CN100444432C - Nickel oxide mixed with cobalt manganese hydroxy base and preparation method thereof - Google Patents

Nickel oxide mixed with cobalt manganese hydroxy base and preparation method thereof Download PDF

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CN100444432C
CN100444432C CNB2006101600554A CN200610160055A CN100444432C CN 100444432 C CN100444432 C CN 100444432C CN B2006101600554 A CNB2006101600554 A CN B2006101600554A CN 200610160055 A CN200610160055 A CN 200610160055A CN 100444432 C CN100444432 C CN 100444432C
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solution
preparation
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mixed
filter cake
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CN101000958A (en
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常照荣
吴锋
汤宏伟
陈中军
朱志红
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Henan Normal University
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Henan Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

This invention discloses a nickel-oxhydroxide doped with cobalt-manganese and its preparation method, relating to a nickel compound, from which, the product prepared has high tap density. The technique program is the formula of Ni1-x-yCoxMnyOOH, in which, 1/5<=x<=2/5, 1/5<=y<=2/5. Its preparation method includes the following steps: (1) the mixed salt solution is prepared by Ni, Mn and Co, which molar ratio is 1:(1/5<=x<=2/5) :(1/5<=y<=2/5), and sodium hydroxide or potassium hydroxide solution is prepared, (2) precipitation reaction, (3) polyacrylamide is accessed into the above slurry for poly deposition, (4) the filter cake is washed, dried, crushed and sift out to get the product. This invention is used for the anode material of lithium battery.

