CN102931396A - Anode material for high-performance alkaline batteries and method for preparing anode material - Google Patents
Anode material for high-performance alkaline batteries and method for preparing anode material Download PDFInfo
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- CN102931396A CN102931396A CN2012104361762A CN201210436176A CN102931396A CN 102931396 A CN102931396 A CN 102931396A CN 2012104361762 A CN2012104361762 A CN 2012104361762A CN 201210436176 A CN201210436176 A CN 201210436176A CN 102931396 A CN102931396 A CN 102931396A
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Abstract
The invention discloses an anode material for high-performance alkaline batteries and a method for preparing the anode material. The anode material is alpha-nickel hydroxide doped with a plurality of metal ions. The alpha-nickel hydroxide is prepared by subjecting a main raw material of nickel salt, a main doping agent of chromium ions and auxiliary doping agents of alkaline-earth metal ions and rare-earth metal ions to co-deposition. The anode material doped with the alpha-nickel hydroxide has the advantages of high stability and specific energy. Secondary nickel electrodes prepared through the anode material have the advantages of being high in active material use ratio, good in electrical conductivity, high in charge acceptance and specific capacity, long in cycle life and the like.
Description
Technical field
The present invention relates to technical field of chemical power, high performance alkaline battery positive electrode that especially a kind of alpha-nickel hydroxide mixes and preparation method thereof.
Background technology
Currently comprise take nickel electrode as anodal battery: several alkaline batteries such as nickel zinc, NI-G, ni-mh, ferronickel, the positive electrode of these alkaline batteries all are to adopt commercially available ball-type nickel hydroxide (Ni (OH)
2) as active material, Ni (OH)
2Comprise α-Ni (OH)
2And β-Ni (OH)
2Two kinds of forms, the used commodity nickel hydroxide of nickel electrode all is β-Ni (OH) at present
2, α-Ni (OH)
2With β-Ni (OH)
2The main distinction is:
1. β-Ni (OH)
2Only relate to electronics in charging process and shift, so theoretical specific capacity only has 289mAh/g, and actual specific energy also reaches 200-250mAh/g, near theoretical capacity, the space that can promote is very little, this means to adopt β-Ni (OH)
2As the battery of active material, volume is large, weight is high, is unfavorable for the further lifting of battery specific energy.α-Ni (OH)
2Charge and discharge process relate to 1.67 electronics and shift, have the theoretical specific capacity of 482mAh/g, adopt α-Ni (OH)
2Be conducive to improve the battery specific energy as active material, be conducive to the battery miniaturization, save the raw material use amount, therefore study high-octane α-Ni (OH)
2Preparation has more meaning with use.
2. with β-Ni (OH)
2During for electrode active material, in the situation that overcharge or floating charge, can generate the less γ-NiOOH of density, this density variation can cause nickel electrode in charge and discharge cycles, volume changes, and then cause nickel electrode to absorb a large amount of electrolyte, and cause barrier film dry, nickel electrode expands, not only destroyed the conductive network of active material, reduced the utilance of active material, also accelerated the oxidation of fluid confluence alloy surface, it is the one of the main reasons that causes nickel series battery early failure that nickel electrode expands.
3. commodity β-Ni (OH)
2Specific area lower, diffusion of protons ability and chemism are all than α-Ni (OH)
2Low is many, therefore adopts α-Ni (OH)
2As the battery of electrode active material, can increase substantially the charging and discharging capabilities of battery, more be applicable to high-power, high-multiplying power discharge use occasion, as: hybrid vehicle, the electrokinetic cell of pure electronic bus.
4. use β-Ni (OH)
2As the battery of electrode material, activity cycle is longer, and uses α-Ni (OH)
2Charge acceptance is stronger, and therefore the electric current fast charging and discharging when cell activation, can save a large amount of electric energy and time greatly, and equipment investment is corresponding minimizing also, improves battery production efficient and reduces the charging energy consumption.
