JP2020057503A - Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for manufacturing all-solid-state lithium-ion battery - Google Patents
Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for manufacturing all-solid-state lithium-ion battery Download PDFInfo
- Publication number
- JP2020057503A JP2020057503A JP2018186849A JP2018186849A JP2020057503A JP 2020057503 A JP2020057503 A JP 2020057503A JP 2018186849 A JP2018186849 A JP 2018186849A JP 2018186849 A JP2018186849 A JP 2018186849A JP 2020057503 A JP2020057503 A JP 2020057503A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- solid
- active material
- ion battery
- electrode active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
【課題】Ｎｂ被覆された全固体リチウムイオン電池用正極活物質の簡便な製造方法を提供する。【解決手段】ニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物前駆体をロッキングミキサー中に投入し、シュウ酸ニオブ水溶液を噴霧してシュウ酸ニオブが被覆された前駆体粉体を作製する工程と、シュウ酸ニオブが被覆された前駆体粉体とリチウム化合物とを混合して焼成する工程とを含む全固体リチウムイオン電池用正極活物質の製造方法。【選択図】なしPROBLEM TO BE SOLVED: To provide a simple method for producing an Nb-coated positive electrode active material for an all-solid-state lithium ion battery. A transition metal hydroxide precursor composed of nickel, cobalt, and manganese is charged into a rocking mixer, and a niobium oxalate aqueous solution is sprayed to produce a precursor powder coated with niobium oxalate. And a step of mixing a precursor powder coated with niobium oxalate and a lithium compound and firing the mixture, and a method for producing a positive electrode active material for an all-solid-state lithium ion battery. [Selection diagram] None
Description
本発明は、全固体リチウムイオン電池用正極活物質の製造方法、及び全固体リチウムイオン電池の製造方法に関する。 The present invention relates to a method for producing a positive electrode active material for an all-solid lithium-ion battery and a method for producing an all-solid-state lithium-ion battery.
現在、使用されているリチウムイオン電池は、正極活物質として層状化合物ＬｉＭｅＯ2（Ｍｅは平均で＋ＩＩＩ価となるように選択されるカチオンであり、レドックスカチオンを必ず含む）、スピネル化合物ＬｉＭｅＱＯ4（Ｑは平均で＋ＩＶ価となるように選択されるカチオン）、オリビン系化合物ＬｉＸ１Ｘ２Ｏ4（Ｘ１は＋ＩＩ価となるように選択されるカチオンであり、レドックスカチオンを必ず含む、Ｘ２は＋Ｖ価となるように選択されるカチオン）や蛍石型化合物Ｌｉ5ＭｅＯ4等を用いており、一方でその特性を生かすことができるよう、電解液その他構成要件が年々改善されてきている。 Currently used lithium ion batteries include, as a positive electrode active material, a layered compound LiMeO 2 (Me is a cation selected to have an average of + III valence and necessarily contains a redox cation), and a spinel compound LiMeQO 4 (Q Is a cation selected to have a + IV valence on average), and the olivine-based compound LiX1X2O 4 (X1 is a cation selected to have a + II valency, always contains a redox cation, and X2 has a + V valence. (A selected cation), a fluorite-type compound Li 5 MeO 4, and the like, and on the other hand, the electrolytic solution and other components are being improved year by year so that the characteristics can be utilized.
ただ、リチウムイオン電池の場合は、電解液は有機化合物が大半であり、たとえ難燃性の化合物を用いたとしても火災に至る危険性が全くなくなるとは言いきれない。こうした液系リチウムイオン電池（以下、液系ＬＩＢとも称する）の代替候補として、電解質を固体とした全固体リチウムイオン電池（以下、全固体ＬＩＢとも称する）が近年注目を集めている（特許文献１等）。その中でも、固体電解質としてＬｉ2Ｓ−Ｐ2Ｓ5などの硫化物やそれにハロゲン化リチウムを添加した全固体リチウムイオン電池が主流となりつつある。 However, in the case of a lithium ion battery, most of the electrolyte is an organic compound, and even if a flame-retardant compound is used, it cannot be said that there is no danger of fire. As an alternative candidate for such a liquid-based lithium-ion battery (hereinafter, also referred to as a liquid-based LIB), an all-solid-state lithium-ion battery (hereinafter, also referred to as an all-solid-state LIB) having a solid electrolyte has attracted attention in recent years (Patent Document 1). etc). Among them, sulfides such as Li 2 S—P 2 S 5 as solid electrolytes and all-solid lithium ion batteries to which lithium halide is added are becoming mainstream.
また、従来、リチウムイオン電池用正極活物質の製造方法として、例えば特許文献１に開示されているように、あらかじめ正極活物質を構成する全元素を含む前駆体原料とリチウム源（水酸化リチウム等）を混合して焼成して酸化物正極活物質を作製した後、ニオブ酸リチウムの前駆体等のコート溶液を酸化物正極活物質の表面上に塗布し、更に焼成を行うことで所望のリチウムイオン電池用正極活物質を作製している。 Conventionally, as a method for producing a positive electrode active material for a lithium ion battery, for example, as disclosed in Patent Document 1, a precursor material containing all elements constituting the positive electrode active material and a lithium source (such as lithium hydroxide) ) Is mixed and baked to produce an oxide positive electrode active material, and then a coating solution such as a lithium niobate precursor is applied on the surface of the oxide positive electrode active material, and further calcination is performed to obtain a desired lithium. We are producing positive electrode active materials for ion batteries.
