CN104752688A - Spherical nickel hydroxide coated with Co(OH)2 on surface and preparation method thereof - Google Patents

Spherical nickel hydroxide coated with Co(OH)2 on surface and preparation method thereof Download PDF

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Publication number
CN104752688A
CN104752688A CN201310751877.XA CN201310751877A CN104752688A CN 104752688 A CN104752688 A CN 104752688A CN 201310751877 A CN201310751877 A CN 201310751877A CN 104752688 A CN104752688 A CN 104752688A
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Prior art keywords
nickel hydroxide
ball
preparation
coated
solution
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Inventor
于丽敏
蒋文全
郭荣贵
李涛
张婧
韩雪
黄小卫
胡运生
郝红蕊
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Beijing General Research Institute for Non Ferrous Metals
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Beijing General Research Institute for Non Ferrous Metals
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses spherical nickel hydroxide coated with Co(OH)2 on the surface and a preparation method of the spherical nickel hydroxide. The method comprises the following steps: adding a cobalt sulfate solution to a base solution containing spherical nickel hydroxide at gradually increasing speed, adding a complexing agent solution and alkali liquor simultaneously, controlling the reaction temperature to be 40-80 DEG C and the stirring speed to be 100-250 r/min, keeping the pH value of a reaction system to be 9-13.5, and controlling the reaction time to be 2-5 hours, so as to form 'gradient eutectic coating'. The Co(OH)2 coated spherical nickel hydroxide electrode material prepared by adopting the method disclosed by the invention has a firm and compact coating layer, is much better than spherical nickel hydroxide which is not coated with cobalt in large current charging and discharging performance and cycling performance, and has good production and use values.