Description

A kind of preparation method of nickel oxide mixed with cobalt manganese hydroxy base
Technical field:
The invention belongs to the preparation method of a kind of compound of nickel, particularly a kind of nickel oxide mixed with cobalt manganese hydroxy base.
Background technology:
The positive electrode of lithium ion battery mainly is LiCoO in the market 2, but cobalt resource is very deficient, costs an arm and a leg and toxic slightly to environment, the substitution material of therefore seeking inexpensive, environmentally friendly and function admirable is unusual active research field at present.Wherein be considered to the most competitive substitution material LiNiO 2And LiMn 2O 4Exist critical defect separately.LiMn 2O 4Aboundresources, cost are low, environmentally friendly, but cycle performance is poor, and particularly the fast problem of capacity attenuation is not still effectively solved under the high temperature.LiNiO 2Though the positive electrode price is low, reversible capacity is high, electrochemical window is wide, but this material synthesis is difficult to control, easily produce the cation mixing, form the non-stoichiometric product, and fail safe is also poor, in order to overcome these defectives, people have carried out big quantity research from the doping vario-property aspect, think with Li (Ni 1/3Co 1/3Mn 1/3) O 2The polynary metal oxide LiNi of doping Co, Mn for representative 1-x-yCo xMn yO 2, (1/10≤x≤2/5,1/10≤y≤2/5) has Co system, Ni system and Mn simultaneously is the advantage of positive electrode: the specific capacity height, good cycle, better heat stability and environmentally friendly, preparation condition is also gentle relatively, material cost is lower, is expected to become lithium ion anode material of new generation.But its tap density of report is low in the document at present, has directly influenced LiNi 1-x-yCo xMn yO 2Volume and capacity ratio, be the bottleneck that further develops of this material of restriction.And the lithium ion anode material precursor doped has the tap density of the nickel oxide of cobalt, manganese element just determining the quality of the chemical properties such as specific capacity of lithium ion anode material.At present the lithium ion anode material presoma of domestic and foreign literature report adopt mostly nickel, cobalt, manganese salt and NaOH coprecipitation reaction, after filtration, the prepared of washing and drying, the products therefrom tap density is low, has directly influenced lithium ion anode material LiNi 1-x-yCo xMn yO 2Tap density.CN1767236 patent disclosure specification is reported the method for the two hydroxyl hydrogen oxide precursor synthesizing lithium ion positive electrodes of a kind of Co-Ni-Mn-LDHs, but this presoma preparation needs to add H 2O 2Oxidation, crystallization time reach 10 to 20 hours, and its structure is the two hydroxyl hydrogen oxides of α-Co-Ni-Mn-LDHs, and tap density is very low.U.S. Patent application (US2005/0089756A1) discloses a kind of continuous processing and has produced high-density Ni 1-x-yCo xMn y(OH) 2Method; but its tap density is only between 1.5-1.91g/cm3; and used ammoniacal liquor not only to increase cost but also contaminated environment in the production process as complexing agent, in preparation process, need inert gas shielding or use hydrazine hydrate to make each metal ion valence state be divalence in order to improve density in addition.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of nickel oxide mixed with cobalt manganese hydroxy base, the nickel oxide mixed with cobalt manganese hydroxy base for preparing with the method has the tap density height.Technical scheme of the present invention is, a kind of preparation method of nickel oxide mixed with cobalt manganese hydroxy base, it is characterized in that: include following operation: the preparation of (1) solution, by Ni: Mn: the Co mol ratio is 1: the proportional arrangement Ni of X: Y, Mn, Co mixing salt solution, 1/5≤X≤2/5 wherein, 1/5≤Y≤2/5, Ni, Co, Mn salt are selected from any of sulfate, nitrate, hydrochloride, acetate; Preparation NaOH or potassium hydroxide solution, the amount of aqueous slkali are determined according to the amount of above-mentioned any salt-mixture, make its reaction back solution be alkalescence; (2) coprecipitation reaction, elder generation under agitation adds above-mentioned mixed salt solution in the reactor after above-mentioned aqueous slkali is put into reactor more gradually, and temperature is controlled at 25-90 ℃, and reaction generates the hydroxide slurry material of doping Co, Mn; (3) polyacrylamide solution is added coagulation in the above-mentioned slurry, again the material behind the coagulation is carried out press filtration, obtain solid filter cake, the polyacrylamide addition is no less than 0.3g by above-mentioned every liter of mixed salt solution and adds; (4) the gained filter cake is dried under 80-140 ℃ of condition, the soluble impurity ion is removed in washing then; (5) material after the washing is dried under 60-140 ℃ of condition, pulverizes 200 mesh sieves and obtains the Ni1-x-yCoxMnyOOH product.
The present invention adopts the chemical coprecipitation of redrying to prepare nickel oxide mixed with cobalt manganese hydroxy base, the tap density height of this product compared with the prior art, the technology simple controllable, the remarkable advantage of friendly environment, products therefrom are γ type six side's layer structures, and ionic valence condition is a trivalent, particle diameter is tiny, there is a large amount of lattice defects in the part, and reactivity is higher, and the anode material for lithium-ion batteries for preparing as presoma has high tap density.