しかしながら、上述のように従来は正極活物質のコア粒子を製造するために少なくとも一度焼成工程があり、さらに、正極活物質のコア粒子の表面上に被覆物を塗布した後、再度焼成工程を行う必要がある。このように、焼成工程が複数回あると、熱処理コストが大きくなり、また生産のリードタイムも嵩んでしまうという問題がある。このため、より簡便な方法で正極活物質を製造することができる技術の開発が望まれている。ここで、全固体リチウムイオン電池用の正極活物質の場合は特許文献１にあるようにＮｂが表面に存在すると特性が大幅に改善することが知られており、この点からもＮｂ被覆の簡便な方法が求められていたが、現在の一般的な転動流動装置では、均一に被覆しようとすると上記コア粒子の転動時間を長くとらねばならず、この間にせっかく被覆した粒子同士がぶつかって割れてしまうリスクがあった。割れた粒子はそのまま転動しているので、そのまま再被覆できれば問題なく全固体リチウムイオン電池用正極活物質として用いることができるが、再被覆がなされないまま転動流動装置から取り出されることがあり、これを正極活物質として全固体リチウムイオン電池を作製すると、時々特性が悪いものができることが判明した。従って、被覆時間の短い簡便なＮｂ被覆方法を開発することが重要となっていた。 However, as described above, conventionally, there is at least one firing step for producing the core particles of the positive electrode active material, and further, after applying the coating on the surface of the core particles of the positive electrode active material, the firing step is performed again. There is a need. As described above, when the firing step is performed a plurality of times, there is a problem that the heat treatment cost increases and the production lead time increases. For this reason, development of a technique that can produce a positive electrode active material by a simpler method is desired. Here, in the case of a positive electrode active material for an all-solid lithium ion battery, it is known that the properties are greatly improved if Nb is present on the surface, as described in Patent Document 1, and from this point also, the Nb coating is simple. However, in the current general rolling fluidizing apparatus, in order to coat uniformly, the rolling time of the core particles must be long, and during this time the coated particles collide with each other. There was a risk of breaking. Since the broken particles are tumbling as they are, they can be used as a positive electrode active material for an all-solid lithium-ion battery without any problems if they can be recoated as they are, but they may be taken out of the tumbling fluidizer without recoating. It has been found that when this is used as a positive electrode active material to produce an all-solid-state lithium-ion battery, a battery sometimes having poor characteristics can be obtained. Therefore, it has been important to develop a simple Nb coating method with a short coating time.
そこで、本発明の実施形態は、Ｎｂ被覆された全固体リチウムイオン電池用正極活物質の簡便な製造方法を提供することを課題とする。 Thus, an object of the present invention is to provide a simple method for producing a cathode active material for an Nb-coated all-solid-state lithium ion battery.
本発明は一実施形態において、ニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物前駆体をロッキングミキサー中に投入し、シュウ酸ニオブ水溶液を噴霧してシュウ酸ニオブが被覆された前駆体粉体を作製する工程と、前記シュウ酸ニオブが被覆された前駆体粉体とリチウム化合物とを混合して焼成する工程とを含む全固体リチウムイオン電池用正極活物質の製造方法である。 In one embodiment, the present invention provides a precursor coated with niobium oxalate by charging a transition metal hydroxide precursor composed of nickel, cobalt and manganese into a rocking mixer and spraying an aqueous niobium oxalate solution. A method for producing a positive electrode active material for an all-solid lithium ion battery, comprising a step of preparing a powder and a step of mixing and firing a lithium compound and a precursor powder coated with niobium oxalate.
本発明の別の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、前記ニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物前駆体におけるニッケルとコバルトとマンガンとの物質量比が、前記ニッケル、コバルト及びマンガンの総物質量を１００とすると、８５〜９０：７〜９：０〜７．５（ただし、０を除く）で表され、前記リチウム化合物がＬｉＯＨ・Ｈ2Ｏである。 The method for producing a positive electrode active material for an all-solid-state lithium ion battery according to another embodiment of the present invention is a method of producing a nickel, cobalt, and manganese material in a transition metal hydroxide precursor composed of nickel, cobalt, and manganese. Assuming that the total amount of nickel, cobalt and manganese is 100, the amount ratio is expressed as 85 to 90: 7 to 9: 0 to 7.5 (excluding 0), and the lithium compound is LiOH.H 2 O.
本発明の更に別の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、前記ニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物前駆体の比表面積が６．９ｍ2／ｇ以上である。 The method for producing a cathode active material for an all-solid-state lithium-ion battery according to still another embodiment of the present invention is characterized in that the transition metal hydroxide precursor composed of nickel, cobalt and manganese has a specific surface area of 6.9 m 2. / G or more.
本発明の別の実施形態は、本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法によって製造された全固体リチウムイオン電池用正極活物質を用いて正極層を形成し、前記正極層、固体電解質層及び負極層を用いて全固体リチウムイオン電池を製造する全固体リチウムイオン電池の製造方法である。 Another embodiment of the present invention is to form a positive electrode layer using an all-solid lithium-ion battery positive electrode active material manufactured by the method for manufacturing an all-solid lithium-ion battery positive electrode active material according to an embodiment of the present invention, This is a method for manufacturing an all-solid lithium-ion battery in which an all-solid-state lithium-ion battery is manufactured using the positive electrode layer, the solid electrolyte layer, and the negative electrode layer.
本発明の実施形態によれば、Ｎｂ被覆された全固体リチウムイオン電池用正極活物質の簡便な製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to embodiment of this invention, the simple manufacturing method of the positive electrode active material for all-solid-state lithium ion batteries coated with Nb can be provided.