In view of α-Ni (OH)
2Plurality of advantages, people are to α-Ni (OH)
2Doping vario-property, preparation technology, electrode prescription done large quantity research.Present α-Ni (OH)
2The preparation method is to adopt the metal ion mixing method, and the metal ion of doped with hydrogen nickel oxide has Al
3+, Zn
2+, Fe
3+, Mn
2+, Co
3+Deng, wherein the price of cobalt is higher, and economic serviceability is bad; And the doping iron ion analyse α-Ni (OH)
2Oxygen evolution potential can reduce, and electrode performance is poisoned; The zinc ion atomic weight is relatively large, has reduced the specific discharge capacity of electrode material.
Chinese patent application number: 200510037576.6 disclose " a kind of nano alpha-nickel hydroxide and preparation method thereof ", the method adopts ultrasonic wave as subsidiary conditions, as dopant, adopt co-electrodeposition method to prepare alpha-nickel hydroxide with trivalent aluminium salt or trivalent iron salt.Yet the less stable of alpha-nickel hydroxide in alkaline electrolyte of this method preparation, the high temperature self discharge is larger, the loaded down with trivial details shortcomings that waits of preparation process, ferric doping has also reduced the activity of alpha-nickel hydroxide in addition, reduced active material utilization, nickel hydroxide electrode has been consisted of poisoning effect;
Chinese patent application number: 200510027346.1 have announced a kind of " microwave-hydrothermal method prepares the method for a beta-phase nickel hydroxide ", the method adopts microwave as subsidiary conditions, adopt aluminium ion as main dopant, adopt metal ions M as secondary dopant, metal ions M is taken from the slaine of the metals such as Y, Ti, Cr, Sc, La, Co, Fe, In, Zn.Aluminium is the metallic element of the most frequently used doping a-nickel hydroxide, but aluminium has many shortcomings as dopant, the first, and aluminium is not active material, does not participate in electrode reaction, so aluminium mixes and to have reduced activity substance content, is unfavorable for the raising of battery specific energy; The second, the doping of aluminium forms intercalation compound with nickel hydroxide, and it is large that the active material volume becomes, and reduced the active material bulk density.
Summary of the invention
In order to solve above-mentioned drawback, problem to be solved by this invention is, a kind of high stable is provided, the doping a-nickel hydroxide anode material of high specific energy, secondary active material of nickel electrode utilance by the preparation of this positive electrode is high, good conductivity, charge acceptance is strong, specific capacity is high, have extended cycle life, and the present invention also provides the preparation method of described positive electrode.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of high performance alkaline battery positive electrode, described positive electrode is the alpha-nickel hydroxide that adopts many kinds of metal ions to mix, the main raw materials of described alpha-nickel hydroxide is nickel salt, chromium ion is as main dopant, and alkaline-earth metal ions and rare earth ion adopt the co-electrodeposition method preparation as auxiliary dopant.
Preferably, described nickel salt is selected from nickelous sulfate, nickel nitrate, a kind of in the nickel chloride.
Preferably, described metal ion is taken from the sulfate of metal ion, nitrate or chloride.
Preferably, described alkaline-earth metal ions is taken from Ca
2+, Mg
2+, Sr
2+, Ba
2+One or more, described rare earth ion is taken from Y
3+, La
3+, Pr
3+, Ce
3+, Sm
3+, Eu
3+In one or more.
Preferably, described nickel salt content is the 70%-98% mol ratio, and described alkaline-earth metal ions content is 0.01～5% of nickel salt molal quantity; Described rare earth ion content is 0.01～5% of nickel salt molal quantity; Content of chromium ion is 2～40% of nickel salt molal quantity.
