CN1226194C - Nano grade nickel oxyhydroxide and process for preparing same - Google Patents

Nano grade nickel oxyhydroxide and process for preparing same Download PDF

Info

Publication number
CN1226194C
CN1226194C CNB031138837A CN03113883A CN1226194C CN 1226194 C CN1226194 C CN 1226194C CN B031138837 A CNB031138837 A CN B031138837A CN 03113883 A CN03113883 A CN 03113883A CN 1226194 C CN1226194 C CN 1226194C
Authority
CN
China
Prior art keywords
reaction
nickel oxide
solution
nickel
divalent
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.)
Expired - Fee Related
Application number
CNB031138837A
Other languages
Chinese (zh)
Other versions
CN1433970A (en
Inventor
周震涛
刘澧蒲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CNB031138837A priority Critical patent/CN1226194C/en
Publication of CN1433970A publication Critical patent/CN1433970A/en
Application granted granted Critical
Publication of CN1226194C publication Critical patent/CN1226194C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to the field of battery materials, more specially a preparation method for nickel oxy-hydroxide as the positive materials of zinc-nickel primary batteries, zinc-nickel secondary batteries and other batteries which use the compounds of nickel as active substances, such as nickel-cadmium batteries, metal hydride nickel batteries, iron-nickel batteries, etc., and nanometer nickel oxy-hydroxide prepared by using the method. In the preparation process of the nanometer nickel oxy-hydroxide, divalent nickel salts are used as raw materials, and sodium hypochlorite is used as an oxidizing agent; a precipitation reaction and an oxidation reaction are simultaneously carried out in an alkaline water solution; in the reaction process, ultrasonic waves are used for realizing oscillation and dispersion; the prepared nanometer oxy-hydroxide has the advantages of small and uniform particle diameter, large specific surface area, high specific capacity of initial discharging, low self-discharging rate, stable electrical property and simple and convenient operation technology; crystal structures are controlled easily.

Description

Nano-grade hydroxy nickel oxide and preparation method thereof
(1) technical field under
The present invention relates to the battery material field, in more detail the preparation method of the positive electrode material hydroxy nickel oxide of zinc nickel primary battery, zinc-nickel secondary batteries and other compound battery that is active substance such as ickel-cadmium cell, metal-hydrogen nickel battery, Hawkins cell etc. with nickel.
The invention still further relates to the nano-grade hydroxy nickel oxide of this method preparation.
(2) background technology
At present, the conventional batteries electrode active material has the branch of Charging state and discharge attitude.If the electrode that initial charging state is different is assembled into battery, certainly exists the unmatched problem of attitude that discharges and recharges, thereby bring difficulty for changing into of battery.In zinc-nickel secondary batteries, because positive active material hydroxide nickel (OH) 2Be the discharge attitude, thereby will to adopt the ZnO that is all the discharge attitude be negative pole is supporting with it, be assembled into ZnO/Ni (OH) 2Must repeatedly discharge and recharge behind the battery and could use after changing into, and because ZnO is soluble in alkaline electrolyte, thereby also influenced the cycle life of zinc-nickel secondary batteries.If adopting the Zn powder is the words of negative electrode active material, because the Zn powder is in Charging state, in order to solve the necessary consistent problem of two electrode charging states, the positive pole that matches also must adopt the hydroxy nickel oxide (NiOOH) that is in Charging state, thereby has just drawn the hydroxide nickel (OH) of the attitude of will discharging 2Be transformed into Charging state hydroxy nickel oxide (NiOOH) preparation with study a question.Nano-grade hydroxy nickel oxide (NiOOH) is because its particle diameter is less, specific surface area is bigger, make its reaction interface bigger as electrode, thereby can reduce the current density of electrode reaction effective unit area, reduce the polarization phenomena of electrode reaction, make it have better electrochemical activation, show excellent chemical property.
Xia Xi etc. (seeing " battery " for details, Vol.32, No.1,2002) adopt solid-phase oxidation method to prepare nano-grade hydroxy nickel oxide β-NiOOH powder sample, and its relevant physical properties and chemical property are characterized.The preparation method of this nano beta-NiOOH is as follows: be respectively accurately to have taken by weighing the fully NiSO of porphyrize at 1: 2 in molar ratio 47H 2O and NaOH place agate mortar, and fine mixing ground about 10min, add an amount of fully oxygenant ammonium persulphate (NH of porphyrize down in alkaline condition again 4) 2S 2O 8, fully mix and grind.Become black and be thick by light green gradually after the system moisture absorption.Till reaction proceeds to color and no longer deepens.Solid product in 80 ℃ of oven dry, gets sample after filtering and washing.Test result shows that the particle of gained sample β-NiOOH is spherical in shape, and size is between 20～40nm.This material is made the work electrode, adopt three-electrode system to carry out the experiment of 5m A constant current charge-discharge.The first discharge specific capacity of this material is very low, only is 35mAh/g, just reaches the highest specific discharge capacity 300mAh/g through this material after the charge and discharge cycles more than 5 times.Yet, make prepared in this way β-NiOOH still have following problem:
(1) adopting the solid state grinding reaction method that reactant is mixed grinds, because diffusion of reactant particulate and motion are severely limited, thereby make multiple reactant difficulty be uniformly dispersed, particle is reunited easily and is grown up, cause reaction to carry out thoroughly inadequately, (transformation efficiency of β-NiOOH) is lower, difficult quality guarantee for reaction product nano-grade hydroxy nickel oxide;
(2) carry out not thoroughly, not exclusively with ammonium persulphate at normal temperatures as the solid state reaction of oxygenant, the oxidation susceptibility of ammonium persulphate is strong inadequately, and (initial discharge capacity that β-NiOOH) is made into behind the alkaline Zn/NiOOH secondary cell is very low to cause the nano-grade hydroxy nickel oxide that obtains.This secondary cell will just can reach higher specific discharge capacity through after repeatedly repeated charge changes into.
Thoroughly fully, the transformation efficiency of product is low inadequately in reaction when (3) preparing hydroxy nickel oxide owing to this method, and when being assembled into battery with this hydroxyl oxidize nickel powder and metal zinc, the initial discharge specific storage of battery is very low.So this hydroxyl oxidize nickel powder is not suitable for using as the positive active material of a zinc-nickel cell.
(4) do not have the alkali doped positively charged ion in the layered crystal structure of this nano-grade hydroxy nickel oxide, make its self-discharge rate bigger, shelf characteric is relatively poor.
(5) production technique of this method is difficult to carry out large-scale industrial production.
(3) summary of the invention
The objective of the invention is to provides a kind of employing liquid phase oxidation reaction legal system to be equipped with the nano-grade hydroxy nickel oxide (preparation method of β-NiOOH) at the problem that prior art exists.The particle diameter of the nano-grade hydroxy nickel oxide for preparing with this method is tiny evenly, specific surface area is big, initial discharge capacity is high, self-discharge rate is low, electric performance stablity, operating procedure are simple, crystalline structure is controlled easily.
The present invention also aims to provide the nano-grade hydroxy nickel oxide of described method preparation.
The preparation method of nano-grade hydroxy nickel oxide of the present invention is to be raw material with the divalent nickel salt, and hypochlorous sodium is an oxygenant, carries out precipitin reaction and oxidizing reaction in alkaline aqueous solution simultaneously; Reaction process adopts ultrasonic wave to carry out vibrating dispersion.
Particularly, be at first divalent nickel salt to be mixed with the aqueous solution, the weight percent that adds with respect to divalent nickel salt is divalent cobalt, divalent zinc salt or the divalence cadmium salt of 1-5%, dissolving mixes and makes reaction solution; Reaction solution dropwise joined in the alkaline aqueous solution that hypochlorous sodium is an oxygenant react; Reaction process adopts ultrasonic wave to carry out vibrating dispersion, and temperature of reaction is 45-65 ℃, and the reaction times is 0.5-5 hour.
Its reaction principle is expressed as follows with reaction formula:
(green) (black)
Liquid phase oxidation reaction carries out in ultra-sonic oscillation are disperseed.Can prevent effectively that like this product particle from further growing up and reunion, control the granularity of product effectively, thereby prepare evenly tiny nano-grade hydroxy nickel oxide of particle diameter.
The self-discharge of hydroxy nickel oxide is caused by the reason of two aspects: first foreign ion such as NO 3 -, CO 3 2-Decomposing produces oxygen causes.This can solve by the foreign matter content that reduces wherein of purifying; It two is that solute alkalimetal ion in the electrolytic solution can be penetrated in the layered crystal structure of hydroxy nickel oxide gradually, and the H in the hydroxy nickel oxide hydroxyl is partly cemented out becomes H +Ion.And these H +OH in ion and the electrolytic solution -Ionic reaction generates water, thereby causes electrolytic solution diluted.
Exoelectrical reaction formula according to hydroxy nickel oxide
The diluted part of O H that consumed of above-mentioned electrolytic solution -Ion, thus cause the self-discharge of the hydroxy nickel oxide of following formula to react acceleration to the right.At the reason that causes the hydroxy nickel oxide self-discharge, present method with the nano-grade hydroxy nickel oxide for preparing in the aqueous solution in advance with the basic metal reaction of mixing, making mixes in the crystalline structure of hydroxy nickel oxide in advance goes up alkali-metal positively charged ion, thereby make the alkali metal cation in the electrolytic solution stablize constant, electrolytic solution can further not diluted, reach the self-discharge that reduces hydroxy nickel oxide, improve the purpose of battery storage performance.
The preparation method is as follows more specifically for nano-grade hydroxy nickel oxide of the present invention:
(1) preparation of nano-grade hydroxy nickel oxide
1. be mixed with the aqueous solution that concentration is 0.1-12M with divalent nickel salt is water-soluble, adding with respect to the divalent nickel salt weight percent is divalent cobalt, divalent zinc salt or the divalence cadmium salt of 1-5%, and dissolving mixes makes reaction solution; Described divalent nickel salt is nickelous chloride, single nickel salt or nickelous nitrate; Water is deionized water, distilled water or tap water; Divalent cobalt is cobalt chloride, Xiao Suangu or rose vitriol; Divalent zinc salt is zinc chloride, zinc sulfate or zinc nitrate; The divalence cadmium salt is Cadmium chloride fine powder, Cadmium Sulphate or cadmium nitrate;
2. be mixed with the alkaline aqueous solution that concentration is 10-14M with potassium hydroxide or sodium hydroxide are water-soluble, add aqueous sodium hypochlorite solution and be mixed with aqueous oxidizing agent solution; The concentration of aqueous sodium hypochlorite solution is 1-5M; The volume ratio of aqueous sodium hypochlorite solution and potassium hydroxide or the sodium hydroxide alkalescence aqueous solution is 1 in the aqueous oxidizing agent solution: 0-0.5;
3. with the 2. the aqueous oxidizing agent solution that obtains of step place ultrasound reactor to carry out ultra-sonic oscillation to disperse, and be heated to 45-65 ℃, dropwise add the 1. reaction solution that obtain of step preparation; The volume ratio of reaction solution and aqueous oxidizing agent solution is 1: 5; Proceed ultra-sonic oscillation after reaction solution adds and disperse reaction; Reaction times is 0.5-5 hour, obtains being the reaction product hydroxy nickel oxide of black colloidal sol shape;
4. with the 3. the reaction product hydroxy nickel oxide water in step wash repeatedly, filter, can't check the existence of chlorion until washings; To place vacuum drying oven to carry out vacuum-drying through the reaction product of washing to the reaction product constant weight.
(2) doping of nano-grade hydroxy nickel oxide
The hydroxy nickel oxide that (1) prepares is poured in the reactor that fills alkaline aqueous solution, and the weight ratio of hydroxy nickel oxide and alkaline aqueous solution is 1: 5-10; Described alkaline aqueous solution is dissolved in deionized water, distilled water or tap water by in potassium hydroxide, sodium hydroxide or the lithium hydroxide one or more and obtains.Its concentration is 10-14M, and temperature of reaction is 45-65 ℃, and the reaction times is 20-60 hour.
On this basis, reaction product hydroxy nickel oxide water is washed repeatedly, filters, be neutral, then reaction product is placed vacuum drying oven to carry out vacuum-drying to the reaction product constant weight until the pH value of washings.
The above-mentioned nickel oxyhydroxide powder for preparing is measured its particle diameter with the low-angle scattering of X-rays method.Its crystalline structure adopts X-ray diffractometer to test.It is that positive active material, zinc powder are that negative electrode active material, potassium hydroxide aqueous solution are that the simulated battery of electrolytic solution made is measured that the electrical property of hydroxy nickel oxide adopts with the hydroxy nickel oxide.
The present invention compared with prior art has following advantage:
(1) the liquid phase oxidation reaction legal system of the present invention novel method that is equipped with the nano-grade hydroxy nickel oxide is carried out in ultra-sonic oscillation are disperseed.So not only can make the precipitin reaction and the oxidizing reaction of carrying out simultaneously carry out more thoroughly, but also reactant and product thereof fully are uniformly dispersed, prevent that more effectively the product particle from further growing up and reunion, control the granularity of product effectively, thereby prepare the more tiny and uniform nano-grade hydroxy nickel oxide of particle diameter.
(2) need not change into through repeated charge repeatedly by the alkaline Zn/NiOOH secondary cell of the nano-grade hydroxy nickel oxide made of the present invention preparation.The first discharge of assembling back battery can reach higher specific discharge capacity.Battery is higher through specific discharge capacity after the charge and discharge cycles repeatedly.This nano-grade hydroxy nickel oxide also is suitable for using as the positive active material of a zinc-nickel cell.
(3) the present invention adopts the method that nano-grade hydroxy nickel oxide and basic metal are mixed in advance and reacts, making mixes in the crystalline structure of hydroxy nickel oxide in advance goes up alkali metal cation, thereby make the self-discharge rate of Zn/NiOOH secondary cell littler, shelf characteric is better.
(4) temperature of reaction of liquid phase oxidation of the present invention can be as required regulating and controlling freely.The quality of prepared nano-grade hydroxy nickel oxide is controlled easily, and production technique is simple, is easy to carry out large-scale industrial production.
(4) embodiment
Embodiment 1
Take by weighing an amount of nickelous chloride (NiCl 26H 2O) be dissolved in tap water and be mixed with 100ml solution, the concentration that makes solution is 0.1M.Add weight percent with respect to nickelous chloride therein and be 1% cobalt chloride, dissolving mixes makes reaction solution.
Measure tap water 200ml, it is joined be mixed with aqueous oxidizing agent solution 500ml in the 300ml aqueous sodium hypochlorite solution then, the concentration of control aqueous sodium hypochlorite solution is 5M.
The above-mentioned aqueous oxidizing agent solution of 500ml placed carry out ultra-sonic oscillation on the ultrasound reactor and disperse, and be heated to 45 ℃, dropwise add the above-mentioned reaction solution of 100ml then.Proceed ultra-sonic oscillation after reaction solution adds and disperse reaction.Reaction times is 0.5 hour.The reaction product hydroxy nickel oxide that obtains is black colloidal sol shape.
Reaction is washed reaction product hydroxy nickel oxide water repeatedly, is filtered after finishing, and can't check until washings till the existence of chlorion.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
Pour the hydroxy nickel oxide that drying obtains into the reaction of mixing in the container that fills the potassium hydroxide alkalescence aqueous solution again.The weight ratio of the hydroxy nickel oxide and the potassium hydroxide alkalescence aqueous solution is 1: 5.The potassium hydroxide alkalescence aqueous solution is dissolved in the tap water preparation by potassium hydroxide and gets, and its concentration is 10M.Temperature of reaction is 45 ℃, and the reaction times is 60 hours.
Once more reaction product hydroxy nickel oxide water is washed repeatedly, filters after reaction finishes, be neutral until the pH value of washings.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
The particle diameter of the above-mentioned nickel oxyhydroxide powder for preparing is measured with the low-angle scattering of X-rays method.Record the scope of the particle diameter of powder at 30-40nm, median size is 35nm.Product is tested through X-ray diffraction, and the result shows that its structure is a β type hydroxy nickel oxide.It is that positive active material, zinc powder are that negative electrode active material, potassium hydroxide aqueous solution are that the simulated battery that electrolytic solution is made is measured that the electrical property of hydroxy nickel oxide adopts with the hydroxy nickel oxide, and the first discharge specific capacity that records its 0.1C multiplying power discharging is 150mAh/g.
Embodiment 2
Take by weighing an amount of single nickel salt (NiSO 47H 2O) be dissolved in distilled water and be mixed with the 100ml aqueous solution.The concentration of the aqueous solution is 12M.Add weight percent with respect to single nickel salt therein and be 1% rose vitriol and be 4% Cadmium chloride fine powder with respect to the weight percent of single nickel salt, dissolving mixes makes reaction solution.
Taking by weighing proper amount of sodium hydroxide is dissolved in distilled water and is mixed with alkaline aqueous solution 167ml.The concentration of the aqueous solution is 14M.High-ranking military officer joins and is mixed with aqueous oxidizing agent solution 500ml in the 333ml aqueous sodium hypochlorite solution then.The concentration of aqueous sodium hypochlorite solution is 1M.
The above-mentioned aqueous oxidizing agent solution of 500ml placed carry out ultra-sonic oscillation on the ultrasound reactor and disperse, and be heated to 65 ℃, dropwise add the above-mentioned reaction solution of 100ml then.Proceed ultra-sonic oscillation after reaction solution adds and disperse reaction.Reaction times is 5 hours.The reaction product hydroxy nickel oxide that obtains is black colloidal sol shape.
Reaction is washed reaction product hydroxy nickel oxide water repeatedly, is filtered after finishing, and can't check until washings till the existence of chlorion.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
Dried hydroxy nickel oxide is poured again into the reaction of mixing in the container of the alkaline aqueous solution that fills sodium hydroxide.The weight ratio of the hydroxy nickel oxide and the sodium hydroxide alkalescence aqueous solution is 1: 10.The potassium hydroxide alkalescence aqueous solution is dissolved in the distilled water preparation by potassium hydroxide and gets.Its concentration is 14M.Temperature of reaction is 65 ℃, and the reaction times is 20 hours.
After reaction finishes reaction product hydroxy nickel oxide water is washed repeatedly, filters, be neutral until the pH value of washings.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
The particle diameter of the above-mentioned nickel oxyhydroxide powder for preparing is measured with the low-angle scattering of X-rays method.Record the scope of the particle diameter of powder at 40-50nm, median size is 45nm.Product is tested through X-ray diffraction, and the result shows that its structure is a β type hydroxy nickel oxide.It is that positive active material, zinc powder are that negative electrode active material, potassium hydroxide aqueous solution are that the simulated battery that electrolytic solution is made is measured that the electrical property of hydroxy nickel oxide adopts with the hydroxy nickel oxide, and the first discharge specific capacity that records its 0.1C multiplying power discharging is 120mAh/g.
Embodiment 3
Take by weighing an amount of nickelous nitrate (NiNO 36H 2O) be dissolved in deionized water and be mixed with the 100ml aqueous solution.The concentration of the aqueous solution is 5M.Add weight percent with respect to nickelous nitrate therein and be 5% cobalt chloride and be 2% zinc chloride with respect to the weight percent of nickelous nitrate, dissolving mixes makes reaction solution.
Take by weighing an amount of potassium hydroxide and be dissolved in deionized water and be mixed with alkaline aqueous solution 50ml, the concentration of the aqueous solution is 12M.Then it is joined and be mixed with aqueous oxidizing agent solution 500ml in the 450ml aqueous sodium hypochlorite solution.The concentration of aqueous sodium hypochlorite solution is 3M.
The above-mentioned aqueous oxidizing agent solution of 500ml placed carry out ultra-sonic oscillation on the ultrasound reactor and disperse, and be heated to 55 ℃, dropwise add the above-mentioned reaction solution of 100ml then.Proceed ultra-sonic oscillation after reaction solution adds and disperse reaction.Reaction times is 1 hour.The reaction product hydroxy nickel oxide that obtains is black colloidal sol shape.
Reaction is washed reaction product hydroxy nickel oxide water repeatedly, is filtered after finishing, and can't check until washings till the existence of chlorion.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
Dried hydroxy nickel oxide is poured again into the reaction of mixing in the container of the alkaline aqueous solution that fills potassium hydroxide.The weight ratio of the hydroxy nickel oxide and the potassium hydroxide alkalescence aqueous solution is 1: 8.The potassium hydroxide alkalescence aqueous solution is dissolved in the deionized water preparation by potassium hydroxide and gets.Its concentration is 12M.Temperature of reaction is 55 ℃, and the reaction times is 50 hours.
After reaction finishes reaction product hydroxy nickel oxide water is washed repeatedly, filters, be neutral until the pH value of washings.Place vacuum drying oven to carry out vacuum-drying reaction product then, be dried to till the reaction product constant weight always.
The particle diameter of the above-mentioned nickel oxyhydroxide powder for preparing is measured with the low-angle scattering of X-rays method.Record the scope of the particle diameter of powder at 25-35nm, median size is 30nm.Product is tested through X-ray diffraction, and the result shows that its structure is a β type hydroxy nickel oxide.It is that positive active material, zinc powder are that negative electrode active material, potassium hydroxide aqueous solution are that the simulated battery that electrolytic solution is made is measured that the electrical property of hydroxy nickel oxide adopts with the hydroxy nickel oxide, and the first discharge specific capacity that records its 0.1C multiplying power discharging is 250mAh/g.
Table 1 for the test result of electrical property under nano-grade hydroxy nickel oxide (B sample in the table) equal conditions of the nano-grade hydroxy nickel oxide (A sample in the table) of the present invention preparation and background technology relatively.Adopt three-electrode system to carry out the electric performance test of sample.Test condition is as follows: 80mg testing sample+20mg graphite+10mg acetylene black+one alkali lye (KOH of 9M), in the testing mould of packing into after mixing thoroughly, in the moulding of suitable pressure lower sheeting as research electrode.The Hg/HgO electrode is made reference electrode, and platinum filament is made supporting electrode, and platinized platinum is made collector, and the KOH of 9M makes electrolytic solution.With test system balance 10h, carry out the experiment that discharges and recharges of 5mA continuous current, the discharge stopping potential is 0V.
Table 1
Cycle index first the 2nd the order 3 the order 4 the order 5 times
The specific discharge capacity of A sample (mAh/g) 250 280 300 320 340
The specific discharge capacity of B sample (mAh/g) 35 180 250 280 300

Claims (3)

1, a kind of preparation method of nano-grade hydroxy nickel oxide is characterized in that divalent nickel salt is mixed with the aqueous solution, and the weight percent that adds with respect to divalent nickel salt is divalent cobalt, divalent zinc salt or the divalence cadmium salt of 1-5%, and dissolving mixes and makes reaction solution; Reaction solution dropwise joined in the alkaline aqueous solution that hypochlorous sodium is an oxygenant react; Reaction process adopts ultrasonic wave to carry out vibrating dispersion, and temperature of reaction is 45-65 ℃, and the reaction times is 0.5-5 hour.
2, the preparation method of nano-grade hydroxy nickel oxide according to claim 1 is characterized in that comprising the following steps:
(1) preparation of nano-grade hydroxy nickel oxide
1. be mixed with the aqueous solution that concentration is 0.1-12M with divalent nickel salt is water-soluble, adding with respect to the divalent nickel salt weight percent is divalent cobalt, divalent zinc salt or the divalence cadmium salt of 1-5%, and dissolving mixes makes reaction solution; Described divalent nickel salt is nickelous chloride, single nickel salt or nickelous nitrate; Water is deionized water, distilled water or tap water; Divalent cobalt is cobalt chloride, Xiao Suangu or rose vitriol; Divalent zinc salt is zinc chloride, zinc sulfate or zinc nitrate; The divalence cadmium salt is Cadmium chloride fine powder, Cadmium Sulphate or cadmium nitrate;
2. be mixed with the alkaline aqueous solution that concentration is 10-14M with potassium hydroxide or sodium hydroxide are water-soluble, add aqueous sodium hypochlorite solution and be mixed with aqueous oxidizing agent solution; The concentration of aqueous sodium hypochlorite solution is 1-5M; The volume ratio of aqueous sodium hypochlorite solution and potassium hydroxide or the sodium hydroxide alkalescence aqueous solution is 1 in the aqueous oxidizing agent solution: 0-0.5;
3. with the 2. the aqueous oxidizing agent solution that obtains of step place ultrasound reactor to carry out ultra-sonic oscillation to disperse, and be heated to 45-65 ℃, dropwise add the 1. reaction solution that obtain of step preparation; The volume ratio of reaction solution and aqueous oxidizing agent solution is 1: 5; Proceed ultra-sonic oscillation after reaction solution adds and disperse reaction; Reaction times is 0.5-5 hour, obtains being the reaction product hydroxy nickel oxide of black colloidal sol shape;
4. with the 3. the reaction product hydroxy nickel oxide water in step wash repeatedly, filter, can't check the existence of chlorion until washings; To place vacuum drying oven to carry out vacuum-drying through the reaction product of washing to the reaction product constant weight;
(2) doping of nano-grade hydroxy nickel oxide
The hydroxy nickel oxide that (1) prepares is poured in the reactor that fills alkaline aqueous solution, and the weight ratio of hydroxy nickel oxide and alkaline aqueous solution is 1: 5-10; Described alkaline aqueous solution is dissolved in deionized water, distilled water or tap water by in potassium hydroxide, sodium hydroxide or the lithium hydroxide one or more and obtains, and its concentration is 10-14M, and temperature of reaction is 45-65 ℃, and the reaction times is 20-60 hour.
3, the preparation method of nano-grade hydroxy nickel oxide according to claim 2, it is characterized in that the reaction product hydroxy nickel oxide water of (2) is washed repeatedly, filters, pH value until washings is neutral, then reaction product is placed vacuum drying oven to carry out vacuum-drying to the reaction product constant weight.
CNB031138837A 2003-03-10 2003-03-10 Nano grade nickel oxyhydroxide and process for preparing same Expired - Fee Related CN1226194C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB031138837A CN1226194C (en) 2003-03-10 2003-03-10 Nano grade nickel oxyhydroxide and process for preparing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB031138837A CN1226194C (en) 2003-03-10 2003-03-10 Nano grade nickel oxyhydroxide and process for preparing same

Publications (2)

Publication Number Publication Date
CN1433970A CN1433970A (en) 2003-08-06
CN1226194C true CN1226194C (en) 2005-11-09

Family

ID=27634216

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB031138837A Expired - Fee Related CN1226194C (en) 2003-03-10 2003-03-10 Nano grade nickel oxyhydroxide and process for preparing same

Country Status (1)

Country Link
CN (1) CN1226194C (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007103111A (en) * 2005-10-03 2007-04-19 Matsushita Electric Ind Co Ltd Alkaline primary battery and manufacturing method of nickel oxyhydroxide
CN100404429C (en) * 2005-11-11 2008-07-23 河南新飞科隆电源有限公司 Method for manufacturing spherical nickel oxyhydroxide
CN100365850C (en) * 2006-02-27 2008-01-30 孝感学院 Nano gamma hydrocarboxyl nickel/high ferrite composite material and preparing method
CN105322142A (en) * 2015-09-26 2016-02-10 河南新太行电源有限公司 Manufacturing method of positive plate of fiber-type cadmium-nickel storage battery
CN110294553A (en) * 2019-08-06 2019-10-01 镇江市和云工业废水处置有限公司 A kind of energy-saving processing method of chemical nickel plating waste solution
CN113149090B (en) * 2021-05-10 2024-03-26 安徽师范大学 Size-controllable transition metal oxide ultrafine nanoparticle and rapid preparation method and application thereof
CN114457370B (en) * 2022-03-23 2023-12-01 安徽工程大学 Vanadium-doped nickel oxyhydroxide nano-sheet and preparation method and application thereof
CN115554947A (en) * 2022-09-26 2023-01-03 宁波九胜创新医药科技有限公司 Method for loading hydroxyl nickel oxide in micro-channel reactor and application thereof
CN116022865A (en) * 2022-11-29 2023-04-28 宁波九胜创新医药科技有限公司 Nanoscale Ni 2 O 3 Nano Ni 2 O 3 Preparation method and application of base heterogeneous catalyst

Also Published As

Publication number Publication date
CN1433970A (en) 2003-08-06

Similar Documents

Publication Publication Date Title
CN108807931B (en) High-nickel material with surface coated with lithium aluminum silicate and surface layer doped with fluorine and preparation method
CN101525160A (en) Preparation method and application of nanometer nickel hydroxide and composite electrode thereof
CN1178313C (en) Alkaline storage battery
CN109671935B (en) Preparation method and application of silicon dioxide/biochar composite material
CN110931741A (en) Tin sulfide quantum dot loaded titanium carbide composite nano material and preparation method thereof
CN1226194C (en) Nano grade nickel oxyhydroxide and process for preparing same
CN107732203A (en) A kind of preparation method of nano ceric oxide/graphene/sulphur composite
CN108598409B (en) Lithium ion battery cathode material FeS/Fe/C and preparation method thereof
CN108862406A (en) A kind of carbonate precursor and its preparation method and application
Ren et al. Preparation of porous spherical α-Ni (OH) 2 and enhancement of high-temperature electrochemical performances through yttrium addition
CN108470892A (en) A kind of nickelic ternary anode material of lithium battery and preparation method of zinc doping
CN104600277A (en) Zinc and cobalt-doped nickel hydroxide/carbon nano composite material and preparation method and application of nano composite material
CN113410460B (en) Three-dimensional ordered macroporous carbon-coated nickel selenide nanocrystalline material, preparation and application
CN110571414B (en) Preparation method of sodium ion battery negative electrode material
CN102205989A (en) Preparation method for cathode material LiMn2O4 of cell
CN1485278A (en) Preparation method for secondary crystal lithium cobalt acid of positive electrode material of lithium ion cell
CN1225407C (en) Nano-range nickel gamma-hydroxy oxide and preparing process thereof
CN1821099A (en) Blended nano alpha-nickel hydroxide and its preparing method
CN105826535A (en) Three-dimensional porous carbon-loaded Na2Ge4O9 compound and preparation method thereof
CN115584032A (en) Ultrathin bimetal organic framework/carbon composite material and preparation method and application thereof
CN115425201A (en) Na 3 V 2 (PO 4 ) 2 F 3 Preparation method of positive electrode material of sodium-ion battery
CN115417465A (en) Nickel disulfide electrode material, preparation method and application
Xiancong et al. Study on the preparation and electrochemical performance of rare earth doped nano-Ni (OH) 2
CN114243007A (en) Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof
CN102509787A (en) Preparation method of doped spherical nanoscale Ni(OH)2

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20051109