（全固体リチウムイオン電池用正極活物質の製造方法）
ニッケル源：コバルト源：マンガン源が、モル比でＮｉ：Ｃｏ：Ｍｎ＝８５〜９０：７〜９：０〜７．５（ただし、Ｍｎ＝０を除く）となるように調製した遷移金属水溶液を準備する。ニッケル源、コバルト源、マンガン源は、それぞれ硫酸塩、硝酸塩、塩酸塩等であってもよい。
(Method of producing positive electrode active material for all solid-state lithium ion battery)
A transition metal aqueous solution prepared such that the nickel source: cobalt source: manganese source is molar ratio of Ni: Co: Mn = 85-90: 7-9-9-0-7.5 (excluding Mn = 0). Prepare The nickel source, cobalt source, and manganese source may be sulfate, nitrate, hydrochloride, and the like, respectively.
次に、当該遷移金属水溶液と、水酸化ナトリウム水溶液と、アンモニア水とを別々の槽に用意し、これらを一つの反応槽に投入して晶析法により反応させる。続いて、反応物をろ過、水洗及び乾燥を行うことで組成式：ＮｉaＣｏbＭｎc（ＯＨ）2［式中、ａ：ｂ：ｃ＝８５〜９０：７〜９：０〜７．５（ただし、ｃ＝０を除く）］で示される前駆体粉体を作製する。 Next, the transition metal aqueous solution, the sodium hydroxide aqueous solution, and the ammonia water are prepared in separate tanks, and these are charged into one reaction tank and reacted by a crystallization method. Subsequently, the reaction product is filtered, washed with water and dried to obtain a composition formula: Ni a Co b M n c (OH) 2 [where a: b: c = 85 to 90: 7 to 9: 0 to 7.0. 5 (excluding c = 0)].
このとき、該ニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物前駆体粉体の比表面積が６．９ｍ2／ｇ以上であるのが好ましい。なお、該比表面積は、例えば水酸化物の製造条件(温度、ｐＨ、雰囲気等)によって当業者が常識と考える程度で制御することができる。当該前駆体粉体の比表面積が６．９ｍ2／ｇ以上であると、前駆体粉体の細孔容積が大きくなり、表面に付着する水分の許容量が向上する。このため、前駆体粉体が水分を多くしても粉体のままで維持できるため、「だま」になり難い。このように水分の影響が低減するため、後述のように焼成工程が１度であっても正極活物質の製造がより容易となる。 At this time, the transition metal hydroxide precursor powder composed of nickel, cobalt and manganese preferably has a specific surface area of 6.9 m 2 / g or more. The specific surface area can be controlled, for example, by hydroxide production conditions (temperature, pH, atmosphere, etc.) to such an extent that a person skilled in the art would consider it common sense. When the specific surface area of the precursor powder is 6.9 m 2 / g or more, the pore volume of the precursor powder is increased, and the allowable amount of water adhering to the surface is improved. For this reason, even if the precursor powder has a large amount of water, the precursor powder can be maintained as it is, so that it does not easily become a "dama". As described above, since the influence of moisture is reduced, the production of the positive electrode active material becomes easier even when the firing step is performed once, as described later.
次に、該前駆体粉体をロッキングミキサー（乾式粉体混合機）に投入する。続いて、Ｎｂを６３〜１８９ｇ／Ｌの濃度で含むシュウ酸ニオブ水溶液を、物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．２７〜０．５５となるように、室温で噴霧時間１７〜３５秒、噴霧後均し時間９００秒、回転数３０Ｈｚ、揺動数３０Ｈｚでロッキングミキサー中の該前駆体粉体表面へ噴霧する操作を行い、ロッキングミキサーによって１０〜１５分撹拌し、シュウ酸ニオブが被覆された前駆体粉体を得る。 Next, the precursor powder is charged into a rocking mixer (dry powder mixer). Subsequently, an aqueous niobium oxalate solution containing Nb at a concentration of 63 to 189 g / L was sprayed at room temperature for 17 to 35 seconds so that the substance percentage Nb / (Ni + Co + Mn) would be 0.27 to 0.55, An operation of spraying the precursor powder surface in a rocking mixer at a averaging time of 900 seconds, a rotation speed of 30 Hz, and a rocking speed of 30 Hz is performed, and the mixture is stirred by a rocking mixer for 10 to 15 minutes to be coated with niobium oxalate. To obtain a precursor powder.
ここで、ロッキングミキサーは、回転と揺動が個別に可変できる乾式粉体混合機であり、回転による拡散混合と揺動による移動混合を同時に行なうことで短時間での均一混合が可能である。 Here, the rocking mixer is a dry powder mixer in which rotation and oscillation can be individually varied, and uniform mixing can be performed in a short time by simultaneously performing diffusion mixing by rotation and moving mixing by oscillation.
続いて、シュウ酸ニオブが被覆された前駆体粉体とリチウム化合物とを乾式混合して焼成する。具体的には、まず、ロッキングミキサーからシュウ酸ニオブが被覆された前駆体粉体を取り出し、該前駆体粉体とＬｉＯＨ・Ｈ2Ｏとを、湿度が４０〜６５％の大気雰囲気にて質量百分率Ｌｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が１．０〜１．０３となるように一つの袋に計量する。次に、袋を粗混合して得た粉体（以下、「粗混合粉」とも称する）を袋から全てヘンシェルミキサーに入れて、１０〜３０Ｈｚで５〜１５分間混合する。 Subsequently, the precursor powder coated with niobium oxalate and the lithium compound are dry-mixed and fired. Specifically, first, a precursor powder coated with niobium oxalate is taken out from a rocking mixer, and the precursor powder and LiOH · H 2 O are mass-mixed in an air atmosphere having a humidity of 40 to 65%. Weigh into one bag so that the percentage Li / (Ni + Co + Mn) is 1.0 to 1.03. Next, the powder obtained by roughly mixing the bags (hereinafter, also referred to as “coarse mixed powder”) is put into the Henschel mixer from the bags and mixed at 10 to 30 Hz for 5 to 15 minutes.
