CN102142547A - Preparation method of spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide - Google Patents
Preparation method of spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide Download PDFInfo
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Abstract
The invention relates to a preparation method of a spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide, comprising the following steps: heating cobalt hydroxide coated spherical nickel hydroxide which is utilized as a precursor, and spraying an alkali metal hydroxide aqueous solution; evenly mixing the precursor with the alkali metal hydroxide aqueous solution; introducing oxygen to oxidize the cobalt hydroxide to convert the cobalt hydroxide into high-valency gamma-hydroxy cobalt oxide; and during oxidation, combining mechanical agitation and ultrasonic agitation to prevent the spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide from gathering and cause alkali metal ions to be embedded into a crystal lattice with the laminated structure of the gamma-hydroxy cobalt oxide. After oxidation reaction is over, a lithium hydroxide alkaline solution at certain temperature is added into an oxidation reaction pot to carry out heat preservation on the spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide; when heat preservation is carried out, mechanical agitation and ultrasonic agitation are adopted to cause the lithium ions to be embedded into the laminated structure of the gamma-hydroxy cobalt oxide; and the obtained spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide is screened by an ultrasonic sieve shaker after being washed and dried.
Description
Technical field
The present invention relates to the battery material field, the preparation method of the positive electrode of the battery that to relate to metal-hydrogen nickel battery (MH/Ni), ickel-cadmium cell and other compound with nickel in more detail be active material is as the positive electrode nickel hydroxide (Ni (OH) of zinc-nickel cell, Hawkins cell etc.
2) the preparation method.
Background technology
The pollution of motor vehicle emission has at present become the key factor of urban atmospheric pollution, and the CO2 emission of China has occupied the whole world the second, and the pressure of reducing emission of carbon dioxide is with increasing.In recent years, the automobile industry of China development has become the world the fourth-largest automobile production state and the third-largest automobile consumption state rapidly.The petroleum resources shortage of China, annual petroleum import amount is with the percentage increase of two digits.Under the background of global resource scarcity and ecological deterioration, electric automobile is because the advantage of its energy source clean, non-pollution discharge progressively substitutes the inexorable trend that traditional fuel-engined vehicle has been development.The automobile industry of China lags behind developed country always; this global automobile industry is changed rare historic opportunities to China is provided, and therefore greatly developing new-energy automobile is to realize that Chinese energy safety, environmental protection and Chinese Automobile Industry ' realize the needs of great-leap-forward, sustainable development.
Electrokinetic cell is the technological core of electric automobile, is called as the heart of electric automobile, and the electric weight that it stores is the part or all of DIRECT ENERGY source of electric automobile.In hybrid vehicle (HEV), plug-in hybrid-power automobile (PHEV), pure electric automobile (PEV), power-driven system is the main part that new-energy automobile is worth, and the cost ratio of electrokinetic cell in power-driven system is then up to 50% ~ 70%.Therefore, the performance of electrokinetic cell and cost have directly determined the development course of new-energy automobile.Corresponding with it, these three kinds of optimal batteries of electric automobile are respectively: MH/Ni battery, lithium ion battery and fuel cell.The main distinction of this three classes battery is: the latter increases than successively than the former energy, but cost increases successively, and the key technology difficulty that need capture also increases successively.The developing direction of electric automobile, at present the most real is hybrid vehicle, comparatively speaking, the technology of Ni-MH power cell is the most ripe, has been the optimal selection of power battery for hybrid electric vehicle.Hybrid vehicle to the basic demand of Ni-MH power cell can reduce following some: (1) high-energy-density; (2) high power density; (3) than long cycle life; (4) good high low temperature charge-discharge performance; (5) battery consistency is good; (6) price is lower; (7) working service is convenient.
In order to satisfy the electrical property demand of Ni-MH power cell high power density, numerous scientific workers are to its positive electrode Ni (OH) that adopts
2Various surface modification treatment have been carried out.The Japan Patent P3363670 of Sanyo Electric Co., Ltd's application has proposed to make the low price cobalt (Co (OH) that is coated on ball shape nickel hydroxide surface by heat treated in the environment of alkaline solution and oxygen coexistence
2) be converted into the good high price cobalt of electric conductivity, promptly hydroxy cobalt oxide makes the ball-shape nickel hydroxide heavy-current discharge performance that covers hydroxy cobalt oxide that very big raising arranged.
The Chinese invention patent 97126317.5 of Panasonic Electric Equipment Industrial Co.,Ltd's application has disclosed a kind of higher active material utilization that has, surface coverage has the alkaline storage battery used nickel hydroxide positive plate active material of high price cobalt/cobalt oxide, and surface coverage high price cobalt/cobalt oxide is to contain K in the crystal structure
+Ion or Na
+γ-the hydroxy cobalt oxide of ion even this material transition is discharged, placed under short-circuit condition, also can well be recovered capacitance by charging modes.