Description

A kind of Surface coating Co (OH) 2ball-shape nickel hydroxide and preparation method thereof
Technical field
The present invention relates to a kind of Surface coating Co (OH) 2the electrode material preparation method of ball-shape nickel hydroxide, belongs to field of functional materials.
Background technology
Ball-shape nickel hydroxide is Ni/MH, Ni/Cd, Ni/H 2etc. the positive electrode active materials of multiple alkaline secondary cell, vital effect is played to the quality containing performances such as the capacity of nickel secondary batteries and cycle lives.The green powder of existing ball-shape nickel hydroxide because of its conductivity not good, cause the internal resistance of cell to increase, constrain its capacity play and self-discharge performance.Ameliorative way general at present adds metallic cobalt or cobalt oxide etc. when manufacturing anode, although make moderate progress to conductivity, but the cobalt directly added is owing to being physical property mechanical mixture, skewness in charge and discharge process and be easy to come off, have influence on battery performance, thus general spherical shape nickel hydroxide can not meet the requirement of high-end secondary cell now.To the cobalt hydroxide of ball shape nickel hydroxide surface coating conducting excellence and prepare cover cobalt type ball-shape nickel hydroxide, the requirement of high end cells to positive electrode can be met well.
At present, Surface coating Co (OH) is carried out to ball-shape nickel hydroxide 2relate to multiple Chinese patent such as 03133524.1, main technique is: the Homogeneous phase mixing liquid of cobalt sulfate solution and nickel sulfate solution and alkali are input to reactor simultaneously, generate cobalt hydroxide and new nickel hydroxide mixed layer at former ball shape nickel hydroxide surface.The subject matter that current discovery this kind of technique exists is: the first, due in coating layer except cobalt hydroxide, also expose in atmosphere containing the nickel hydroxide composition that part is newly-generated, nickel can be caused in oxidizing process oxidized, cause active material utilization to reduce; The second, coating layer defective tightness, causes coating layer in battery charge and discharge process easily to come off, affects the performance of electrical property.
Chinese patent 99107434.3 is open separately has a kind of method to be adopt the mode of integration charging to feed in raw material, namely first cobalt sulfate solution to be joined gradually in nickel sulfate solution and to stir, the nickel sulfate solution being mixed with different amount cobaltous sulfate is joined reaction system simultaneously, improve the cobalt concentration in coating layer gradually.There is nickel hydroxide problem newly-generated containing part in coating layer equally in the method, although improve the adhesion of coating layer and ball, complex process simultaneously, causes in production and be difficult to control.
Summary of the invention
The object of the invention is to develop in a kind of coating layer and no longer comprise nickel hydroxide composition, but the gradient eutectic method for coating of the tightness of coating layer and ball can be increased again simultaneously, prepare Surface coating Co (OH) 2ball-shape nickel hydroxide, to solve some technical problems existed at present.
For achieving the above object, the present invention is by the following technical solutions:
A kind of Surface coating Co (OH) 2the preparation method of ball-shape nickel hydroxide, the method comprises the steps:
A. reaction solution is prepared
Preparation cobalt sulfate solution, cobalt concentration is at 0.01 ~ 1.5mol/L;
Preparation alkali hydroxide soln, wherein alkali metal is Na or K, alkali concn 0.2 ~ 8mol/L;
Preparation enveloping agent solution, complexing agent is NH 3or EDTA, complexing agent concentration 0.01 ~ 2mol/L;
B. the preparation of end liquid in reactor
Ball-shape nickel hydroxide to be covered is joined in reactor, adds deionized water, control the mass ratio of ball-shape nickel hydroxide and deionized water between 1: 2 ~ 12; Add alkali lye, adjust end liquid pH value between 9 ~ 13.5; Add part complexing agent again, the concentration of complexing agent in end liquid is in the scope of >0 ~ 0.02mol/L;
C. coated Co (OH) 2reaction
After end liquid prepares, open and stir and heat up, reaction temperature controls at 40 ~ 80 DEG C; Open cobalt sulfate solution measuring pump, complexing agent measuring pump and alkali lye measuring pump, each reaction solution is pumped in end liquid and reacts; Wherein, it is 5 ~ 10mL/min that cobalt sulfate solution initially adds speed, reacts after 30 ~ 60 minutes, and adjustment cobalt sulfate solution liquid inlet volume, increases progressively with the flow of 0.05 ~ 0.5mL/min, reach 10 ~ 30mL/min to cobalt sulfate solution flow; Enveloping agent solution adds speed between 5 ~ 10mL/min, adjusts speed of agitator simultaneously between 100 ~ 250r/min, is formed " gradient eutectic is coated "; Intermittently pump into alkali lye, keep the pH value of reaction system between 9 ~ 13.5; The sample size of cobaltous sulfate is according to Co/Ni (OH) 2be 1 ~ 5wt%; Reaction time is 2 ~ 5 hours;
D. reprocessing
The product prepared by step C carries out Separation of Solid and Liquid, solids wash post-drying, sieves to obtain coated Co (OH) 2ball-shape nickel hydroxide product.
Ball-shape nickel hydroxide of the present invention can be commercially available ball-shape nickel hydroxide.
On the other hand, the invention provides a kind of Surface coating C o(OH) 2ball-shape nickel hydroxide, it adopts method as above to prepare.
" gradient eutectic is coated " of the present invention mechanism is theoretical according to nonhomogen-ous nucleation, in the crystal nucleation and growth course of heterogeneous system, cenotype is formed or grows in existing solid phase, the recruitment of its system surface Gibbs free energy is less than the recruitment of self nucleation (homogeneous nucleation) system surface Gibbs free energy, so heterogeneous nucleation has precedence over the homogeneous nucleation in system.Can realize heterogeneous coated by the pH value of the hierarchy of control, degree of supersaturation and stirring etc.Initial long response time, to ensure coated interface close and firm, after forming tight coating layer, increases inlet amount gradually, continues gradient growth in tight cover surface.
Beneficial effect of the present invention is: the first, no longer comprises new nickel hydroxide in coating layer, thus avoids nickel to expose the problem of oxidation; The second, technological process is simple, and coating layer is tight, stable.Adopt coated Co (OH) prepared by the inventive method 2ball-shape nickel hydroxide electrode material, coating layer is firm, fine and close, and high rate during charging-discharging and cycle performance, significantly better than the ball-shape nickel hydroxide performance of not coated cobalt, have good production and application and are worth.