続いて、混合した粉体（以下、「混合粉」とも称する）をアルミナ匣鉢に充填する。次に、焼成炉中に酸素を充填し、該アルミナ匣鉢を焼成炉中に入れて、酸素雰囲気下で、３５０℃で２時間、続いて４９０℃で８時間、７５０℃で４時間焼成する。これを室温まで冷却した後、焼成炉から該アルミナ匣鉢をドライエアー中に取り出し、ロールクラッシャーとＡＣＭパルベライザーで解砕して正極活物質を得る。 Subsequently, the mixed powder (hereinafter, also referred to as “mixed powder”) is filled in an alumina sagger. Next, oxygen is filled in the firing furnace, and the alumina sagger is placed in the firing furnace, and fired at 350 ° C. for 2 hours, subsequently at 490 ° C. for 8 hours, and at 750 ° C. for 4 hours under an oxygen atmosphere. . After cooling to room temperature, the alumina sagger is taken out of the firing furnace into dry air, and crushed by a roll crusher and an ACM pulverizer to obtain a positive electrode active material.
上記の方法によれば、焼成工程が１度でよいため、熱処理コストが低減し、生産のリードタイムも減少する。このように、本発明の実施形態に係る製造方法によれば、非常に簡便な方法でＮｂ被覆正極活物質を製造することができる。また、当該正極活物質は、リチウムニッケルコバルトマンガン複合酸化物の表面にＮｂが均一に被覆されている。 According to the above method, the firing step only needs to be performed once, so that the heat treatment cost is reduced and the production lead time is also reduced. As described above, according to the manufacturing method according to the embodiment of the present invention, the Nb-coated positive electrode active material can be manufactured by a very simple method. Further, in the positive electrode active material, the surface of the lithium nickel cobalt manganese composite oxide is uniformly coated with Nb.
（全固体リチウムイオン電池の製造方法）
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法によって製造された全固体リチウムイオン電池用正極活物質を用いて正極層を形成し、固体電解質層、当該正極層及び負極層を備えた全固体リチウムイオン電池を作製することができる。
(Method of manufacturing all-solid lithium-ion battery)
A positive electrode layer is formed using the positive electrode active material for an all solid lithium ion battery manufactured by the method for manufacturing a positive electrode active material for an all solid lithium ion battery according to the embodiment of the present invention, and a solid electrolyte layer, the positive electrode layer, and the negative electrode are formed. An all-solid lithium-ion battery with layers can be made.
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。 Hereinafter, examples for better understanding of the present invention and its advantages will be provided, but the present invention is not limited to these examples.
（実施例１）
硫酸ニッケル：硫酸コバルト：硫酸マンガンがモル比で９０：７：３となるように調製した遷移金属水溶液、水酸化ナトリウム水溶液、アンモニア水を別々の槽に用意し、これらを一つの反応槽に投入して晶析法により反応させ、ろ過、水洗及び乾燥を行うことで組成式：Ｎｉ0.90Ｃｏ0.07Ｍｎ0.03（ＯＨ）2で示される前駆体粉体を得た。この前駆体（以下、コア前駆体とも称する）の平均粒径Ｄ５０は６μｍであり、比表面積（ＢＥＴ）は６．９ｍ2/ｇであった。
(Example 1)
A transition metal aqueous solution, a sodium hydroxide aqueous solution, and an aqueous ammonia solution prepared so that the molar ratio of nickel sulfate: cobalt sulfate: manganese sulfate is 90: 7: 3 are prepared in separate tanks, and these are charged into one reaction tank. The mixture was reacted by a crystallization method, filtered, washed with water and dried to obtain a precursor powder represented by a composition formula: Ni 0.90 Co 0.07 Mn 0.03 (OH) 2 . This precursor (hereinafter, also referred to as core precursor) had an average particle size D50 of 6 μm and a specific surface area (BET) of 6.9 m 2 / g.
次に、コア前駆体の粉体をロッキングミキサーに投入した。続いて、Ｎｂを６３〜１８９ｇ／Ｌの濃度で含むシュウ酸ニオブ水溶液を、室温で噴霧時間１７秒、噴霧後均し時間９００秒、回転数３０Ｈｚ、揺動数３０Ｈｚでロッキングミキサー中の該前駆体粉体表面へ噴霧する操作を行い、ロッキングミキサーによって２０分撹拌した。 Next, the powder of the core precursor was charged into a rocking mixer. Subsequently, an aqueous niobium oxalate solution containing Nb at a concentration of 63 to 189 g / L was sprayed at room temperature for 17 seconds, after spraying for 900 seconds, at a rotation speed of 30 Hz and a rocking speed of 30 Hz, and the precursor in a rocking mixer was used. The operation of spraying on the body powder surface was performed, and the mixture was stirred for 20 minutes by a rocking mixer.
