CN100389069C - Ni-Mn-Co oxide with secondary sphere structure and process for preparing same - Google Patents
Ni-Mn-Co oxide with secondary sphere structure and process for preparing same Download PDFInfo
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Abstract
The present invention relates to a secondary spherical nickel, manganese and cobalt oxide and a preparing method thereof. The proportion of the nickel, the manganese and the cobalt of the secondary spherical nickel, manganese and cobalt oxide is Ni: Mn: Co =x: y: z, x+y+z =1, x/y=0.9-1.1, z=0 to 0.4. The preparing method of the present invention is that under an ammonia condition, the pH value of reaction is controlled, and a nickel, manganese and cobalt hydroxide with a secondary spherical structure is synthesized through a cocrystallization method; hydroxide precipitation is calcined at the temperature of 400 to 900 DEG C, the secondary spherical nickel, manganese and cobalt oxide is decomposed and obtained, and the nickel, the cobalt, the manganese and the oxygen in the compound are combined through chemical bonds but are not in simple physical mixing. The manufactured nickel, manganese and cobalt oxide has a secondary spherical structure and the characteristic of high tap density. The nickel, manganese and cobalt oxide used as a precursor of anode materials for preparing lithium ion batteries has the advantages of low cost, high specific energy, good cycle performance, etc.
Description
Technical field
The invention belongs to the energy and material preparing technical field, be specifically related to a kind of Ni-Mn-Co-O thing and preparation method thereof with unique secondary spherical structure.
Background technology
Lithium ion battery, because of have high-voltage, energy density is big, self-discharge is little, have extended cycle life, non-environmental-pollution, is the charge power supply of high-grade electronic product first-selection, uses very extensive.The oxide compound such as the LiCoO of lithium and transition metal (as Co, Ni, Mn etc.)
2, LiNiO
2, LiMn
2O
4All can be used as the positive electrode material of lithium ion battery.The cobalt acid lithium of laminate structure uses at most, also has the lithium nickelate of laminate structure and the lithium manganate of spinel structure.Their leading indicator has reversible capacity, platform voltage, cyclical stability, security and price etc. that quality is respectively arranged.
Reduce cost, improve the quality, manufacture excellent performance and low-cost positive electrode material is one of key issue of high-capacity lithium ion cell development.Carry out doping vario-property to reduce cost for cobalt acid lithium more, in Chinese patent 991194462, mix metal element A l, Ni etc.; Take to mix metallic elements such as Co, Cr for lithium nickelate and lithium manganate improves structural stability or coat layer of substance contacting with isolated and electrolytic solution outside particle more, as United States Patent (USP) 6274272,6551571, Chinese patent application 00173472 etc., to introduce other compositions but mix and coat, bring greater loss to capacity.
In recent years, it is initial feed with nickel oxide (NiO), Manganse Dioxide (MnO2) and tricobalt tetroxide (Co3O4) powder that employing is also arranged, and after mixing by physical mechanical, adds Quilonum Retard (Li
2CO
3), prepare nickel manganese oxygen plus plate material for lithium through solid state sintering, to reduce cost.Yet, owing to adopt single metal oxide powder, must bring the ununiformity of material, thereby cause product behind the sintering to be difficult to obtain not having the material of dephasign by the simple physics mechanically mixing, make capacity attenuation fast, defectives such as comprehensive electrochemical properties reduction.In addition, adopt this method, many important physical indexs of each metal oxide such as granular size, shape characteristic etc. are all needed to be strict with and control, this is to bringing very big difficulty on the production application.
Summary of the invention
The present invention has overcome present anode material for lithium-ion batteries cost height, nickel manganese cobalt is the shortcoming of the bad and complicated process of preparation of positive electrode material performance, provides that a kind of cost is low, tap density is high, the secondary ball nickel magnesium cobalt hydroxide and the simple and convenient preparation method thereof that are used to produce the high-performance and low-cost precursor of lithium ionic cell positive material of stay in grade.