Description of drawings:
Fig. 1 is embodiment sample (Ni 1/3Co 1/3Mn 1/3OOH) X-ray diffracting spectrum,
Fig. 2 is Li (Ni 1/3Co 1/3Mn 1/3) O 2X-ray diffracting spectrum.
Embodiment:
With the following Examples the present invention is elaborated,
Embodiment 1,
(1) solution preparation, compound concentration is 4.0mol/dm 3NaOH solution 1000ml; In Ni: Mn: the Co mol ratio is that 1: 1: 1 ratio compound concentration is 1.5mol/dm 3NiSO 4, CoSO 4, MnSO 4Mixed solution 1000ml.
(2) earlier above-mentioned sodium hydroxide solution is put into reactor, and then above-mentioned metal mixed salting liquid is under agitation added in the reactor gradually, reaction temperature is set in 50 ℃, the hydroxide slurry material of obtain behind the reaction 1.5h mixing Co, Mn.
(3) polyacrylamide solution of 100ml 0.6% is joined in the slurry of gained and carry out coagulation, then the press filtration of coagulation thing is formed filter cake.
(4) with above-mentioned filter cake under 120 ℃ of conditions dry 6 hours, the soluble impurity ion was removed in washing then.
(5) carry out the dry back second time, crushing screening at 120 times, obtain Ni 1/3Co 1/3Mn 1/3The OOH presoma, its tap density 2.21g/cm 3
Embodiment 2,
(1) solution preparation, compound concentration is 6.0mol/dm 3KOH solution 1000ml; In Ni: Mn: the Co mol ratio is that 2: 2: 1 ratio compound concentration is 1.5mol/dm 3NiSO 4, CoSO 4, MnSO 4Mixed solution 1000ml;
(2) earlier above-mentioned potassium hydroxide solution is put into reactor, and then above-mentioned metal mixed salting liquid is under agitation added in the reactor gradually, reaction temperature is set in 80 ℃, the hydroxide slurry material of obtain behind the reaction 0.5h mixing Co, Mn;
(3) polyacrylamide solution of 120ml 0.6% is joined in the slurry of gained and carry out coagulation, then the press filtration of coagulation thing is formed filter cake;
(4) with above-mentioned filter cake under 135 ℃ of conditions dry 4 hours, the soluble impurity ion was removed in washing then;
(5) under 100 ℃, carry out the dry back second time, crushing screening, obtain Ni 2/5Co 1/5Mn 2/5The OOH presoma, its tap density 2.23g/cm 3
Embodiment 3,
(1) solution preparation, compound concentration is 2.0mol/dm 3NaOH solution 1500ml; In Ni: Mn: the Co mol ratio is that 2: 1: 2 ratio compound concentration is 1.2mol/dm 3NiCl 2, CoCl 2, MnCl 2Mixed solution 1000ml;
(2) earlier above-mentioned sodium hydroxide solution is put into reactor, and then above-mentioned metal mixed salting liquid is under agitation added in the reactor gradually, reaction temperature is set in 30 ℃, the hydroxide slurry material of obtain behind the reaction 2h mixing Co, Mn;
(3) polyacrylamide solution of 200ml 0.3% is joined in the slurry of gained and carry out coagulation, then the press filtration of coagulation thing is formed filter cake;
(4) with above-mentioned filter cake under 100 ℃ of conditions dry 8 hours, the soluble impurity ion was removed in washing then.
(5) under 80 ℃, carry out the dry back second time, crushing screening, obtain Ni 2/5Co 2/5Mn 1/5The OOH presoma, its tap density 2.15g/cm 3
Embodiment 4,
(1) solution preparation, compound concentration is 8.0mol/dm 3NaOH solution 800ml; In Ni: Mn: the Co mol ratio is that 1: 1: 1 ratio compound concentration is 2.0mol/dm 3Ni (NO 3) 2, Co (NO 3) 2, Mn (NO 3) 2Mixed solution 1000ml;
(2) earlier above-mentioned sodium hydroxide solution is put into reactor, and then above-mentioned metal mixed salting liquid is under agitation added in the reactor gradually, reaction temperature is set in 60 ℃, the hydroxide slurry material of obtain behind the reaction 1h mixing Co, Mn;
(3) polyacrylamide solution of 60ml 0.6% is joined in the slurry of gained and carry out coagulation, then the press filtration of coagulation thing is formed filter cake;
(4) with above-mentioned filter cake under 85 ℃ of conditions dry 12 hours, the soluble impurity ion was removed in washing then.
(5) under 60 ℃, carry out the dry back second time, crushing screening, obtain Ni 1/3Co 1/3Mn 1/3The OOH presoma, its tap density 2.10g/cm 3
Comparative example 1,
With NiSO 4, CoSO 4, MnSO 4Be mixed with 1.5mol/dm by a certain percentage 3Mixed solution 1000ml (mol ratio of Ni, Mn, Co is 1: 1: 1).Reaction temperature is set in 50 ℃, under agitation with certain speed mixed solution is added 1000ml 4.0mol/dm 3NaOH solution in, reaction does not add the polyacrylamide coagulation behind the 2h, adopts common primary drying method directly with the slurries filtration, the flush away foreign ion that generate, dry 6h at 120 ℃, obtains comparative sample through pulverizing, tap density 1.4g/cm 3
Comparative example 2,
Adopt continuous flow method with 1.5mol/dm 3Mixed salt solution (mol ratio of Ni, Mn, Co is 1: 1: 1), ammoniacal liquor and 6.0mol/dm 3NaOH solution under strong mixing, add simultaneously in the reactor with certain flow velocity, 50 ℃ of control reaction temperature, the pH value is controlled to be 12.5, product flows out in company with mother liquor continuously from the reactor overfall, through separate, washing, oven dry, spherical Ni 1/3Co 1/3Mn 1/3(OH) 2,, make that each ionic valence condition of product is a divalence, tap density 1.85g/cm owing to there is the reduction of ammoniacal liquor to stop the oxidation of metal ion 3