次に、該前駆体粉体とＬｉＯＨ・Ｈ2Ｏとを、湿度が６０％の大気雰囲気にて質量百分率Ｌｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が１．０１となるように一つの袋に計量した。次に、袋を膨らませたまま開口部を手で握って粉が漏れないようにして、握ってない方の手を袋の底にあてて両方の手で袋を揺らして粗混合した。この粗混合した粉体（以下、「粗混合粉」とも称する）を袋から全てヘンシェルミキサーに入れて、１０〜３０Ｈｚで５〜１５分間混合した。 Next, the precursor powder and LiOH.H 2 O were weighed in one bag so that the mass percentage Li / (Ni + Co + Mn) became 1.01 in an air atmosphere with a humidity of 60%. Next, while the bag was inflated, the opening was grasped by hand to prevent the powder from leaking, and the hand not grasping was placed on the bottom of the bag, and the bag was shaken with both hands to perform coarse mixing. All of the coarsely mixed powder (hereinafter also referred to as “coarse mixed powder”) was put into a Henschel mixer from the bag and mixed at 10 to 30 Hz for 5 to 15 minutes.
続いて、混合した粉体（以下、「混合粉」とも称する）をアルミナ匣鉢に充填した。次に、焼成炉中に酸素を充填し、該アルミナ匣鉢を焼成炉中に入れて０．１ＭＰａの酸素雰囲気とし、７５０℃で８時間焼成した。これを室温まで冷却した後、焼成炉から該アルミナ匣鉢をドライエアー中に取り出し、ロールクラッシャーとＡＣＭパルベライザーで解砕して実施例１の正極活物質とした。実施例１の正極活物質の組成は、物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。また、被覆部のＮｂ被覆量を、前駆体の組成分析結果、及びシュウ酸ニオブのニオブ濃度に基づいて算出した。 Subsequently, the mixed powder (hereinafter, also referred to as “mixed powder”) was filled in an alumina sagger. Next, the firing furnace was filled with oxygen, and the alumina sagger was placed in the firing furnace to form an oxygen atmosphere of 0.1 MPa and fired at 750 ° C. for 8 hours. After cooling to room temperature, the alumina sagger was taken out of the firing furnace into dry air, and crushed with a roll crusher and an ACM pulverizer to obtain a positive electrode active material of Example 1. The composition of the positive electrode active material of Example 1 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn). = 0.27. Further, the Nb coating amount of the coating portion was calculated based on the composition analysis result of the precursor and the niobium concentration of niobium oxalate.
（実施例２）
コア前駆体の組成と平均粒径Ｄ５０及び比表面積を表１の通りとした以外は、実施例１と同様の方法でＮｂ被覆正極活物質を作製した。実施例２の正極活物質の組成は、物質量比でＮｉ：Ｃｏ：Ｍｎ＝８７：９：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。
(Example 2)
An Nb-coated positive electrode active material was produced in the same manner as in Example 1, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Example 2 was as follows: Ni: Co: Mn = 87: 9: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn). = 0.27.
（実施例３）
コア前駆体の表面のＮｂが被覆した部分（表１の被覆部）のＮｂ被覆量、シュウ酸ニオブの添加量、被覆時間を表１に示す通りとした以外は、実施例２と同様の方法でＮｂ被覆正極活物質を作製した。実施例３の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝８７：９：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Example 3)
A method similar to that of Example 2 except that the Nb coating amount, the addition amount of niobium oxalate, and the coating time of the Nb-coated portion (coated portion in Table 1) on the surface of the core precursor were as shown in Table 1. Thus, an Nb-coated positive electrode active material was prepared. The composition of the positive electrode active material of Example 3 was Ni: Co: Mn = 87: 9: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
（実施例４）
コア前駆体の平均粒径Ｄ５０及び比表面積を表１の通りとした以外は、実施例１と同様の方法でＮｂ被覆正極活物質を作製した。実施例４の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０３、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。
(Example 4)
An Nb-coated positive electrode active material was produced in the same manner as in Example 1, except that the average particle diameter D50 and the specific surface area of the core precursor were as shown in Table 1. The composition of the positive electrode active material of Example 4 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.03 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.27.
（実施例５）
コア前駆体の組成と平均粒径Ｄ５０及び比表面積を表１の通りとした以外は、実施例３と同様の方法でＮｂ被覆正極活物質を作製した。実施例５の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０３、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Example 5)
An Nb-coated positive electrode active material was produced in the same manner as in Example 3, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Example 5 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.03 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
（実施例６）
コア前駆体の組成と平均粒径Ｄ５０及び比表面積を表１の通りとした以外は、実施例３と同様の方法でＮｂ被覆正極活物質を作製した。実施例６の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝８５：７．５：７．５、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Example 6)
An Nb-coated positive electrode active material was produced in the same manner as in Example 3, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Example 6 was Ni: Co: Mn = 85: 7.5: 7.5 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
実施例１〜６の正極活物質の粒子断面をＥＰＭＡで観察したところ、いずれもリチウムニッケルコバルトマンガン複合酸化物の表面にＮｂが均一に被覆されており、粒子表面にリチウムニッケルコバルトマンガン複合酸化物が露出していることはなかった。 When the cross section of the particles of the positive electrode active materials of Examples 1 to 6 was observed by EPMA, the surface of the lithium nickel cobalt manganese composite oxide was uniformly coated with Nb, and the surface of the particles was lithium nickel cobalt manganese composite oxide. Was never exposed.