The present invention is intended to for developing low-cost high-performance multi-element metal lithium oxide compound anode material for lithium-ion batteries provides suitable presoma, and it has the oxyhydroxide and the oxide compound of the high-active multiple metal of secondary spherical structure.Secondary ball high-active multiple material is meant the simultaneous material of metallic element more than three kinds or three kinds except that lithium ion,, cobalt nickeliferous, manganese salt solution comprising adopting, the oxide compound of gained after oxyhydroxide of producing by coprecipitation method that contains nickel, cobalt, manganese and the roasting thereof, the ratio of each metal is mol ratio Ni: Mn: Co=x: y: z in the multi-component, x+y+z=1 wherein, x/y=0.9-1.1, z=0～0.4.Nickel-cobalt in this compound-manganese-oxygen is to mix by the combination of chemical bond rather than simple physics.The special secondary spherical structure that nickel magnesium cobalt hydroxide has, and the surface arranges small-particle closely, and this coating of particles is sheet, strip, closely spherical, and the specific surface area of this nickel magnesium cobalt hydroxide is 5-50m
2/ g, tap density is 1.0-2.0g/cm
3, middle particle diameter is 5-20 μ m.The Ni-Mn-Co-O thing has special secondary spherical structure, and promptly small-particle is closely arranged on sphere aggregates and surface, and this coating of particles is sheet, strip, closely spherical, and the specific surface area of this Ni-Mn-Co-O thing is 2-25m
2/ g, tap density is 1.2-2.5g/cm
3, middle particle diameter is 5-20 μ m.
The inventive method comprises the following steps:
1) Ni: Mn: Co=x: y: z in molar ratio, x+y+z=1 wherein, x/y=0.9-1.1, z=0～0.4, the preparing metal total concn be 1～1.5mol/L+the divalent nickel salt ,+divalent manganese salt and+mixed aqueous solution of divalent cobalt salt; Compound concentration is the NaOH solution of 1～10mol/L; Compound concentration is the NH of 5～10mol/L
4 +Solion;
2) with above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=2～8: 1, the effect of ammonia is and cobalt, nickel, manganese complexing the formation speed and the shape of control oxyhydroxide; Adding NaOH solution is 9.0～13.0 with the control pH value in reaction; Temperature of reaction is at 30～90 ℃; Reacted after 20～30 hours ageing 10～20 hours, the pH of control ageing process is consistent with the pH of reaction process; Separating also, washing precipitation gets secondary ball nickel magnesium cobalt hydroxide; Regulate the particle diameter of the speed control product of stirring velocity;
3) at the 400-900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxide, calcination time is 3-15 hour, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure.
The invention has the beneficial effects as follows: cocrystallization obtains uniform nickel magnesium cobalt hydroxide under the ammonia environment, nickel-cobalt in this compound-manganese-oxygen is to mix by the combination of chemical bond rather than simple physics, microtexture shows the secondary spherical looks, have secondary spherical structure and the high characteristics of tap density with the prepared Ni-Mn-Co-O thing of this presoma, be used to prepare lithium ion battery as the positive electrode material presoma and have advantages such as cost is low, specific energy is high, good cycle.The multi-element metal of this preparation secondary spherical structure is that oxyhydroxide and oxide compound novel process have originality, for preparation secondary ball low-cost and high-performance anode material for lithium-ion batteries finds a new approach, has reduced cost.
Description of drawings
Fig. 1 is the sem photograph of secondary ball nickel magnesium cobalt hydroxide;
Fig. 2 is the sem photograph of Ni-Mn-Co oxide with secondary sphere structure;
Embodiment
Embodiment 1:
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the rose vitriol that 1: 1 preparing metal total concn is 1mol/L, single nickel salt, manganous sulfate; Compound concentration is the NaOH solution of 1mol/L; Compound concentration is the NH of 5mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=8: 1; Adding NaOH solution is 13.0 with the control pH value in reaction; Temperature of reaction is at 30 ℃; Reacted after 30 hours ageing 10 hours, the pH of control ageing process is consistent with the pH of reaction process; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.70g/cm
3, specific surface area is 9.6m
2/ g, middle particle diameter D
50=7.2 μ m.
