CN101391798B - Doped nickel-base alkaline secondary cell anode material and preparation method thereof - Google Patents
Doped nickel-base alkaline secondary cell anode material and preparation method thereof Download PDFInfo
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- CN101391798B CN101391798B CN2008101553340A CN200810155334A CN101391798B CN 101391798 B CN101391798 B CN 101391798B CN 2008101553340 A CN2008101553340 A CN 2008101553340A CN 200810155334 A CN200810155334 A CN 200810155334A CN 101391798 B CN101391798 B CN 101391798B
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Abstract
The invention relates to an impure nickel base alkaline secondary battery cathode material and a preparation method thereof. Three preparation methods are used for compounding the material, namely, hydrothermal, chemical coating and mechanical mixing. The material has better charge and discharge, discharging capacity, high and low temperature performance, and cycle life than power crystal which is not doped with (Ni4Al(OH)10)OH hydrate. For example, a sample mixed with zinc which is compounded by hydrothermal contain (Ni4AlZny(OH)(10+2y))OH and ZnO; and both show good crystallinity. SEM showsthat (Ni4AlZny(OH)(10+2y))OH is crystal ribbon and Zno is clavate crystal; the material has good charge and discharge reversibility, and is a nickel base alkaline secondary battery cathode material with good performance. Compared with the sample which is not doped with (Ni4Al(OH)10)OH, the sample which is doped with calcium and yttric has better high temperature performance.
Description
Technical field
The present invention relates to a kind of [Ni of doping
4Al (OH)
10] positive electrode and preparation method thereof of OH nickel-base alkaline secondary cell, belong to the technical field that battery material is made.
Background technology
Nickel-base alkaline secondary cell comprises metal-hydrogen nickel battery (hereinafter to be referred as Ni-MH battery), ickel-cadmium cell, Hawkins cell, zinc-nickel cell or the like, and they all use nickel hydroxide as positive electrode.Wherein, metal-hydrogen nickel battery is a kind of novel high-energy secondary cell, have high energy density, good overcharging resisting discharge capability, use cost is low, but and heavy-current discharge, can sealing, premium properties such as memory-less effect and Environmental compatibility be good.In recent years, fast development along with mobile communication, notebook computer and electric vehicle, people also propose higher requirement to the performance of battery, than discharge capacity, longer useful life, also require to possess high rate during charging-discharging as bigger quality (volume) in the electric vehicle field.
The key of high-performance secondary cell is to have the electrode material of good charge-discharge performance.Nickel hydroxide has two kinds of crystal formations, α-and β-Ni (OH)
2Structurally, β-Ni (OH)
2Belong to hexagonal crystal system (P3ml-D
3The 3d space group), has similar water magnesite structure; α-Ni (OH)
2For having the hydroxide hydrate of layer structure, interlayer contains large quantity of moisture, also can embed as OH
-, NO
3 -, CO
3 2-, SO
4 2-Deng anion.The respectively corresponding two kinds of crystal formations of their Charging state NiOOH, β-NiOOH and γ-NiOOH.In the normal charge and discharge process of nickel electrode, β-Ni (OH)
2With β-NiOOH change, α-NiOOH and γ-Ni (OH)
2Change.β-Ni (OH)
2With β-NiOOH electricity to a problem is arranged, when overcharging exactly, β-NiOOH can change into γ-NiOOH.Because the density of γ-NiOOH is than β-Ni (OH)
2Density is much smaller, thereby nickel electrode serious electrode will take place will expand when overcharging, and electrode be caused irreversible infringement, thereby seriously influence the cycle life of battery.And α-Ni (OH)
2And the conversion invertibity height between γ-NiOOH, reaction speed is fast, and the average valence of adding Ni among γ-NiOOH can be greater than 3.5, by α-Ni (OH)
2The nickel electrode of forming has higher weight ratio capacity, longer cycle life and the charging and discharging currents density of Geng Gao.