（比較例１）
硫酸ニッケル：硫酸コバルト：硫酸マンガンがモル比で９０：７：３となるように調製した遷移金属水溶液、水酸化ナトリウム水溶液、アンモニア水を別々の槽に用意し、これらを一つの反応槽に投入して晶析法により反応させ、ろ過、水洗及び乾燥を行うことで組成式：Ｎｉ0.90Ｃｏ0.07Ｍｎ0.03（ＯＨ）2で示される前駆体粉体を得た。この前駆体（コア前駆体とも称する）の平均粒径Ｄ５０は６μｍであり、比表面積（ＢＥＴ）は６．９ｍ2/ｇであった。次に、当該前駆体と水酸化リチウムを実施例１と同様の方法で混合した後、アルミナ匣鉢に充填した。次に、焼成炉中に酸素を充填し、該アルミナ匣鉢を焼成炉中に入れて０．１ＭＰａの酸素雰囲気とし、７５０℃で８時間焼成した。これを室温まで冷却した後、焼成炉から該アルミナ匣鉢をドライエアー中に取り出し、ロールクラッシャーとＡＣＭパルベライザーで解砕し、正極材を得た。
(Comparative Example 1)
A transition metal aqueous solution, a sodium hydroxide aqueous solution, and an aqueous ammonia solution prepared so that the molar ratio of nickel sulfate: cobalt sulfate: manganese sulfate is 90: 7: 3 are prepared in separate tanks, and these are charged into one reaction tank. The mixture was reacted by a crystallization method, filtered, washed with water and dried to obtain a precursor powder represented by a composition formula: Ni 0.90 Co 0.07 Mn 0.03 (OH) 2 . This precursor (also referred to as core precursor) had an average particle size D50 of 6 μm and a specific surface area (BET) of 6.9 m 2 / g. Next, the precursor and lithium hydroxide were mixed in the same manner as in Example 1, and then charged into an alumina sagger. Next, the firing furnace was filled with oxygen, and the alumina sagger was placed in the firing furnace to form an oxygen atmosphere of 0.1 MPa and fired at 750 ° C. for 8 hours. After cooling to room temperature, the alumina sagger was taken out of the firing furnace in dry air, and crushed with a roll crusher and an ACM pulverizer to obtain a positive electrode material.
続いて、当該正極材の粉体をロッキングミキサーに投入した。Ｎｂを６３〜１８９ｇ／Ｌの濃度で含むシュウ酸ニオブ水溶液を、室温で噴霧時間１７秒、噴霧後均し時間９００秒、回転数３０Ｈｚ、揺動数３０Ｈｚでロッキングミキサー中の該前駆体粉体表面へ噴霧する操作を行い、５００℃で６時間焼成した。これを室温まで冷却した後、焼成炉から該アルミナ匣鉢をドライエアー中に取り出し、ロールクラッシャーとＡＣＭパルベライザーで解砕し、比較例１の正極活物質とした。比較例１の正極活物質の組成は、物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。 Subsequently, the powder of the positive electrode material was put into a rocking mixer. The precursor powder in a rocking mixer was sprayed with an aqueous niobium oxalate solution containing Nb at a concentration of 63 to 189 g / L at room temperature for a spraying time of 17 seconds, a spraying time of 900 seconds, a rotation speed of 30 Hz, and a rocking speed of 30 Hz. An operation of spraying on the surface was performed, and firing was performed at 500 ° C. for 6 hours. After cooling to room temperature, the alumina sagger was taken out of the firing furnace in dry air, and crushed with a roll crusher and an ACM pulverizer to obtain a positive electrode active material of Comparative Example 1. The composition of the positive electrode active material of Comparative Example 1 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn). = 0.27.
（比較例２）
コア前駆体の組成、平均粒径Ｄ５０、比表面積を表１の通りとした以外は、比較例１と同様の方法でＮｂ被覆正極活物質を作製した。比較例２の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝８７：９：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。
(Comparative Example 2)
An Nb-coated positive electrode active material was produced in the same manner as in Comparative Example 1, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Comparative Example 2 was Ni: Co: Mn = 87: 9: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.27.
（比較例３）
被覆部のＮｂ被覆量、シュウ酸ニオブの添加量、被覆時間を表１の通りとした以外は、比較例２と同様の方法でＮｂ被覆正極活物質を作製した。比較例３の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝８７：９：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Comparative Example 3)
An Nb-coated positive electrode active material was produced in the same manner as in Comparative Example 2, except that the coating amount of Nb, the amount of niobium oxalate added, and the coating time were as shown in Table 1. The composition of the positive electrode active material of Comparative Example 3 was Ni: Co: Mn = 87: 9: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
（比較例４）
コア前駆体の平均粒径Ｄ５０、比表面積を表１の通りとした以外は、比較例１と同様の方法でＮｂ被覆正極活物質を作製した。比較例４の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０３、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．２７であった。
(Comparative Example 4)
An Nb-coated positive electrode active material was produced in the same manner as in Comparative Example 1, except that the average particle size D50 and the specific surface area of the core precursor were as shown in Table 1. The composition of the positive electrode active material of Comparative Example 4 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.03 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.27.