Accompanying drawing explanation
Fig. 1 is that embodiment 1-4 prepares gained sample and not coated Co (OH) is used in contrast 22C charging/1C discharge cycles the curve of ball-shape nickel hydroxide sample.
Fig. 2 is that embodiment 1-4 prepares gained sample and not coated Co (OH) is used in contrast 2the 3C charge and discharge cycles curve of ball-shape nickel hydroxide sample.
Fig. 3 is that embodiment 2 prepares the coated Co of gained sample (OH) 2ball-shape nickel hydroxide SEM schemes.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
In following examples, ball-shape nickel hydroxide is common commercially available ball-shape nickel hydroxide.
Embodiment 1
Preparation cobalt concentration 0.2mol/L cobalt sulfate solution; The NaOH solution of preparation 0.8mol/L; Preparation 1.2mol/L ammonia spirit; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 20L, add ammonia spirit in end liquid, make NH 3in end liquid, concentration is 0.02mol/L, adds alkali lye and adjusts end liquid pH value to be 11; Stirring is warming up to 55 DEG C and keeps, according to Co/Ni (OH) 2(wt.%) quantitative cobalt sulfate solution and ammonia spirit inputted in reactor by the ratio of 1% in 5 hours, wherein cobalt sulfate solution initial charge speed is 6mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.1mL/min, until reach 10mL/min; Ammonia spirit continues charging with 5mL/min flow, and the charging of NaOH solution adjusts for benchmark 12 at any time to keep the pH value of system, and stirring frequency is 200r/min.Charging terminates rear continuation and stirs 1h, carries out Separation of Solid and Liquid, washing, oven dry, sieves to obtain sample 1.
Embodiment 2:
Preparation cobalt concentration 0.5mol/L cobalt sulfate solution; The NaOH solution of preparation 1.2mol/L; Preparation 0.2mol/LEDTA solution; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 20L, in end liquid, add EDTA solution, make EDTA concentration in end liquid be 0.01mol/L, add alkali lye and adjust end liquid pH value to be 13; Stirring is warming up to 50 DEG C and keeps, according to Co/Ni (OH) 2(wt.%) quantitative cobalt sulfate solution and EDTA solution inputted in reactor by the ratio of 2% in 3.5 hours, wherein cobalt sulfate solution initial charge speed is 5mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.25mL/min, until reach 15mL/min; EDTA solution continues charging with 10mL/min flow, and the charging of NaOH solution adjusts for benchmark 13.5 at any time to keep the pH value of system, and stirring frequency is 220r/min.Charging terminates rear continuation and stirs 1h, carries out Separation of Solid and Liquid, washing, oven dry, sieves to obtain sample 2.
Embodiment 3:
Preparation cobalt concentration 0.8mol/L cobalt sulfate solution; The NaOH solution of preparation 1.8mol/L; Preparation 0.4mol/LEDTA solution; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 24L, in end liquid, add EDTA solution, make EDTA concentration in end liquid be 0.01mol/L, add alkali lye and adjust end liquid pH value to be 12; Stirring is warming up to 55 DEG C and keeps, according to Co/Ni (OH) 2(wt.%) quantitative cobalt sulfate solution and ammonia spirit inputted in reactor by the ratio of 3% in 3.5 hours, wherein cobalt sulfate solution initial charge speed is 5mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.15mL/min, until reach 14mL/min; EDTA solution continues charging with 8mL/min flow, and the charging of NaOH solution adjusts for benchmark 13 at any time to keep the pH value of system, and stirring frequency is 200r/min.Charging terminates rear continuation and stirs 1h, carries out Separation of Solid and Liquid, washing, oven dry, sieves to obtain sample 3.
Embodiment 4:
Preparation cobalt concentration 1.5mol/L cobalt sulfate solution; The NaOH solution of preparation 6mol/L; Preparation 1.0mol/LEDTA solution; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 30L, in end liquid, add EDTA solution, make EDTA concentration in end liquid be 0.02mol/L, add alkali lye and adjust end liquid pH value to be 10; Stirring is warming up to 60 DEG C and keeps, according to Co/Ni (OH) 2(wt.%) quantitative cobalt sulfate solution and ammonia spirit inputted in reactor by the ratio of 5% in 4 hours, wherein cobalt sulfate solution initial charge speed is 5mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.05mL/min, until reach 10mL/min; EDTA solution continues charging with 5mL/min flow, and the charging of NaOH solution adjusts for benchmark 11 at any time to keep the pH value of system, and stirring frequency is 200r/min.Charging terminates rear continuation and stirs 1h, carries out Separation of Solid and Liquid, washing, oven dry, sieves to obtain sample 4.
Embodiment 5
Gained sample prepared by embodiment 1-4 and contrast sample and do not cover Co (OH) 2ball-shape nickel hydroxide sample carries out normal temperature electrochemical property test with three electrode forms, its discharge and recharge system is respectively 1C discharge and recharge (1C/1C), 2C charges 1C electric discharge (2C/1C), 3C discharge and recharge (3C/3C).
Table 1 prepares gained sample for embodiment 1-4 and not coated Co (OH) is used in contrast 2the specific discharge capacity test result of ball-shape nickel hydroxide sample under different discharge and recharge system.
Fig. 1, Fig. 2 are that embodiment 1-4 prepares gained sample and not coated Co (OH) is used in contrast 2the cycle performance test result of ball-shape nickel hydroxide sample.
Specific discharge capacity test result under table 1, different discharge and recharge system
1C/1C specific discharge capacity mAh/g 2C/1C specific discharge capacity mAh/g 3C/3C specific discharge capacity mAh/g
Do not cover cobalt sample 270 244.5 160
Embodiment 1 285 268 195
Embodiment 2 280 280 228.3
Embodiment 3 279 286.8 224.8
Embodiment 4 273 279 209
From electric performance test result, prepared by embodiment 1-4, cover Co (OH) 2the chemical property of ball-shape nickel hydroxide is better than the ball-shape nickel hydroxide of not coated cobalt, and especially high rate during charging-discharging and cycle performance are all obviously better than not coated Co (OH) 2ball-shape nickel hydroxide.
Fig. 3 is coated Co (OH) prepared by embodiment 2 2ball-shape nickel hydroxide SEM schemes.Schemed from SEM, coating layer is firmly fine and close, without fine particle between the ball-shape nickel hydroxide particle after coated, Co (OH) in coated process is described 2with spherical Ni (OH) 2for core carries out crystallization nucleation.

Claims (2)

1. a Surface coating Co (OH) 2the preparation method of ball-shape nickel hydroxide, is characterized in that, the method comprises the steps:
A. reaction solution is prepared
Preparation cobalt sulfate solution, cobalt concentration is at 0.01 ~ 1.5mol/L;
Preparation alkali hydroxide soln, wherein alkali metal is Na or K, alkali concn 0.2 ~ 8mol/L;
Preparation enveloping agent solution, complexing agent is NH 3or EDTA, complexing agent concentration 0.01 ~ 2mol/L;
B. the preparation of end liquid in reactor
Ball-shape nickel hydroxide to be covered is joined in reactor, adds deionized water, control the mass ratio of ball-shape nickel hydroxide and deionized water between 1: 2 ~ 12; Add alkali lye, adjust end liquid pH value between 9 ~ 13.5; Add part complexing agent again, the concentration of complexing agent in end liquid is in the scope of >0 ~ 0.02mol/L;
C. coated Co (OH) 2reaction
After end liquid prepares, open and stir and heat up, reaction temperature controls at 40 ~ 80 DEG C; Open cobalt sulfate solution measuring pump, complexing agent measuring pump and alkali lye measuring pump, each reaction solution is pumped in end liquid and reacts; Wherein, it is 5 ~ 10mL/min that cobalt sulfate solution initially adds speed, reacts after 30 ~ 60 minutes, and adjustment cobalt sulfate solution liquid inlet volume, increases progressively with the flow of 0.05 ~ 0.5mL/min, reach 10 ~ 30mL/min to cobalt sulfate solution flow; Enveloping agent solution continues charging with the speed that adds of 5 ~ 10mL/min, adjusts speed of agitator simultaneously between 100 ~ 250r/min, is formed " gradient eutectic is coated "; Intermittently pump into alkali lye, keep the pH value of reaction system between 9 ~ 13.5; The sample size of cobaltous sulfate is according to Co/Ni (OH) 2be 1 ~ 5wt%; Reaction time is 2 ~ 5 hours.
D. reprocessing
The product prepared by step C carries out Separation of Solid and Liquid, solids wash post-drying, sieves to obtain coated Co (OH) 2ball-shape nickel hydroxide product.
2. a Surface coating Co (OH) 2ball-shape nickel hydroxide, is characterized in that, it adopts the method for claim 1 to prepare.
CN201310751877.XA 2013-12-31 2013-12-31 Spherical nickel hydroxide coated with Co(OH)2 on surface and preparation method thereof Pending CN104752688A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105552350A (en) * 2015-12-14 2016-05-04 韶关中弘金属实业有限公司 Production technology of spherical cobalt-coated nickel hydroxide
CN114314682A (en) * 2021-12-13 2022-04-12 上海应用技术大学 Preparation method of metal cobalt-coated cobalt aluminum hydroxide supercapacitor material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728521A (en) * 2009-11-28 2010-06-09 内蒙古科技大学 Preparation method of Co-covered nickel hydroxide anode material with surface covered by rare earth compound
CN103204555A (en) * 2013-04-26 2013-07-17 先进储能材料国家工程研究中心有限责任公司 Method for preparing spherical nickel hydroxide with surface coated by gamma-hydroxy cobaltous oxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728521A (en) * 2009-11-28 2010-06-09 内蒙古科技大学 Preparation method of Co-covered nickel hydroxide anode material with surface covered by rare earth compound
CN103204555A (en) * 2013-04-26 2013-07-17 先进储能材料国家工程研究中心有限责任公司 Method for preparing spherical nickel hydroxide with surface coated by gamma-hydroxy cobaltous oxide

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Title
赫文秀等: "覆钴型氢氧化镍的电化学性能研究", 《人工晶体学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105552350A (en) * 2015-12-14 2016-05-04 韶关中弘金属实业有限公司 Production technology of spherical cobalt-coated nickel hydroxide
CN105552350B (en) * 2015-12-14 2018-10-30 韶关中弘金属实业有限公司 A kind of spherical shape covers cobalt nickel hydroxide production technology
CN114314682A (en) * 2021-12-13 2022-04-12 上海应用技术大学 Preparation method of metal cobalt-coated cobalt aluminum hydroxide supercapacitor material
CN114314682B (en) * 2021-12-13 2023-06-27 上海应用技术大学 Preparation method of metallic cobalt coated cobalt aluminum hydroxide supercapacitor material

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Application publication date: 20150701