α-Ni (OH)
2A fatal shortcoming is arranged, and is exactly that it is unstable under alkali condition.In addition, its density is little, causes the unit volume discharge capacity less.Research through a large amount of it is found that to Ni (OH)
2The doping trivalent metal ion is as Al
3+Can make its Stability Analysis of Structuresization, and still have than β-Ni (OH)
2The charging and discharging currents density of higher weight ratio capacity, longer cycle life and Geng Gao.For example, our granted patent ZL200610037887.7 has just reported that a kind of ideal consists of [Ni
4Al (OH)
10] excellent properties of hydrate of OH.Our big quantity research has proved absolutely that this material is the ideal material of electrokinetic cell.
In order to make electrode active material under various environmental conditions, bring into play its maximum performance, need to add multiple additives usually.For example, patent 200610165433.8 has just been reported to mix with mechanical ball millings such as Zn, Co, Mn, Ca, rare earth elements and has been improved the trial of electrode high-temperature behavior.Similarly, [the Ni that finds for us
4Al (OH)
10] hydrate of OH, being applied in order to impel it, we have also carried out multiple doping research, and purpose is to improve its efficiency for charge-discharge, discharge capacity, high-temperature behavior, cycle life or the like.
Summary of the invention
Technical problem: the nickel-base alkaline secondary cell anode material and preparation method thereof that the purpose of this invention is to provide a kind of doping of a kind of good stability, high-performance, low price.
Technical scheme: the positive electrode that is used for nickel-base alkaline secondary cell of the present invention is Li
+, Mg
2+, Ca
2+, Co
2+, Mn
2+, Zn
2+, Cd
2+, Y
3+, rare earth element Ln
3+In [the Ni of one or more doped with metal elements
4Al (OH)
10] the OH powder crystal; The mol ratio of Ni, Al, doping metals M is 4:1:x in the electrode material of this doping, wherein 0＜x≤1.5.
The synthetic following steps that comprise of one of this preparation method's hydro-thermal:
1.) preparation hybrid metal saline solution: Ni wherein
2+Concentration is 0.2～0.8moll
-1, Al
3+Concentration be 0.05～0.2moll
-1, doped metal ion total concentration be 0.06～0.3moll
-1
2.) preparation aqueous alkali: soluble in water alkali metal hydroxide or ammoniacal liquor, its concentration is 0.5moll
-1～2.0moll
-1
3.) aqueous alkali is equipped with in the reactor of hybrid metal saline solution slow adding the under inert gas shielding, 80～120 ℃ of reactions 1～24 hour, the pH value of final mixed reaction solution was 7～10, and the product that obtains is suspended in the water;
4.) suspension that step 3) is obtained is transferred in the water heating kettle of inner liner polytetrafluoroethylene, handles 8～120 hours down 120～200 ℃ of temperature, and the suspension after the hydrothermal treatment consists after filtration, washing, vacuumize, grinds, and obtains powder crystal;
5) powder crystal with gained after the above-mentioned grinding places alkali hydroxide soln, and in inert gas shielding, temperature is 80～120 ℃, behind reaction 1～24h, suspension filtered, washing, vacuumize, grinds under good the stirring, promptly gets [the Ni that mixes
4Al (OH)
10] OH electrode powder crystal sample.
Step 1) and step 2) in the aqueous solution collocation method, the water of use has removed the wherein CO of dissolving in advance
2, inert gas is N
2Or Ar gas.
Chemical coating method among this preparation method comprises following steps:
A. with [Ni
4Al (OH)
10] to be immersed in concentration be 0.05～0.2moll to the OH powder
-1Treat in the solution of doped metal ion that stirring at room 1～8 hour forms suspension-turbid liquid,
B. with aqueous slkali 500 rev/mins～1500 rev/mins of stir speed (S.S.)s, slowly join under the inert gas shielding in the suspension-turbid liquid of step 1), regulate pH value 7～9, stirring at room was reacted 1～24 hour; Aqueous slkali comprises at least a aqueous solution in lithium hydroxide, NaOH, potassium hydroxide or the ammoniacal liquor, and its concentration is 0.5～2.0moll
-1,
C. step 2) the product water heat treatment that obtains is 8～120 hours, 120～200 ℃ of temperature; Subsequent filtration, washing, 60 ℃ of following dryings of vacuum 1～3 day are ground, and promptly get product.