（比較例５）
コア前駆体の組成、平均粒径Ｄ５０、比表面積を表１の通りとした以外は、比較例３と同様の方法でＮｂ被覆正極活物質を作製した。比較例５の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝９０：７：３、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０３、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Comparative Example 5)
An Nb-coated positive electrode active material was prepared in the same manner as in Comparative Example 3, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Comparative Example 5 was Ni: Co: Mn = 90: 7: 3 in mass ratio, Li / (Ni + Co + Mn) = 1.03 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
（比較例６）
コア前駆体の組成、平均粒径Ｄ５０、比表面積を表１の通りとした以外は、比較例３と同様の方法でＮｂ被覆正極活物質を作製した。比較例６の正極活物質の組成は物質量比でＮｉ：Ｃｏ：Ｍｎ＝８５：７．５：７．５、かつ質量百分率でＬｉ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝１．０１、かつ物質量百分率Ｎｂ／（Ｎｉ＋Ｃｏ＋Ｍｎ）＝０．５５であった。
(Comparative Example 6)
An Nb-coated positive electrode active material was prepared in the same manner as in Comparative Example 3, except that the composition of the core precursor, the average particle diameter D50, and the specific surface area were as shown in Table 1. The composition of the positive electrode active material of Comparative Example 6 was Ni: Co: Mn = 85: 7.5: 7.5 in mass ratio, Li / (Ni + Co + Mn) = 1.01 in mass percentage, and mass percentage Nb / (Ni + Co + Mn) = 0.55.
−電池特性の評価（全固体リチウムイオン電池）−
実施例および比較例の正極活物質と、ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5とを、７：３の質量比で秤量し、混合して正極合剤とした。内径１０ｍｍの金型中にＬｉ−Ｉｎ合金、ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5、正極合剤、Ａｌ箔をこの順で充填し、５００ＭＰａでプレスした。このプレス後の成形体を、金属製治具を用いて１００ＭＰａで拘束することにより、全固体リチウムイオン電池を作製した。この電池について、充放電レート０．０５Ｃで得られた初期放電容量（２５℃、充電上限電圧：３．７Ｖ、放電下限電圧：２．５Ｖ）を測定した。次に充放電レート１Ｃで充放電を１０回繰り返した（５５℃、充電上限電圧：３．７Ｖ、放電下限電圧：２．５Ｖ）。充放電レート１Ｃでの１回目の放電で得られた容量を放電容量１とし、充放電レート１Ｃでの１０回目の放電で得られた容量を放電容量２とし、（放電容量２）／（放電容量１）の比を百分率としてサイクル特性：「１０サイクル（％）」とした。
試験条件及び評価結果を表１に示す。
-Evaluation of battery characteristics (All-solid-state lithium-ion battery)-
Positive active materials of Examples and Comparative Examples, a LiI-Li 2 S-P 2 S 5, 7: weighed at a weight ratio of 3, and a positive electrode mixture by mixing. Li-an In alloy into a mold having an inner diameter of 10mm, LiI-Li 2 S- P 2 S 5, the positive electrode mixture, filling the Al foil in this order, and pressed at 500 MPa. The pressed compact was restrained at 100 MPa using a metal jig to produce an all-solid-state lithium-ion battery. For this battery, the initial discharge capacity (25 ° C., charge upper limit voltage: 3.7 V, discharge lower limit voltage: 2.5 V) obtained at a charge / discharge rate of 0.05 C was measured. Next, charge / discharge was repeated 10 times at a charge / discharge rate of 1 C (55 ° C., charge upper limit voltage: 3.7 V, discharge lower limit voltage: 2.5 V). The capacity obtained by the first discharge at the charge / discharge rate 1C is defined as the discharge capacity 1, the capacity obtained by the 10th discharge at the charge / discharge rate 1C is defined as the discharge capacity 2, and (discharge capacity 2) / (discharge capacity) The cycle characteristics were defined as "10 cycles (%)" with the ratio of the capacity 1) as a percentage.
Table 1 shows the test conditions and evaluation results.
前駆体の組成及び処理方法が同様の実施例１と比較例１とを対比すると、実施例１は焼成工程が１回で済むにもかかわらず、比較例１に対して電池特性が同程度または優れていた。
同様に、実施例２〜６についても、焼成工程が１回で済むにもかかわらず、前駆体の組成及び処理方法がそれぞれ同様である比較例２〜６に対して電池特性が同程度または優れていた。
Comparing Example 1 and Comparative Example 1 in which the precursor composition and the treatment method are the same, Example 1 has the same or better battery characteristics as Comparative Example 1 even though only one firing step is required. It was excellent.