A kind of preparation method of high performance alkaline battery positive electrode, its preparation process is:
The first step: first with alkali salt, nickel salt, chromic salts, several compounds of rare earth metal salt are dissolved in deionized water, add polyvinylpyrrolidone or polyethylene glycol as dispersant, it is 0.5～10g/L that dispersant adds concentration, is configured to the solution that nickel ion concentration is 0.5～5mol/L;
Second step: get potassium hydroxide or NaOH that molal quantity is equivalent to 2～3 times of nickel ion molal quantitys, get the natrium carbonicum calcinatum that molal quantity is equivalent to potassium hydroxide or NaOH molal quantity 0.1～10%, water dissolves, and is configured to the solution of 0.1～6mol/L, as precipitation reagent;
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 20～60 ℃, reaction time is 0.5～12h, when pH value of reaction system between 8～12, can be considered reaction and finish, continued to leave standstill 8～24 hours, and obtained blackish green precipitation;
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 70～100 ℃ in vacuum is dried to constant weight, is high performance alkaline battery positive electrode of the present invention.
Beneficial effect of the present invention is:
1. adopt chromium ion as main dopant, chromium ion participates in reaction in electrode, and its Reactive Mechanism of Electrode is: CrO
2+ e
-+ H
2O==Cr(OH
)
3So the chromium element is active material, the electrode specific energy is quite favourable for improving.
2. the chromium element is stable under alkali condition, enters the nickel hydroxide lattice in the doping process, prevents that nickel hydroxide from crystal occurring and subsiding, and nickel hydroxide is played stabilization.
3. the charging potential of chromium element is higher than nickel, therefore can prevent that nickel hydroxide from overcharging, and the chromium element can also improve the discharge platform of nickel hydroxide.
4. the alkali earth metal price is more cheap, can improve the overpotential for oxygen evolution of nickel hydroxide battery, and then suppresses to produce oxygen in the anodal charging process, improves battery hermetization and fail safe.
5. rare earth element can improve the high-temperature behavior of electrode, reduces the self-discharge rate of nickel electrode, therefore adopts rear-earth-doped nickel hydroxide, and the storge quality of battery is superior, has also widened the serviceability temperature scope of battery.
6. after thulium mixes, can improve the real density of nickel hydroxide, this for improve electrode to be coated with the cream amount quite favourable, therefore also just improved the specific energy of battery.
7. adopt the chromium element, alkaline-earth metal, after rare earth doped, the ion diffusivity of nickel hydroxide increases substantially, reduce the nickel electrode impedance, therefore increased substantially the charge-discharge magnification of electrode, improved active material utilization, the specific power that this is conducive to improve battery is conducive to the miniaturization of battery.
The present invention will be further described below in conjunction with embodiment.
Description of drawings
Accompanying drawing is product and the commercially available β-Ni (OH) of embodiment 1-4
2Discharge curve.
Embodiment
Embodiment 1: the first step: get the 2mol nickel chloride and be dissolved in 1 liter of deionized water, add chromium sulfate 0.3mol, magnesium sulfate 0.01mol, calcium nitrate 0.02mol, lanthanum nitrate 0.03mol, fully dissolving adds polyvinylpyrrolidone as dispersant in solution, interpolation concentration is 0.5g/L, is configured to the solution that nickel ion concentration is 2mol/L.
Second step: get 4.5mol NaOH, get the 0.05mol natrium carbonicum calcinatum, with deionized water the two is dissolved, be configured to the solution that naoh concentration is 2mol/L, as precipitation reagent.
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 25 ℃, and the reaction time is 5, when the pH of reaction system value is 9, can be considered reaction and finish, continued to leave standstill 8 hours, obtain blackish green precipitation.
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 100 ℃ in vacuum is dried to constant weight, is doped alpha-Ni of the present invention (OH)
2
Embodiment 2: the first step: get the 1mol nickelous sulfate and be dissolved in 1 liter of deionized water, add chromic nitrate 0.3mol, barium chloride 0.05mol, praseodymium nitrate 0.02mol, fully dissolving adds polyethylene glycol as dispersant in solution, interpolation concentration is 1g/L, is configured to the solution that nickel ion concentration is 1mol/L.
Second step: get 2.5mol NaOH, get the 0.2mol natrium carbonicum calcinatum, with deionized water the two is dissolved, be configured to the solution that naoh concentration is 5mol/L, as precipitation reagent.
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 28 ℃, and the reaction time is 8, when the pH of reaction system value is 8, can be considered reaction and finish, continued to leave standstill 10 hours, obtain blackish green precipitation.