Mechanical mixture mode among this preparation method is:
D. with Zn (NO
3)
2Press the 1:2 mixed in molar ratio with the aqueous solution of NaOH, 120～200 ℃ of hydrothermal treatment consists 8～120 hours, can obtain the ZnO crystallite then,
E. [the Ni of ZnO that drying is crossed and preparation
4Al (OH)
10] the OH sample powder, the mixed of pressing 0.5:1,1:1,1.5:1, abundant mixing in agate mortar or ball mill, electrode is used for making.
Only contain a kind of anion in the hybrid metal saline solution, use A
N-Expression, n is anionic valence state; Be nitrate anion, chloride ion, perchlorate, acetate, a kind of in the sulfate radical.
Beneficial effect: what the present invention relates to is a kind of nickel-hydrogen battery positive pole material---[the Ni of doping
4Al (OH)
10] OH hydrate and preparation method thereof, the material that obtains thus have have extended cycle life, high low temperature high rate during charging-discharging is good, energy density is high advantage.For example, the Zinc material of mixing of hydrothermal method preparation contains [Ni
4AlZn
y(OH)
10+2y] OH and ZnO two-phase, the former is crystallization in the form of sheets, and the latter is the bar-shaped crystallization of micron-sized length.Composition n when sample
Ni: n
Al: n
ZnDuring=4:1:1, at current density 800mAg
-1Following charging, 400mAg
-1During discharge, maximum discharge capacity can reach 315mAhg
-1, when being circulated to 255 times under the similarity condition, its discharge capacity still has 310mAhg
-1At 2000mAg
-1High current density down during discharge, capacity also has 300mAhg
-1The sample of doping calcium, yttrium and plain [Ni
4Al (OH)
10] OH compares, and has better high-temperature behavior.
Embodiment
This electrode material is Li
+, Mg
2+, Ca
2+, Co
2+, Mn
2+, Zn
2+, Cd
2+, Y
3+, rare earth element Ln
3+In [the Ni of one or more doped with metal elements
4Al (OH)
10] the OH powder crystal; The mol ratio of Ni, Al, doping metals M is 4:1:x in the electrode material of this doping, wherein 0＜x≤1.5.
Each metal ion species mode of mixing and the method for preparing electrode all are identical, are the example explanation with the sample preparation of doping zinc only here:
1. [the Ni of doping of Zn
4Al (OH)
10] preparation of OH positive electrode
1.1 hydrothermal synthesis method:
At first the distilled water that obtain solution is used boils, to remove wherein dissolved gases.
By nickel, aluminium, zinc mol ratio is 4:1:x (0＜x≤1.5) preparation mixing salt solution and aqueous slkali.Ni in the mixed-salt aqueous solution
2+Concentration at 0.2～0.8moll
-1, Al
3+Concentration at 0.05～0.2moll
-1, Zn
2+Concentration at 0.05～0.35moll
-1Preferably use the salt of the monobasic acid of nickel aluminium zinc such as nitric acid, hydrochloric acid, perchloric acid, acetic acid or the like, but also can use sulfate.Alkali uses at least a aqueous solution in lithium hydroxide, NaOH, potassium hydroxide or the ammoniacal liquor, and its concentration is 0.5～2.0moll
-1
500～1500 rev/mins of stir speed (S.S.)s, inert gas shielding slowly adds in the mixing salt solution down with aqueous slkali, and the pH when precipitation reaction is finished is between 7～10.After the aqueous slkali adding finishes, under 80～120 ℃ of steady temperatures, continue in reactor, to stir 1～24 hour.Then the suspension-turbid liquid that forms is moved in the water heating kettle of teflon lined, be warming up to 120～200 ℃, be incubated 8～120 hours, naturally cool to room temperature subsequently, filter, washing, 60 ℃ in vacuum dry 1～3 day down, grinding.
It is some to get the above-mentioned sample that makes, and placing concentration is 0.5～2moll
-1In the alkali hydroxide soln (the two mol ratio is between 1:2～1:5), at inert atmosphere protection, reaction temperature is under 80～120 ℃, and mixing is filtered after stirring 1～24h, washing and dry, promptly obtains [the Ni of Zn doping
4Al (OH)
10] electrode material of OH.[the Ni that Zn mixes
4Al (OH)
10] the XRD figure spectrum and the SEM image of OH material show, after hydrothermal treatment consists, generated two-phase, i.e. [the Ni of sheet
4AlZn
y(OH)
10+2y] OH and needle-like ZnO mutually.