Similarly, the battery characteristics of Examples 2 to 6 are comparable to or superior to those of Comparative Examples 2 to 6 in which the precursor composition and the treatment method are the same, though the firing step is only required once. I was
Claims (4)
前記シュウ酸ニオブが被覆された前駆体粉体とリチウム化合物とを混合して焼成する工程と、
を含む全固体リチウムイオン電池用正極活物質の製造方法。 A step of introducing a hydroxide precursor of a transition metal composed of nickel, cobalt and manganese into a rocking mixer, spraying an aqueous niobium oxalate solution to prepare a precursor powder coated with niobium oxalate,
A step of mixing and baking the precursor powder coated with the niobium oxalate and a lithium compound,
A method for producing a positive electrode active material for an all-solid lithium ion battery, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018186849A JP7118843B2 (en) | 2018-10-01 | 2018-10-01 | Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for producing all-solid-state lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018186849A JP7118843B2 (en) | 2018-10-01 | 2018-10-01 | Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for producing all-solid-state lithium-ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020057503A true JP2020057503A (en) | 2020-04-09 |
| JP7118843B2 JP7118843B2 (en) | 2022-08-16 |
Family
ID=70107539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018186849A Active JP7118843B2 (en) | 2018-10-01 | 2018-10-01 | Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for producing all-solid-state lithium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7118843B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113380995A (en) * | 2021-04-29 | 2021-09-10 | 厦门大学 | Modification method of lithium-rich cathode material |
| JP2021170494A (en) * | 2020-04-16 | 2021-10-28 | 日産自動車株式会社 | Rechargeable battery |
| KR20230061171A (en) * | 2021-10-28 | 2023-05-08 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
| KR20230061730A (en) * | 2021-10-29 | 2023-05-09 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015002120A (en) * | 2013-06-17 | 2015-01-05 | 住友金属鉱山株式会社 | Nickel cobalt manganese composite hydroxide, and method for manufacturing the same |
| JP2017098196A (en) * | 2015-11-27 | 2017-06-01 | 住友金属鉱山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and method for manufacturing coating liquid |
| JP2018073686A (en) * | 2016-10-31 | 2018-05-10 | 住友化学株式会社 | Positive electrode active material precursor for lithium secondary battery and method of producing positive electrode active material for lithium secondary battery |
-
2018
- 2018-10-01 JP JP2018186849A patent/JP7118843B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015002120A (en) * | 2013-06-17 | 2015-01-05 | 住友金属鉱山株式会社 | Nickel cobalt manganese composite hydroxide, and method for manufacturing the same |
| JP2017098196A (en) * | 2015-11-27 | 2017-06-01 | 住友金属鉱山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and method for manufacturing coating liquid |
| JP2018073686A (en) * | 2016-10-31 | 2018-05-10 | 住友化学株式会社 | Positive electrode active material precursor for lithium secondary battery and method of producing positive electrode active material for lithium secondary battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021170494A (en) * | 2020-04-16 | 2021-10-28 | 日産自動車株式会社 | Rechargeable battery |
| CN113380995A (en) * | 2021-04-29 | 2021-09-10 | 厦门大学 | Modification method of lithium-rich cathode material |
| CN113380995B (en) * | 2021-04-29 | 2022-08-12 | 厦门大学 | A kind of modification method of lithium-rich cathode material |
| KR20230061171A (en) * | 2021-10-28 | 2023-05-08 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
| KR102707545B1 (en) | 2021-10-28 | 2024-09-13 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
| KR20230061730A (en) * | 2021-10-29 | 2023-05-09 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
| KR102707546B1 (en) | 2021-10-29 | 2024-09-13 | 주식회사 에코프로비엠 | Method for manufacturing positive electrode active material for solid secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7118843B2 (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5742935B2 (en) | Positive electrode active material particles, and positive electrode and all solid state battery using the same | |
| JP6744880B2 (en) | Positive electrode active material for lithium ion battery, method for producing positive electrode active material for lithium ion battery, positive electrode for lithium ion battery and lithium ion battery | |
| JP6943985B2 (en) | Positive electrode for solid-state battery, solid-state battery, and method for manufacturing solid-state battery | |
| JP7109334B2 (en) | Method for manufacturing positive electrode for all-solid-state lithium-ion battery and method for manufacturing all-solid-state lithium-ion battery | |
| JP2020057503A (en) | Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for manufacturing all-solid-state lithium-ion battery | |
| JP6737930B1 (en) | Positive electrode active material for all-solid-state lithium-ion battery, positive electrode for all-solid-state lithium-ion battery, all-solid-state lithium-ion battery, and method for producing positive-electrode active material for all-solid-state lithium-ion battery | |
| JP7118851B2 (en) | Method for manufacturing positive electrode active material for all-solid-state lithium-ion battery, and method for manufacturing all-solid-state lithium-ion battery | |
| US20160351898A1 (en) | Method for preparing a positive active material for a lithium secondary battery | |
| CN104078669B (en) | A kind of preparation method of polynary positive pole material | |
| CN103137976B (en) | Nano composite material and preparation method thereof and positive electrode and battery | |
| JP6640434B1 (en) | Positive electrode active material for all-solid-state lithium-ion battery, positive electrode for all-solid-state lithium-ion battery, all-solid-state lithium-ion battery | |
| JP2016526008A5 (en) | ||
| JP7392464B2 (en) | Positive electrode active material for all-solid-state lithium ion secondary battery, its manufacturing method, and all-solid-state lithium ion secondary battery | |
| CN111180689A (en) | Micron hollow porous composite spherical sodium ion battery cathode material and preparation method thereof | |
| CN108023068B (en) | 4.40V high-voltage lithium cobaltate material and preparation method thereof | |
| KR20190116999A (en) | Positive electrode active material, its manufacturing method, and positive electrode and lithium ion battery | |
| JP6984185B2 (en) | Positive electrode active material, positive electrode and sodium ion battery, and method for manufacturing positive electrode active material | |
| CN103996838A (en) | Lithium zirconate-cladded lithium-rich positive material for lithium ion battery and preparation method thereof | |
| Lin et al. | Stabilization of high-energy cathode materials of metal-ion batteries: Control strategies and synthesis protocols | |
| CN115312735A (en) | Positive electrode material and preparation method and application thereof | |
| CN106654224B (en) | A kind of cobalt acid lithium composite material and preparation method, positive electrode | |
| CN107732234A (en) | A kind of Er, Zr metal ion mixing and doping tertiary cathode material and preparation method thereof | |
| JP2003146662A (en) | Lithium-nickel-manganese complex oxide, method for manufacturing the same and use of the same | |
| JP7292026B2 (en) | Method for producing positive electrode active material for all-solid-state lithium-ion battery, and method for producing all-solid-state lithium-ion battery | |
| CN108417783A (en) | Niobium manganese modified tin oxide coated nickel cobalt lithium manganate positive electrode material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210916 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220615 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220712 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220803 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7118843 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |