let come in contact with the gas containing carbon dioxide gas. Contact temperature at this time is more than 200 600 ° C. or less, the contact time is less between at least 30 10 hours.
その２ｇを１００ｇの水に分散させた際の上澄の水素イオン濃度がｐＨで１１．４未満であり、余剰の水酸化リチウムの量が０．４重量％未満であり、
以下の工程をこの順で行うことを特徴とする、低アルカリ性ニッケルリチウム金属複合酸化物粉体の製造方法。
工程１：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。
工程２：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。
工程３：上記共沈殿物を濾過、洗浄して、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。
工程４：上記前駆体ケーキを乾燥する。
工程５：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。
工程６：混合物を酸素存在下で焼成する。
工程７：焼成して得られたニッケルリチウム金属複合酸化物を、炭酸ガスを含む気体と接 触させる。この時の接触温度は２００以上６００℃以下、接触時間は１０時間以上３０時 間以下である。 It consists of nickel lithium metal composite oxide represented by the following general formula (2) ,
Its 2g hydrogen ion concentration of supernatant when dispersed in 100g water is less than 11.4 in pH, the amount of excess lithium hydroxide Ri der less than 0.4 wt%,
The manufacturing method of the low alkaline nickel lithium metal complex oxide powder characterized by performing the following processes in this order .
Step 1: The raw materials nickel sulfate and cobalt sulfate are dissolved in water.
Step 2: A coprecipitate of nickel hydroxide and cobalt hydroxide is formed.
Process 3: The said coprecipitate is filtered and wash | cleaned, and the precursor cake which consists of nickel hydroxide and cobalt hydroxide is obtained.
Step 4: The precursor cake is dried.
Step 5: Add aluminum hydroxide and lithium hydroxide powder to the dried precursor powder, and mix by applying a shearing force.
Step 6: The mixture is fired in the presence of oxygen.
Step 7: The calcined nickel lithium-metal composite oxide obtained by, let come in contact with the gas containing carbon dioxide gas. Contact temperature at this time is more than 200 600 ° C. or less, the contact time is less between at least 30 10 hours.
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