At the 900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 3 hours, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure, records its tap density 1.80g/cm
3, specific surface area is 18m
2/ g, middle particle diameter D
50=8.31 μ m.
Get these composite oxides 40g, be after 1/1 the mol ratio and Quilonum Retard thorough mixing by Li/ (Ni+Mn+Co), place retort furnace, be warming up to 700 ℃ of following constant temperature 10hr, the fine grinding in autogenous mill of cooling back was placed in the retort furnace 850 ℃ of following constant temperature 10hr in 30 minutes, temperature rise rate is 2 ℃/min, make secondary ball lithium-nickel-manganese-cobalt oxidation thing, have tangible secondary spherical structure, record tap density 2.35g/cm
3, specific surface area is 0.46m
2/ g, middle particle diameter D
50=8.5 μ m.Gained secondary ball lithium-nickel-manganese-cobalt oxidation thing is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 170mAh/g (4.5V vs.Li), after 20 circulations, and specific storage decay 1.30%.
Embodiment 2
Ni: Mn: Co=1.1 in molar ratio: the mixed aqueous solution of the rose vitriol that 1: 0.1 preparing metal total concn is 1.5mol/L, single nickel salt, manganous sulfate; Compound concentration is the NaOH solution of 10mol/L; Compound concentration is the NH of 10mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=2: 1; Adding NaOH solution is 9.0 with the control pH value in reaction; Temperature of reaction is at 90 ℃; Reacted after 20 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of reaction process; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.580g/cm
3, specific surface area is 11.6m
2/ g, middle particle diameter D
50=6.2 μ m.
At the 400 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 15 hours, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure, has obvious secondary ball feature, records its tap density 1.95g/cm
3, specific surface area is 10.5m
2/ g, middle particle diameter D
50=7.91 μ m.
Embodiment 3
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the Xiao Suangu that 1.1: 0.5 preparing metal total concns are 1.5mol/L, nickelous nitrate, manganese nitrate solution; Compound concentration is the NaOH solution of 8mol/L; Compound concentration is the NH of 6mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=4: 1; Adding NaOH solution is 12.0 with the control pH value in reaction; Temperature of reaction is at 70 ℃; Reacted after 30 hours ageing 15 hours, the pH of control ageing process is consistent with the pH of reaction process; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.9g/cm
3, specific surface area is 7.1m
2/ g, middle particle diameter D
50=6.9 μ m.
At the 800 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 10 hours, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure, has obvious secondary ball feature, records tap density 2.35g/cm
3, specific surface area is 8m
2/ g, middle particle diameter D
50=9.5 μ m.
Embodiment 4
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the cobalt chloride that 0.9: 0.9 preparing metal total concn is 1.2mol/L, nickelous chloride, manganous nitrate; Compound concentration is the NaOH solution of 2mol/L; Compound concentration is the NH of 10mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=5: 1; Adding NaOH solution is 10.0 with the control pH value in reaction; Temperature of reaction is at 40 ℃; Reacted after 25 hours ageing 15 hours, the pH of control ageing process is consistent with the pH of reaction process; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.20g/cm3, and specific surface area is 15.1m2/g, middle particle diameter D50=9.1 μ m.
At the 500 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 15 hours, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure, has obvious secondary ball feature, record tap density 1.6g/cm3, specific surface area is 22m2/g, middle particle diameter D50=6.31 μ m.
Claims (3)
1. Ni-Mn-Co oxide with secondary sphere structure, it is characterized in that: have secondary spherical structure Ni-Mn-Co-O thing, wherein the ratio of nickel manganese cobalt is: Ni: Mn: Co=x: y: z, x+y+z=1, x/y=0.9-1.1, z=0～0.4.
2. the preparation method of a Ni-Mn-Co oxide with secondary sphere structure the steps include:
(1), Ni: Mn: Co=x: y: z in molar ratio, x+y+z=1 wherein, x/y=0.9-1.1, z=0～0.4, the preparing metal total concn be 1～1.5mol/L+the divalent nickel salt ,+divalent manganese salt and+mixed aqueous solution of divalent cobalt salt; Compound concentration is the NaOH solution of 1～10mol/L; Compound concentration is the NH of 5～10mol/L
4 +Solion;
(2), with above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The add-on of ionic compound is mol ratio NH
4 +/ (Ni+Mn+Co)=2～8: 1; Adding NaOH solution is 9.0～13.0 with the control pH value in reaction; Temperature of reaction is at 30～90 ℃; Reacted after 20～30 hours ageing 10～20 hours, the pH of control ageing process is consistent with the pH of reaction process; Separating also, washing precipitation gets secondary ball nickel magnesium cobalt hydroxide;
(3), at the 400-900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxide, calcination time is 3-15 hour, decomposes to obtain Ni-Mn-Co oxide with secondary sphere structure.
3. the preparation method of Ni-Mn-Co oxide with secondary sphere structure according to claim 2 is characterized in that:
Described nickel salt, manganese salt and cobalt salt are a kind of in vitriol, nitrate and the muriate or two kinds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9059465B2 (en) | 2008-04-17 | 2015-06-16 | Jx Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion battery, positive electrode for secondary battery, and lithium ion battery |
| US20130136991A1 (en) | 2011-11-30 | 2013-05-30 | Lawrence Livermore National Security, Llc | High energy/power density nickel oxide/hydroxide materials and nickel cobalt oxide/hydroxide materials and production thereof |
| CN103172118A (en) * | 2013-03-19 | 2013-06-26 | 南通瑞翔新材料有限公司 | Method for preparing spherical cobaltosic oxide and manganese oxide |
| CN105810939A (en) * | 2014-12-31 | 2016-07-27 | 北京当升材料科技股份有限公司 | Preparation method of low-sulfur multi-element positive electrode material |
| CN105140505A (en) * | 2015-06-30 | 2015-12-09 | 贵州省分析测试研究院 | Preparation method for cobalt-manganese-nickel oxides |
| KR101768374B1 (en) * | 2016-04-29 | 2017-08-14 | 주식회사 엘지화학 | Composite transition metal oxide precursor and preparing method thereof, and cathode active material using the same |
| JP6836369B2 (en) * | 2016-10-31 | 2021-03-03 | 住友化学株式会社 | Method for manufacturing positive electrode active material precursor for lithium secondary battery and positive electrode active material for lithium secondary battery |
| CN107973349B (en) * | 2017-11-24 | 2020-01-10 | 贵州大龙汇成新材料有限公司 | Aluminum-doped nickel-manganese binary precursor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547277A (en) * | 2003-12-16 | 2004-11-17 | 湖南晶鑫科技股份有限公司 | Manganese nickel cobalt composite lithium-inserting oxide and manufacturing method thereof |
| CN1622371A (en) * | 2004-12-30 | 2005-06-01 | 清华大学 | Process for preparing high density spherical nickel-cobalt lithium manganate as anode material of lithium ion cell |
| CN1774400A (en) * | 2003-04-17 | 2006-05-17 | 清美化学股份有限公司 | Lithium-nickel-cobalt-maganese containing composite oxide, material for positive electrode active material for lithium secondary battery, and methods for producing these |
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| CN1774400A (en) * | 2003-04-17 | 2006-05-17 | 清美化学股份有限公司 | Lithium-nickel-cobalt-maganese containing composite oxide, material for positive electrode active material for lithium secondary battery, and methods for producing these |
| CN1547277A (en) * | 2003-12-16 | 2004-11-17 | 湖南晶鑫科技股份有限公司 | Manganese nickel cobalt composite lithium-inserting oxide and manufacturing method thereof |
| CN1622371A (en) * | 2004-12-30 | 2005-06-01 | 清华大学 | Process for preparing high density spherical nickel-cobalt lithium manganate as anode material of lithium ion cell |
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