Chinese invention patent " process of surface cobalt-coating of high-density ball-shape nickel hydroxide " (Chinese invention patent number 99107434.3) adopts a kind of dynamic integration feeding manner to make to cover transition zone of existence between bag cobalt floor and the former spherical nickel hydroxide particle cobalt layer and combine firmly by transition zone and ball-shape nickel hydroxide particle; Chinese invention patent " preparation method of coated gamma-hydroxy cobalt oxide nickel hydroxide " (Chinese invention patent number 200710035313.0) coats one deck cobalt hydroxide at ball shape nickel hydroxide surface earlier, and then under high-concentration sodium hydroxide and oxygen condition surface coated cobaltous hydroxide layer is oxidized to γ-hydroxy cobalt oxide.
Oxidation reaction takes place in the cobalt ball-shape nickel hydroxide that will cover that said method adopted under the condition of alkaline aqueous solution and oxygen coexistence, its basic reaction principle divides following two steps to carry out:
The first step, the Co of ball shape nickel hydroxide surface (OH)
2Dissolve in the alkaline aqueous solution that is reflected at ball shape nickel hydroxide surface according to following reaction equation ㈠, form the complex ion (HCoO of cobalt
2 -), this reaction is cobalt stripping reaction;
In second step, the complex ion of cobalt contacts the back with oxygen oxidized, shown in following reaction equation ㈡, generates hydroxy cobalt oxide deposit at high price at ball shape nickel hydroxide surface, and this reaction is the cobalt oxidation deposition reaction;
㈠：Co(OH)
2 + OH
- →?HCoO
2 - +?H
2O ；
㈡：HCoO
2 -+?1/2H
2O?+?1/4O
2?→?CoOOH?+?OH
-?。
But owing to adopt above method all to need the Co (OH) of elder generation with ball nickel surface
2Use the thermokalite stripping, again it is oxidized to the alkali insoluble matter-hydroxy cobalt oxide of high price, so the tiny particle of some ball-shape nickel hydroxides can pass through its surface C o (OH)
2Stripping and depositing again of CoOOH and bond to reunite and form bigger ball-shape nickel hydroxide particle aggregate together, and alkali lye can also with carbon dioxide in air (CO
2) reaction generation carbonate, carbonate plays the effect of bonding agent in the dry run of the ball-shape nickel hydroxide that covers hydroxy cobalt oxide, also can cause the tiny particle of some ball-shape nickel hydroxides to be reunited.The generation of reuniting descends the flowability of the ball-shape nickel hydroxide particle that covers hydroxy cobalt oxide, be not easy to be filled in the foaming nickel hole the thicker and embrittlement of battery pole piece thickness of making, easy part during battery winding, cause battery short circuit, can not assemble high-capacity battery.
Reunite in order to stop the bonding of ball-shape nickel hydroxide in oxidizing process of covering hydroxy cobalt oxide, Chinese patent ZL 02151988.9 at first by contain lithium hydroxide (LiOH) at bag cobalt nickel hydroxide shot-like particle jet surface, concentration is the alkali of 30 ~ 50% caustic-alkali aqueous solutions, bag cobalt nickel hydroxide shot-like particle and alkali mix, again the shot-like particle that mixes is sieved through 20 ~ 150 mesh sieves, carry out thermal oxidation to mixing shot-like particle, prevent that bonding because of the ball-shape nickel hydroxide particle from causing the generation of particle cluster.
Yet, even use the preparation-obtained ball-shape nickel hydroxide positive electrode that covers hydroxy cobalt oxide of said method still to have following problem:
(1), still unavoidably has parts of fine granule bonding in the oxidizing process after adding alkaline aqueous solution and reunite together owing to the particle that covers the hydroxy cobalt oxide ball-shape nickel hydroxide is tiny;
(2) LiOH that contains in the caustic-alkali aqueous solution and the carbon dioxide in air generation lithium carbonate that reacts, lithium carbonate plays the effect of bonding agent in the oxidizing process of covering the hydroxy cobalt oxide ball-shape nickel hydroxide, this bonding that will aggravate to cover the fine particle of hydroxy cobalt oxide ball-shape nickel hydroxide is reunited;
(3) adopt 20 ~ 150 purpose screen clothes to sieve the shot-like particle that mixes in the production, can produce more not sieving materials, therefore influenced the harvest rate of product.
Summary of the invention
The objective of the invention is to the problem that exists at prior art and the preparation method of a kind of γ of covering-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode is provided.Unite less with the γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle that covers that this method prepares, the surface conductivity height, the high power discharge performance is good, discharge capacity recovery rate height, operating procedure is easily understood, product quality is controlled easily.