Do not find Ca (OH) with mixing in calcium (only change Zn into Ca, other the is constant) sample of making of method
2The existence of phase, [Ni
4Al (OH)
10] OHyCa (OH)
2Be the gear-like flaky crystal, and Ca
2+Do not enter [Ni
4Al (OH)
10] in the OH lattice.
1.2 coating mode:
Will be by [the Ni of patented technology ZL200610037887.7 preparation
4Al (OH)
10] the OH sample powder is immersed in the solution (0.05～1.0moll of doping metals
-1) in, stirring at room 1～8 hour.Then with alkali hydroxide soln 500～1500 rev/mins of stir speed (S.S.)s, inert gas shielding adds down slowly in this suspension-turbid liquid, regulates pH to 7～9, stirring at room reaction 1～24 hour.Aqueous slkali comprises at least a aqueous solution in lithium hydroxide, NaOH, potassium hydroxide or the ammoniacal liquor, and its concentration is 0.5～2.0moll
-1
The product water heat treatment that obtains 8～120 hours, 120～200 ℃ of temperature.Subsequent filtration, washing, 60 ℃ of following dryings of vacuum 1～3 day are ground, and promptly get product.
1.3 mechanical mixture mode:
The ZnO that drying the is crossed and [Ni of preparation
4Al (OH)
10] the OH sample powder, mix by a certain percentage, make wherein that ZnO content is not higher than 10%, in agate mortar, fully grind mixing and get final product.
2. [the Ni of doping of Zn
4Al (OH)
10] the anodal preparation of OH
With [the Ni that mixes
4Al (OH)
10] OH sample, nickel powder, cobalt powder according to the 50:160:40 mixed after, add an amount of PTFE and CMC emulsion and grind evenly, be attached on the nickel foam both side surface, 60～100 ℃ of vacuumizes are after 24 hours, the mould of packing into, exerting pressure is 5～30MPa, makes φ 15mm circular electrode sheet; Use the nickel wire to pick out lead, make electrode, carry out electro-chemical test.
Discharging and recharging the starting stage, the electrode discharge capacity that adopt that hydro-thermal is synthetic, coating mode and mechanical mixture mode makes but after 100 circulations, coats and electrode capacity that the mechanical mixture mode makes begins to significantly decrease much at one, 255 circulations, capacity has been reduced to 280mAhg
-1And the synthetic sample capacity of hydro-thermal does not almost change, and has shown good cyclical stability.
[Ni to the Zn doping
4Al (OH)
10] the OH electrode carried out the discharge capacity test under the different discharge current densities.Experiment finds that along with the increase of current density, discharge capacity reduces gradually.Sample is at small electric current density (100mAg
-1) when discharging, capacity is 319mAhg
-1At 2000mAhg
-1Under the discharge current density, capacity still has 300mAhg
-1Therefore, [the Ni of doping of Zn
4Al (OH)
10] the OH electrode material has high rate during charging-discharging preferably.
Claims (5)
1. the nickel-base alkaline secondary cell anode material of a doping is characterized in that this electrode material is Li
+, Mg
2+, Ca
2+, Co
2+, Mn
2+, Zn
2+, Cd
2+, Y
3+, rare earth element Ln
3+In [the Ni of one or more doped with metal elements
4Al (OH)
10] the OH powder crystal; The mol ratio of Ni, Al, doping metals M is 4: 1 in the electrode material of this doping: x, wherein 0＜x≤1.5.