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 90 ℃ in vacuum is dried to constant weight, is doped alpha-Ni of the present invention (OH)
2
Embodiment 3: the first step: get the 3mol nickelous sulfate and be dissolved in 1 liter of deionized water, add chromium chloride 0.7mol, strontium nitrate 0.02mol, magnesium chloride 0.01mol, samaric nitrate 0.02mol, fully dissolving adds polyethylene glycol as dispersant in solution, interpolation concentration is 1g/L, is configured to the solution that nickel ion concentration is 3mol/L.
Second step: get 7mol NaOH, get the 0.3mol natrium carbonicum calcinatum, with deionized water the two is dissolved, be configured to the solution that naoh concentration is 5mol/L, as precipitation reagent.
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 28 ℃, and the reaction time is 8, when the pH of reaction system value is 11, can be considered reaction and finish, continued to leave standstill 12 hours, obtain blackish green precipitation.
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 85 ℃ in vacuum is dried to constant weight, is doped alpha-Ni of the present invention (OH)
2
Embodiment 4: the first step: get the 2mol nickelous sulfate and be dissolved in 4 liters of deionized waters, add chromium chloride 0.8mol, calcium nitrate 0.03mol, europium nitrate 0.02mol, fully dissolving, add polyvinylpyrrolidone as dispersant in solution, interpolation concentration is 1g/L, is configured to the solution that nickel ion concentration is 0.5mol/L.
Second step: get 5mol NaOH, get the 0.5mol natrium carbonicum calcinatum, with deionized water the two is dissolved, be configured to the solution that naoh concentration is 5mol/L, as precipitation reagent.
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 20 ℃, and the reaction time is 10h, when the pH of reaction system value is 10, can be considered reaction and finish, continued to leave standstill 9 hours, obtain blackish green precipitation.
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 110 ℃ in vacuum is dried to constant weight, is α-Ni of the present invention (OH)
2
With doped alpha-Ni of the present invention (OH)
2With commercially available ball-type nickel hydroxide---β-Ni (OH)
2Compare:
Take by weighing respectively the doped alpha-Ni (OH) of certain mass
2With commercially available ball-type nickel hydroxide, add conductive agent nickel powder, electrically conductive graphite, the polyfluortetraethylene of binding element emulsion mixes, nickel hydroxide, nickel powder, electrically conductive graphite, the mass ratio of polytetrafluoroethylene is 85:5: 5:5, and drips several ethanol furnishing slurries, after the volatilization thickening, slurry is compressed on the nickel screen with wire, then dry 12h under the room temperature.As work electrode, platinum filament and saturated calomel electrode are respectively as auxiliary electrode and reference electrode with the electrode obtained, and the KOH solution of 6mol/L forms three-electrode system as electrolyte.Work electrode soaked 5h in electrolyte after, in 0～0.5V potential range, 20 times it is activated with the electrochemical workstation circulation, and the 0.5C current discharge carries out the constant current charge-discharge test on battery test system.The product of embodiment 1-4 and commercially available β-Ni (OH)
2Discharge curve as shown in drawings.
α-Ni (OH) that embodiment 4 is prepared
2With commercially available material β-Ni (OH)
2Compare: take by weighing respectively the bi-material of same weight, the electrode of made is done cycling life test, and the cycle life correction data is as shown in the table:
Claims (7)
1. high performance alkaline battery positive electrode, it is characterized in that, described positive electrode is the alpha-nickel hydroxide that adopts many kinds of metal ions to mix, the main raw materials of described alpha-nickel hydroxide is nickel salt, chromium ion is as main dopant, alkaline-earth metal ions and rare earth ion adopt the co-electrodeposition method preparation as auxiliary dopant.
2. a kind of high performance alkaline battery positive electrode as claimed in claim 1 is characterized in that, described nickel salt content is the 70%-98% mol ratio, and described alkaline-earth metal ions content is 0.01～5% of nickel salt molal quantity; Described rare earth ion content is 0.01～5% of nickel salt molal quantity; Content of chromium ion is 2～40% of nickel salt molal quantity.