The preparation method of the γ of covering of the present invention-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode comprises following 3 preparation processes:
Step ⑴: with the ball-shape nickel hydroxide that coats cobalt hydroxide as presoma, at first presoma is inserted in the airtight oxidation reactor and heat, adopt mechanical agitation that the presoma surface temperature is kept evenly, reaching the alkali metal hydroxide aqueous solution that will have uniform temperature after the uniform temperature again joins in the oxidation reactor in the spray mode, stirring and evenly mixing is evenly soaked into the presoma surface by alkali metal hydroxide aqueous solution; The aerating oxygen nickel hydroxide material that the surface coated in the airtight oxidation reactor cobalt hydroxide carries out surface oxidation treatment then, opens airtight oxidation reactor simultaneously, makes the O of feeding
2Moisture in the product is taken away, γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle is covered in formation, adopt ultrasonic stirring and mechanical agitation to cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle simultaneously in oxidizing process and unite, and alkali metal ion can be embedded in the lattice of γ-hydroxy cobalt oxide stratiform structure with prevention.Its reaction principle is shown in following reaction equation:
㈢：Co(OH)
2 + OH
-?→?HCoO
2 - +?H
2O?；
㈣：HCoO
2 -+?H
2O?+?O
2?+?AOH?→?γ-Co
(1-x)A
xOOH·n?H
2O?+?OH
- 。
A is alkali metallic sodium ion (Na in the formula
+), potassium ion (K
+) in a kind of or Na
+Ion and K
+The mixture of ion, the alkali metal ion molal quantity in γ-hydroxy cobalt oxide stratiform structure is inserted in the X representative, and the hydrone molal quantity in γ-hydroxy cobalt oxide stratiform structure is inserted in the n representative.
Reaction equation ㈢ is the cobalt stripping reaction that ball shape nickel hydroxide surface covers cobaltous hydroxide layer, reaction equation ㈣ is the cobalt oxidation intercalation, specifically be when oxidation reaction is carried out, under the ultrasonic wave effect, there is the part alkali metal ion to be inserted in the layer structure of hydroxy cobalt oxide, generated γ-hydroxy cobalt oxide.γ-hydroxy cobalt oxide is a kind of non-stoichiometric compound with layer structure, owing to contain in the layer structure+alkali metal ion of 1 valency, and in order to keep the balance of electric charge, the Co of valency partly+3
3+Ion can be converted into higher valence state+4 valency Co
4+Ion, therefore in γ-hydroxy cobalt oxide the chemical valence of cobalt have+3 valencys and+4 valencys appraise at the current rate for two kinds, average valence can be greater than+3 valencys, its theoretical chemical valence is up to+3.67 valencys, far above common beta-hydroxy cobalt oxide (among the β-CoOOH) cobalt+chemical valence of 3 valencys, make γ-hydroxy cobalt oxide have higher conductivity, and its reduction potential is also lower, can not be reduced easily+Co of divalent
2+Ion, because+Co of divalent
2+Ion is very easily dissolving in alkali lye, thereby causes conductive network destroyed.Do the long-term overdischarge of MH/Ni battery of positive electrode active materials making, under short-circuit condition, place even cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide, also can its capacity well is restored by charging modes with this.
Step ⑵: in oxidation reactor, add LiOH alkaline aqueous solution after oxidation reaction finishes product further is incubated processing, in insulation, adopt ultrasonic stirring and mechanical agitation, make Li with uniform temperature
+Alkali-Metal Na in ion and γ-hydroxy cobalt oxide lattice
+Ion or K
+Ion generation intercalation displacement reaction and entering in γ-hydroxy cobalt oxide lattice.Its intercalation displacement reaction principle is shown in reaction equation ㈤:
㈤：γ-Co
(1-x)A
xOOH·n?H
2O?+?Z?Li
+?→?γ-Co
(1-y-z)A
yLi
zOOH·n?H
2O?+?A
+。
A represents Alkali-Metal Na in the formula
+Ion, K
+A kind of or Na in the ion
+Ion and K
+The mixture of ion, X represents the preceding alkali metal ion molal quantity that inserts in γ-hydroxy cobalt oxide stratiform structure of intercalation displacement reaction, Y represents the alkali metal ion molal quantity in γ-hydroxy cobalt oxide stratiform structure after the intercalation displacement reaction, and Z represents the Li that inserts after the intercalation displacement reaction in γ-hydroxy cobalt oxide stratiform structure
+The ion molal quantity, the hydrone molal quantity in γ-hydroxy cobalt oxide stratiform structure is inserted in the n representative.
After the insulation processing, Li
+Ion enters in γ-hydroxy cobalt oxide lattice, makes with this capacity that covers the MH/Ni battery that γ-hydroxy cobalt oxide ball-shape nickel hydroxide makes as positive electrode active materials highlyer, and interior pressure is littler.
Step ⑶: the γ-hydroxy cobalt oxide ball-shape nickel hydroxide that covers that obtains is carried out the washing and drying processing, to adopt the ultrasonic wave vibrating sieving machine to sieve through the product of washing and drying then, effectively stoped and covered γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and unite, significantly improved high power discharge performance and the overdischarge capacity restoration performance of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode.