2. the preparation method of a nickel-base alkaline secondary cell anode material that is used to mix as claimed in claim 1 is characterized in that this preparation method's synthetic following steps that comprise of hydro-thermal:
1) preparation hybrid metal saline solution: wherein Ni2+ concentration is 0.2～0.8moll
-1, Al
3+Concentration be 0.05～0.2moll
-1, doped metal ion concentration be 0.06～0.3moll
-1
2) preparation aqueous alkali: soluble in water alkali metal hydroxide or ammoniacal liquor, its concentration is 0.5moll
-1～2.0moll
-1
3) aqueous alkali is equipped with in the reactor of hybrid metal saline solution slow adding the under inert gas shielding, 80～120 ℃ of reactions 1～24 hour, the pH value of final mixed reaction solution was 7～10, and the product that obtains is suspended in the water;
4) suspension that step 3) is obtained is transferred in the water heating kettle of inner liner polytetrafluoroethylene, handles 8～120 hours down 120～200 ℃ of temperature, and the suspension after the hydrothermal treatment consists after filtration, washing, vacuumize, grinds, and obtains powder crystal;
5) powder crystal with gained after the above-mentioned grinding places alkali hydroxide soln, and in inert gas shielding, temperature is 80～120 ℃, behind reaction 1～24h, suspension filtered, washing, vacuumize, grinds under good the stirring, promptly gets [the Ni that mixes
4Al (OH)
10] OH electrode powder crystal sample;
This preparation method's chemical coating method comprises following steps:
A) with [Ni
4Al (OH)
10] to be immersed in concentration be 0.05～0.2moll to the OH powder
-1Treat in the solution of doped metal ion that stirring at room 1～8 hour forms suspension-turbid liquid,
B) with aqueous slkali 500 rev/mins～1500 rev/mins of stir speed (S.S.)s, slowly join under the inert gas shielding in the suspension-turbid liquid of step a), regulate pH value 7～9, stirring at room was reacted 1～24 hour; Aqueous slkali comprises at least a aqueous solution in lithium hydroxide, NaOH, potassium hydroxide or the ammoniacal liquor, and its concentration is 0.5～2.0moll
-1,
C) the product water heat treatment that obtains of step b) is 8～120 hours, 120～200 ℃ of temperature; Subsequent filtration, washing, 60 ℃ of following dryings of vacuum 1～3 day are ground, and promptly get product;
This preparation method's mechanical mixture mode is:
A) with Zn (NO
3)
2With the aqueous solution of NaOH by 1: 2 mixed in molar ratio, 120～200 ℃ of hydrothermal treatment consists 8～120 hours, can obtain the ZnO crystallite then,
B) [the Ni of ZnO that drying is crossed and preparation
4Al (OH)
10] the OH sample powder, by 0.5: 1,1: 1,1.5: 1 mixed, abundant mixing in agate mortar, used to make electrode.
3. the preparation method of the nickel-base alkaline secondary cell anode material that is used to mix according to claim 2 is characterized in that only containing a kind of anion in the hybrid metal saline solution, uses A
N-Expression, n is anionic valence state; Be nitrate anion, chloride ion, perchlorate, acetate, a kind of in the sulfate radical.
4. the preparation method of the nickel-base alkaline secondary cell anode material that is used to mix according to claim 2 is characterized in that step 1) and step 2) in the aqueous solution compound method, the water of use has removed the wherein O of dissolving in advance
2And CO
2
5. the preparation method of the nickel-base alkaline secondary cell anode material that is used to mix according to claim 2 is characterized in that inert gas is N
2Or Ar gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101553340A CN101391798B (en) | 2008-10-17 | 2008-10-17 | Doped nickel-base alkaline secondary cell anode material and preparation method thereof |
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|---|---|---|---|
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| CN101391798B true CN101391798B (en) | 2011-09-07 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944606B (en) * | 2010-08-31 | 2012-09-19 | 东南大学 | Super-alkaline secondary battery anode and preparation method thereof |
| JP6090673B2 (en) * | 2012-09-28 | 2017-03-08 | 株式会社Ｇｓユアサ | Alkaline storage battery and positive electrode material for alkaline storage battery |
| CN104157464B (en) * | 2014-09-04 | 2017-02-01 | 福州大学 | Doping type supercapacitor electrode material |
| CN110494394A (en) * | 2017-03-15 | 2019-11-22 | 尤米科尔公司 | For manufacturing the nitrate method of transition metal hydroxide precursor |
| CN108376769B (en) * | 2018-01-30 | 2020-03-27 | 电子科技大学 | Preparation method of composite positive electrode material of lithium ion battery |
| CN108878990B (en) * | 2018-06-01 | 2020-08-25 | 河南师范大学 | Iron-nickel secondary battery and preparation method thereof |
| CN109616658B (en) * | 2018-12-17 | 2021-10-19 | 中科廊坊过程工程研究院 | Selenium and sulfate radical co-doped high-nickel cathode material and preparation method and application thereof |
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