3. a kind of high performance alkaline battery positive electrode as claimed in claim 1 or 2 is characterized in that, described metal ion is taken from the sulfate of metal ion, nitrate or chloride.
4. a kind of high performance alkaline battery positive electrode as claimed in claim 1 or 2 is characterized in that, described alkaline-earth metal ions is taken from Ca
2+, Mg
2+, Sr
2+, Ba
2+One or more, described rare earth ion is taken from Y
3+, La
3+, Pr
3+, Ce
3+, Sm
3+, Eu
3+In one or more.
5. a kind of high performance alkaline battery positive electrode as claimed in claim 1 or 2 is characterized in that, described nickel salt is selected from nickelous sulfate, nickel nitrate, a kind of in the nickel chloride.
6. a kind of high performance alkaline battery positive electrode as claimed in claim 1 or 2 is characterized in that, described nickel salt adopts nickelous sulfate, and alkaline-earth metal ions adopts calcium nitrate, and rare earth ion adopts europium nitrate, and chromium ion adopts chromium chloride.
7. the preparation method of a high performance alkaline battery positive electrode, its preparation process is:
The first step: first with alkali salt, nickel salt, chromic salts, several compounds of rare earth metal salt are dissolved in deionized water, add polyvinylpyrrolidone or polyethylene glycol as dispersant, it is 0.5～10g/L that dispersant adds concentration, is configured to the solution that nickel ion concentration is 0.5～5mol/L;
Second step: get potassium hydroxide or NaOH that molal quantity is equivalent to 2～3 times of nickel ion molal quantitys, get the natrium carbonicum calcinatum that molal quantity is equivalent to potassium hydroxide or NaOH molal quantity 0.1～10%, water dissolves, and is configured to the solution of 0.1～6mol/L, as precipitation reagent;
The 3rd step: stir the metal salt solution that the first step makes, the precipitation reagent that second step is prepared slowly adds, the control rate of addition, reaction temperature is 20～60 ℃, reaction time is 0.5～12h, when reacting system PH value between 8～12, can be considered reaction and finish, continued to leave standstill 8～24 hours, and obtained blackish green precipitation;
The 4th step: the 3rd step gained precipitation is through washing and filtering repeatedly, neutral to filtrate, and 70～100 ℃ in vacuum is dried to constant weight, is high performance alkaline battery positive electrode of the present invention.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585843A (en) * | 2018-11-12 | 2019-04-05 | 昆明理工大学 | A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor |
| CN112635736A (en) * | 2020-12-22 | 2021-04-09 | 中国科学院长春应用化学研究所 | Preparation method of active substance composite material of nickel hydroxide battery positive electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331845A (en) * | 1998-12-24 | 2002-01-16 | H.C.施塔克公司 | Nickel mixed hydroxide, method for producing same, and use thereof as cathode material in alkaline batteries |
| CN101982402A (en) * | 2010-09-10 | 2011-03-02 | 广东工业大学 | Multi-element doped nano alpha-Ni(OH)2 material and preparation method thereof |
-
2012
- 2012-11-05 CN CN2012104361762A patent/CN102931396A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331845A (en) * | 1998-12-24 | 2002-01-16 | H.C.施塔克公司 | Nickel mixed hydroxide, method for producing same, and use thereof as cathode material in alkaline batteries |
| CN101982402A (en) * | 2010-09-10 | 2011-03-02 | 广东工业大学 | Multi-element doped nano alpha-Ni(OH)2 material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585843A (en) * | 2018-11-12 | 2019-04-05 | 昆明理工大学 | A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor |
| CN109585843B (en) * | 2018-11-12 | 2021-09-21 | 昆明理工大学 | Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor |
| CN112635736A (en) * | 2020-12-22 | 2021-04-09 | 中国科学院长春应用化学研究所 | Preparation method of active substance composite material of nickel hydroxide battery positive electrode |
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Application publication date: 20130213 |