The preparation method is as follows more specifically for the preparation method of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide of the present invention:
The oxidation step of the ball-shape nickel hydroxide precursor of surface coating cobalt hydroxide is among the step ⑴:
1. the ball-shape nickel hydroxide precursor that takes by weighing an amount of coating cobalt hydroxide places airtight oxidation reactor, be heated to 80 ~ 150 ℃, adopted mechanical agitation 5 ~ 30 minutes, the presoma surface temperature is kept evenly, churned mechanically mixing speed is 50 ~ 500 rev/mins;
2. it is soluble in water and to be mixed with mass percent be 40 ~ 80% alkaline aqueous solution to take by weighing an amount of alkali metal hydroxide, described alkali metal hydroxide is one or more in potassium hydroxide (KOH) or the NaOH (NaOH), the temperature of alkaline aqueous solution is 100 ~ 150 ℃, and water is deionized water, distilled water or running water;
Alkaline aqueous solution of 2. preparing in the step is joined in the oxidation reactor in the spray mode, coating the ball-shape nickel hydroxide of cobalt hydroxide and the mass ratio of alkaline aqueous solution is 10:0.5 ~ 2, adopting churned mechanically mixing time is 5 ~ 20 minutes, make and cover the cobalt hydroxide ball shape nickel hydroxide surface and evenly soaked into by alkali lye, churned mechanically mixing speed is 50 ~ 500 rev/mins;
The ball-shape nickel hydroxide insulation treatment step that covers γ-hydroxy cobalt oxide among the step ⑵ is:
1. it is soluble in water and to be mixed with mass percent be 0.1 ~ 1% LiOH alkaline aqueous solution to take by weighing an amount of LiOH, and the temperature of LiOH alkaline aqueous solution is 50 ~ 100 ℃, and water is deionized water, distilled water or running water;
2. with the 1. the LiOH alkaline aqueous solution that obtains of step preparation add in the oxidation reactor after (1) step reaction finishes, the addition of LiOH alkaline aqueous solution is 1:0.1 ~ 0.5 with the mass ratio that covers the ball-shape nickel hydroxide product of γ-hydroxy cobalt oxide, the temperature that insulation is handled is 50 ~ 100 ℃, and the time is 20 ~ 120 minutes; Insulating process adopts ultrasonic stirring and mechanical agitation simultaneously, makes Li
+Alkali-Metal Na in ion and γ-hydroxy cobalt oxide lattice
+Ion or K
+Ion generation displacement reaction and entering in γ-hydroxy cobalt oxide lattice, the frequency of ultrasonic stirring device is 20 ~ 40KHz, churned mechanically mixing speed is 50 ~ 500 rev/mins.
The ball-shape nickel hydroxide washing drying and screening step of covering γ-hydroxy cobalt oxide in the step (3) is:
1. (2) step insulation is handled that the product water that obtains washs repeatedly, suction filtration, until through the product P H value of washing less than 8, the temperature of slurry is 50 ~ 80 ℃, water is deionized water or distilled water;
2. with the 1. the product in step place drier dry, baking temperature is 70 ~ 100 ℃, be 2 ~ 6 hours drying time, until the mass percent of product water content less than 1.5%;
3. adopt the ultrasonic wave vibrating sieving machine that product that 2. obtains is sieved, the order number of screen cloth is 50 ~ 200 orders, and the frequency of ultrasonic wave vibrating sieving machine is 20 ~ 40KHz, and what obtain that outward appearance is black covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide product.
The product that obtains according to above-mentioned preparation method is for covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode, and the crystal structure of this material sample adopts X-ray diffractometer (XRD) to test; The content of alkali metal ion adopts Atomic Absorption Spectrometer (AAS) test in the sample, adopt the surface topography of scanning electron microscopy (SEM) observation sample, adopt laser particle analyzer working sample particle size distribution, it is that positive active material, hydrogen-storage alloy powder are that negative electrode active material, foaming nickel are that matrix, KOH+NaOH+LiOH ternary system alkaline aqueous solution are that No. five (AA type) MH/Ni batteries that electrolyte is made discharge and recharge mensuration that the sample electrical property adopts with this sample.
The present invention compared with prior art has following advantage:
(1) preparation method of the γ of covering of the present invention-hydroxy cobalt oxide ball-shape nickel hydroxide carries out in ultrasonic stirring and mechanical agitation, so not only can make the oxidation reaction of the cobalt hydroxide that is coated on ball shape nickel hydroxide surface carry out more thoroughly, but also reactant and product thereof fully are uniformly dispersed, more effectively prevent the reunion of product particle, thus prepare do not unite, flowability better covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide;
(2) preparation method of the present invention will be covered γ-hydroxy cobalt oxide ball-shape nickel hydroxide and be incubated in the LiOH alkaline aqueous solution, adopt ultrasonic stirring in the insulating process, make Li under the ultrasonic wave effect
+Na in ion and the hydroxy cobalt oxide stratiform lattice structure
+Ion or K
+Ion generation intercalation displacement reaction enters in γ-hydroxy cobalt oxide lattice, compare that to cover the method that γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and alkaline aqueous solution add simultaneously in oxidizing process more even, required addition also still less, make this agglomerated particle that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide still less, because the high price cobalt/cobalt oxide of this surface coating is to contain Li in the crystal structure
+γ-the hydroxy cobalt oxide of ion, thus make the capacity of the MH/Ni battery of making as positive electrode active materials with this material higher, and interior pressure is littler, even overdischarge, place under short-circuit condition, also can battery capacity well be recovered by charging modes;
(3) γ-hydroxy cobalt oxide ball-shape nickel hydroxide product that covers of the present invention's preparation adopts the ultrasonic wave vibrating sieving machine to sieve after washing drying, has stoped the reunion of product, has effectively reduced the not ratio of sieving materials, has significantly improved product harvest rate;
(4) the every technological parameter that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide of the present invention preparation can be as required regulating and controlling voluntarily.The prepared quality of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide is controlled easily, and production technology is simple, is easy to carry out large-scale industrial production.
Description of drawings
Fig. 1 is the scanning electron microscope sem collection of illustrative plates that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample that preparation method of the present invention makes;
Fig. 2 is the XRD figure spectrum of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide that preparation method of the present invention makes.
Embodiment
Embodiment 1
The ball-shape nickel hydroxide that takes by weighing 5Kg coating cobalt hydroxide places airtight oxidation reactor as precursor, is heated to 80 ℃, adopts mechanical agitation 10 minutes, makes the presoma surface temperature keep uniformity, and churned mechanically mixing speed is 500 rev/mins.
The NaOH that takes by weighing 200g is dissolved in the deionized water and is mixed with NaOH quality percentage composition is 80% 250g alkaline aqueous solution, and the temperature of alkaline aqueous solution is 100 ℃.
The 250g alkaline aqueous solution of above-mentioned preparation is joined in the airtight oxidation reactor in the spray mode, adopt mechanical agitation, mixing time is 5 minutes, makes to cover the cobalt hydroxide ball shape nickel hydroxide surface and evenly soaked into by alkali lye, and churned mechanically mixing speed is 500 rev/mins.
Feed O
2In airtight oxidation reactor, O
2Flow be 5 meters
3/ hour, open the vent valve of airtight oxidation reactor simultaneously, make O
2When carrying out oxidation reaction, the moisture in the product is discharged together, in oxidation reaction process, adopt ultrasonic stirring and mechanical agitation to combine simultaneously to cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and unite, and make Alkali-Metal Na with prevention
+Ion can be embedded in the lattice of γ-hydroxy cobalt oxide stratiform structure.The frequency of ultrasonic stirring device is 20KHz, and churned mechanically mixing speed is 500 rev/mins, and reaction temperature is 100 ℃, and the reaction time is 3 hours.
The LiOH that takes by weighing 50g is dissolved in the deionized water and is mixed with LiOH quality percentage composition is 0.1% 50Kg LiOH alkaline aqueous solution, and the temperature of LiOH alkaline aqueous solution is 50 ℃.
The LiOH alkaline aqueous solution that above-mentioned preparation is obtained joins in the above-mentioned oxidation reactor, be incubated processing to covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide, the temperature that insulation is handled is 50 ℃, and the time is 120 minutes, in insulating process, adopt ultrasonic stirring and mechanical agitation simultaneously, make Li
+Na in ion and γ-hydroxy cobalt oxide lattice
+The part generation displacement reaction of ion and entering in γ-hydroxy cobalt oxide lattice, the frequency of ultrasonic stirring device is 20KHz, churned mechanically mixing speed is 500 rev/mins.
The product that above-mentioned insulation is obtained with deionized water wash repeatedly, suction filtration, until through the product P H value of washing less than 8, the temperature of slurry is 50 ℃.
The product that above-mentioned washing is obtained places drier to carry out drying, and baking temperature is 70 ℃, and be 6 hours drying time, until the mass percent of product water content less than 1.5%.
Adopt the ultrasonic wave vibrating sieving machine that the product that above-mentioned drying obtains is sieved then, the order number of screen cloth is 50 orders, and the frequency of ultrasonic wave vibrating sieving machine is 20KHz, and what obtain that outward appearance is black covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide product.
The above-mentioned crystal structure that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample for preparing adopts XRD to test, and the result shows that its crystal structure is β-Ni (OH)
2Li in the sample
+Ion and Na
+The content of ion adopts the AAS test, records Li in the sample
+The quality percentage composition of ion is 0.0852%, Na
+The quality percentage composition of ion is 0.2528%.Adopt the surface topography of SEM observation sample, find to cover between γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample particle and do not reunite.Adopt laser particle analyzer working sample particle size distribution, record the scope of the particle size distribution of sample at 4 ~ 22 μ m, the D50 median particle diameter is 11.5 μ m.It is that positive active material, hydrogen-storage alloy powder are that negative electrode active material, foaming nickel are that matrix, KOH+NaOH+LiOH ternary system alkaline aqueous solution are that No. five (AA type) MH/Ni batteries that electrolyte is made discharge and recharge mensuration that the sample electrical property adopts with this sample, record its 10C high-multiplying power discharge specific capacity up to 230mAh/g, the capacity restoration rate that battery recharges after adopting 5 ohm of (Ω) resistance to continue one week of overdischarge in 60 ℃ of baking ovens is up to 99%.
Embodiment 2
The ball-shape nickel hydroxide that takes by weighing 5Kg coating cobalt hydroxide places airtight oxidation reactor as precursor, is heated to 150 ℃, adopts mechanical agitation 30 minutes, makes the presoma surface temperature keep uniformity, and churned mechanically mixing speed is 50 rev/mins.
The potassium hydroxide (KOH) that takes by weighing 400g is dissolved in the distilled water and the quality percentage composition that is mixed with KOH is 40% 1Kg alkaline aqueous solution, and the temperature of alkaline aqueous solution is 150 ℃.
The 1Kg alkaline aqueous solution of above-mentioned preparation is joined in the airtight oxidation reactor in the spray mode, adopt mechanical agitation, mixing time is 20 minutes, makes to cover the cobalt hydroxide ball shape nickel hydroxide surface and evenly soaked into by alkali lye, and churned mechanically mixing speed is 50 rev/mins.
Feed O
2In airtight oxidation reactor, O
2Flow be 30 meters
3/ hour, open the vent valve of airtight oxidation reactor simultaneously, make O
2When carrying out oxidation reaction, the moisture in the product is discharged together, in oxidation reaction process, adopt ultrasonic stirring and mechanical agitation to combine simultaneously to cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and unite, and make alkali metal K with prevention
+Ion can be embedded in the lattice of γ-hydroxy cobalt oxide stratiform structure.The frequency of ultrasonic stirring device is 40KHz, and churned mechanically mixing speed is 50 rev/mins, and reaction temperature is 165 ℃, and the reaction time is 0.5 hour.
Taking by weighing that the 100g lithium hydroxide is dissolved in the distilled water and is mixed with the LiOH mass percent is 1% 10Kg LiOH alkaline aqueous solution, and the temperature of LiOH alkaline aqueous solution is 100 ℃.
The LiOH alkaline aqueous solution that above-mentioned preparation is obtained joins in the above-mentioned oxidation reactor, be incubated processing to covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide, the temperature that insulation is handled is 100 ℃, and the time is 20 minutes, adopt ultrasonic stirring and mechanical agitation in the insulating process simultaneously, make Li
+K in ion and γ-hydroxy cobalt oxide lattice
+The part generation displacement reaction of ion and entering in γ-hydroxy cobalt oxide lattice, the frequency of ultrasonic stirring device is 40KHz, churned mechanically mixing speed is 50 rev/mins.
The product that above-mentioned insulation is obtained with distilled water wash repeatedly, suction filtration, until through the product P H value of washing less than 8, the temperature of slurry is 80 ℃.
The product that above-mentioned washing is obtained is put and is carried out drying in the drier, and baking temperature is 100 ℃, and be 2 hours drying time, until the mass percent of product water content less than 1.5%.
Adopt the ultrasonic wave vibrating sieving machine that the product that above-mentioned drying obtains is sieved, the order number of screen cloth is 200 orders, and the frequency of ultrasonic wave vibrating sieving machine is 40KHz, and what obtain that outward appearance is black covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide product.
The above-mentioned crystal structure that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample for preparing adopts XRD to test, and the result shows that its crystal structure is β-Ni (OH)
2Li in the sample
+Ion and K
+The content of ion adopts the AAS test, records Li in the sample
+The quality percentage composition of ion is 0.1258%, K
+The quality percentage composition of ion is 0.2328%.Adopt the surface topography of SEM observation sample, find to cover between γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample particle and do not reunite.Adopt laser particle analyzer working sample particle size distribution, record the scope of the particle size distribution of sample at 5 ~ 24 μ m, the D50 median particle diameter is 12.5 μ m.It is that positive active material, hydrogen-storage alloy powder are that negative electrode active material, foaming nickel are that matrix, KOH+NaOH+LiOH ternary system alkaline aqueous solution are that No. five (AA type) MH/Ni batteries that electrolyte is made discharge and recharge mensuration that the sample electrical property adopts with this sample, record its 10C high-multiplying power discharge specific capacity up to 235mAh/g, the capacity restoration rate that battery recharges after adopting 5 Ω resistance to continue one week of overdischarge in 60 ℃ of baking ovens is up to 100%.
Embodiment 3
The ball-shape nickel hydroxide that takes by weighing 5Kg coating cobalt hydroxide places airtight oxidation reactor as precursor, is heated to 130 ℃, adopts mechanical agitation 20 minutes, makes the presoma surface temperature keep uniformity, and churned mechanically mixing speed is 250 rev/mins.
The KOH that takes by weighing the NaOH of 165g and 165g respectively is dissolved in the running water and is mixed with NaOH and the quality percentage composition of KOH respectively accounts for 30% NaOH and KOH mixed-alkali aqueous solution 550g, and the temperature of the mixed-alkali aqueous solution is 130 ℃.
The 550g mixed-alkali aqueous solution of above-mentioned preparation is joined in the airtight oxidation reactor in the spray mode, adopt mechanical agitation, mixing time is 10 minutes, makes to cover the cobalt hydroxide ball shape nickel hydroxide surface and evenly soaked into by alkali lye, and churned mechanically mixing speed is 250 rev/mins.
Feed O
2In airtight oxidation reactor, O
2Flow be 15 meters
3/ hour, open the vent valve of airtight oxidation reactor simultaneously, make O
2When carrying out oxidation reaction, the moisture in the product is discharged together, in oxidation reaction process, adopt ultrasonic stirring and mechanical agitation to combine simultaneously to cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and unite, and make Alkali-Metal Na with prevention
+Ion and K
+Ion can be embedded in the lattice of γ-hydroxy cobalt oxide stratiform structure.The frequency of ultrasonic stirring device is 30KHz, and churned mechanically mixing speed is 250 rev/mins, and reaction temperature is 130 ℃, and the reaction time is 1.5 hours.
The lithium hydroxide that takes by weighing 90g is dissolved in running water, and to be mixed with LiOH quality percentage composition be 0.3% LiOH alkaline aqueous solution 30Kg, and the temperature of LiOH alkaline aqueous solution is 80 ℃.
The LiOH alkaline aqueous solution that above-mentioned preparation is obtained joins in the above-mentioned oxidation reactor, be incubated processing to covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide, the temperature that insulation is handled is 80 ℃, and the time is 60 minutes, adopt ultrasonic stirring and mechanical agitation in the insulating process simultaneously, make Li
+Na in ion and γ-hydroxy cobalt oxide lattice
+Ion and K
+The part generation displacement reaction of ion and entering in γ-hydroxy cobalt oxide lattice, the frequency of ultrasonic stirring device is 30KHz, churned mechanically mixing speed is 250 rev/mins.
The product that above-mentioned insulation is obtained with deionized water wash repeatedly, suction filtration, until through the product P H value of washing less than 8, the temperature of slurry is 65 ℃.
The product that above-mentioned washing is obtained is put and is carried out drying in the drier, and baking temperature is 90 ℃, and be 3 hours drying time, until the mass percent of product water content less than 1.5%.
Adopt the ultrasonic wave vibrating sieving machine that the product that above-mentioned drying obtains is sieved, the order number of screen cloth is 100 orders, and the frequency of ultrasonic wave vibrating sieving machine is 30KHz, and what obtain that outward appearance is black covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide product.
The above-mentioned crystal structure that covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample for preparing adopts XRD to test, and the result shows that its crystal structure is β-Ni (OH)
2Li in the sample
+Ion, K
+Ion and Na
+The content of ion adopts the AAS test, records Li in the sample
+The quality percentage composition of ion is 0.0973%, K
+The quality percentage composition of ion is 0.1528%, Na
+The quality percentage composition of ion is 0.1419%.Adopt the surface topography of SEM observation sample, find to cover between γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample particle and do not reunite.Adopt laser particle analyzer working sample particle size distribution, record the scope of the particle size distribution of sample at 6 ~ 26 μ m, the D50 median particle diameter is 13.0 μ m.It is that positive active material, hydrogen-storage alloy powder are that negative electrode active material, foaming nickel are that matrix, KOH+NaOH+LiOH ternary system alkaline aqueous solution are that No. five (AA type) MH/Ni batteries that electrolyte is made discharge and recharge mensuration that the sample electrical property adopts with this sample, record its 10C high-multiplying power discharge specific capacity up to 245mAh/g, the capacity restoration rate that battery recharges after adopting 5 Ω resistance to continue one week of overdischarge in 60 ℃ of baking ovens is up to 101%.
Cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode and accompanying drawing as can be known according to what above-mentioned 3 embodiment obtained, as seen, this covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide sample spherical particle agglomeration does not take place in Fig. 1; As seen, be respectively 19.064,33.031,38.442 places at 2 θ angles and shown significantly three strongest ones peak in Fig. 2, the crystal structure that shows sample is β-Ni (OH).
The above only is preferred embodiment of the present invention, is not technology contents of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (5)
1. preparation method of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode, it is characterized in that: its preparation process is:
With the ball-shape nickel hydroxide that coats cobalt hydroxide as presoma, at first presoma is inserted in the airtight oxidation reactor and heat, adopt mechanical agitation that the presoma surface temperature is kept evenly, reaching the alkali metal hydroxide aqueous solution that will have uniform temperature after the uniform temperature again joins in the oxidation reactor in the spray mode, stirring and evenly mixing is evenly soaked into the presoma surface by alkali metal hydroxide aqueous solution; The aerating oxygen nickel hydroxide material that the surface coated in the airtight oxidation reactor cobalt hydroxide carries out surface oxidation treatment then, opens airtight oxidation reactor simultaneously, makes the O of feeding
2Moisture in the product is taken away, γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle is covered in formation, adopt ultrasonic stirring and mechanical agitation to cover γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle simultaneously in oxidizing process and unite, and alkali metal ion can be embedded in the lattice of γ-hydroxy cobalt oxide stratiform structure with prevention;
⑵ in oxidation reactor, add LiOH alkaline aqueous solution after oxidation reaction finishes product further is incubated processing, in insulation, adopt ultrasonic stirring and mechanical agitation, make Li with uniform temperature
+Alkali-Metal Na in ion and γ-hydroxy cobalt oxide lattice
+Ion or K
+Ion generation intercalation displacement reaction and entering in γ-hydroxy cobalt oxide lattice;
⑶ carry out the washing and drying processing to the γ-hydroxy cobalt oxide ball-shape nickel hydroxide that covers that obtains, to adopt the ultrasonic wave vibrating sieving machine to sieve through the product of washing and drying then, effectively stoped and covered γ-hydroxy cobalt oxide ball-shape nickel hydroxide particle and unite, significantly improved high power discharge performance and the overdischarge capacity restoration performance of covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode.
2. preparation method according to claim 1 is characterized in that:
The oxidation step of the ball-shape nickel hydroxide precursor of surface coating cobalt hydroxide is among the step ⑴:
1. the ball-shape nickel hydroxide precursor that takes by weighing an amount of coating cobalt hydroxide places airtight oxidation reactor, be heated to 80 ~ 150 ℃, adopted mechanical agitation 5 ~ 30 minutes, the presoma surface temperature is kept evenly, churned mechanically mixing speed is 50 ~ 500 rev/mins;
2. it is soluble in water and to be mixed with mass percent be 40 ~ 80% alkaline aqueous solution to take by weighing an amount of alkali metal hydroxide, described alkali metal hydroxide is one or more in potassium hydroxide (KOH) or the NaOH (NaOH), the temperature of alkaline aqueous solution is 100 ~ 150 ℃, and water is deionized water, distilled water or running water;
3. preparation method according to claim 1 is characterized in that:
The ball-shape nickel hydroxide insulation treatment step that covers γ-hydroxy cobalt oxide among the step ⑵ is:
1. it is soluble in water and to be mixed with mass percent be 0.1 ~ 1% LiOH alkaline aqueous solution to take by weighing an amount of LiOH, and the temperature of LiOH alkaline aqueous solution is 50 ~ 100 ℃, and water is deionized water, distilled water or running water;
2. with the 1. the LiOH alkaline aqueous solution that obtains of step preparation add in the oxidation reactor after (1) step reaction finishes, the addition of LiOH alkaline aqueous solution is 1:0.1 ~ 0.5 with the mass ratio that covers the ball-shape nickel hydroxide product of γ-hydroxy cobalt oxide, the temperature that insulation is handled is 50 ~ 100 ℃, and the time is 20 ~ 120 minutes; Insulating process adopts ultrasonic stirring and mechanical agitation simultaneously, makes Li
+Alkali-Metal Na in ion and γ-hydroxy cobalt oxide lattice
+Ion or K
+Ion generation displacement reaction and entering in γ-hydroxy cobalt oxide lattice, the frequency of ultrasonic stirring device is 20 ~ 40KHz, churned mechanically mixing speed is 50 ~ 500 rev/mins.
4. preparation method according to claim 1 is characterized in that: the ball-shape nickel hydroxide washing drying and screening step of covering γ-hydroxy cobalt oxide in the step (3) is:
1. (2) step insulation is handled that the product water that obtains washs repeatedly, suction filtration, until through the product P H value of washing less than 8, the temperature of slurry is 50 ~ 80 ℃, water is deionized water or distilled water;
2. with the 1. the product in step place drier dry, baking temperature is 70 ~ 100 ℃, be 2 ~ 6 hours drying time, until the mass percent of product water content less than 1.5%;
3. adopt the ultrasonic wave vibrating sieving machine that product that 2. obtains is sieved, the order number of screen cloth is 50 ~ 200 orders, and the frequency of ultrasonic wave vibrating sieving machine is 20 ~ 40KHz, and what obtain that outward appearance is black covers γ-hydroxy cobalt oxide ball-shape nickel hydroxide product.
5. claim 1 or 2 or 3 or 4 described preparation methods: utilize product that this preparation method obtains for covering γ-hydroxy cobalt oxide ball-shape nickel hydroxide positive electrode.
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