Claims (1)

1, a kind of preparation method of nickel oxide mixed with cobalt manganese hydroxy base is characterized in that: include following operation:
(1) solution preparation, by Ni: Mn: the Co mol ratio is 1: the proportional arrangement Ni of X: Y, Mn, Co mixing salt solution, 1/5≤X≤2/5,1/5≤Y≤2/5 wherein, Ni, Co, Mn salt are selected from any of sulfate, nitrate, hydrochloride, acetate; Preparation NaOH or potassium hydroxide solution, the amount of aqueous slkali are determined according to the amount of above-mentioned any salt-mixture, make its reaction back solution be alkalescence;
(2) coprecipitation reaction, elder generation under agitation adds above-mentioned mixed salt solution in the reactor after above-mentioned aqueous slkali is put into reactor more gradually, and temperature is controlled at 25-90 ℃, and reaction generates the hydroxide slurry material of doping Co, Mn;
(3) polyacrylamide solution is added coagulation in the above-mentioned slurry, again the material behind the coagulation is carried out press filtration, obtain solid filter cake, the polyacrylamide addition is no less than 0.3g by above-mentioned every liter of mixed salt solution and adds;
(4) the gained filter cake is dried under 80-140 ℃ of condition, the soluble impurity ion is removed in washing then;
(5) material after the washing is dried under 60-140 ℃ of condition, pulverizes 200 mesh sieves and obtains Ni 1-x-yCo xMn yThe OOH product.
CNB2006101600554A 2006-12-27 2006-12-27 Nickel oxide mixed with cobalt manganese hydroxy base and preparation method thereof Expired - Fee Related CN100444432C (en)

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CN107123799A (en) * 2017-05-18 2017-09-01 格林美（无锡）能源材料有限公司 The preparation method of lithium secondary cell with high capacity positive active material and its presoma
CN108666562B (en) * 2018-04-17 2021-03-26 宁波大学 Cobalt-manganese-doped tin dioxide nanotube and preparation method thereof
CN113277572B (en) * 2021-07-22 2021-11-26 金驰能源材料有限公司 Low-sodium-sulfur-nickel-cobalt composite hydroxide precursor and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050089756A1 (en) * 2000-11-06 2005-04-28 Tanaka Chemical Corporation High density cobalt-manganese coprecipitated nickel hydroxide and process for its production
CN1614801A (en) * 2003-11-07 2005-05-11 中国科学院上海微***与信息技术研究所 Multi-component composite positive material for lithium ion battery and preparing method thereof
CN1691379A (en) * 2004-04-30 2005-11-02 深圳市比克电池有限公司 Anode material of lithium ion battery and electrode, battery thereof and method for preparing the same material
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050089756A1 (en) * 2000-11-06 2005-04-28 Tanaka Chemical Corporation High density cobalt-manganese coprecipitated nickel hydroxide and process for its production
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
CN1614801A (en) * 2003-11-07 2005-05-11 中国科学院上海微***与信息技术研究所 Multi-component composite positive material for lithium ion battery and preparing method thereof
CN1691379A (en) * 2004-04-30 2005-11-02 深圳市比克电池有限公司 Anode material of lithium ion battery and electrode, battery thereof and method for preparing the same material

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