CN100500578C - Method for modifying spherical nickel hydroxide by nano carbon technique - Google Patents
Method for modifying spherical nickel hydroxide by nano carbon technique Download PDFInfo
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- CN100500578C CN100500578C CNB200710024530XA CN200710024530A CN100500578C CN 100500578 C CN100500578 C CN 100500578C CN B200710024530X A CNB200710024530X A CN B200710024530XA CN 200710024530 A CN200710024530 A CN 200710024530A CN 100500578 C CN100500578 C CN 100500578C
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Abstract
The present invention discloses technological process of preparing spherical nickel hydroxide modified with nanometer carbon and as the active positive electrode material. The spherical nickel hydroxide is modified electrochemically in alkaline condition. The process is simple and has homogeneous deposition, and the prepared modified positive electrode material is used for alkaline accumulator, especially high power nickel-hydrogen battery, and has over 20 % raised conductivity, about 20 % reduced nickel consumption, cobaltous oxide consumption reduced from 5-10 % to 0.5-2 %, capacity of raising the performance of the battery greatly and lowered production cost.
Description
Technical field
The present invention relates to a kind of preparation method of battery material, be specifically related to the nano carbon modifying method of a kind of nickel electrode with positive electrode material-ball-shape nickel hydroxide.
Background technology
Nickel electrode is the positive pole of alkaline cadmium nickel, iron nickel, hydrogen nickel, zinc-nickel cell, and the raising of nickel electrode high power performance all obtains to improve to the state of the art of the Edison battery of all nickel electrodes.Present superpower particularly, the long lifetime, the development of nickel metal hydride battery cheaply, satisfying hybrid vehicle, power vehicle, electric bicycle, battery-operated motor cycle, the pressing for of industries such as power tool.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of novel nano carbon technique modifying spherical nickel hydroxide, the characteristic that has high discharge voltage plateau, low internal resistance with this material as the Edison battery of positive electrode material, be applicable to the Edison battery of high power discharge, reduced the usage quantity of nickel, cobalt, the more conventional Edison battery of cost descended about 20%.
Purpose of the present invention can reach by following measure:
A kind of nano carbon technique is modified the method for nickel hydroxide, comprises the following steps:
(1) in the sodium hydroxide solution of 0.05～0.1mol/L, adds Ni (OH)
2, make Ni (OH)
2Concentration reach 0.1～5mol/L, and add Ni (OH)
25～10% graphite of quality makes mixed solution;
(2) with mixed solution 40～100 ℃ and stir under place electric field, feed direct current by the current density of every square centimeter of 0.05～0.5mA and react, the bath voltage at electric field anode and cathode two ends is 1.5～1.85V;
(3) with mixed solution after 40～80 ℃ down precipitation is shelved, feed ultrasonic wave to mixed solution concussion 2～5h;
(4) mixed solution staticly settled, filter, wash, obtain the nickel hydroxide that nano carbon is modified after the drying.
Purpose of the present invention specifically can reach by following measure:
A kind of preparation method of novel nano carbon technique modifying spherical nickel hydroxide comprises the following steps:
(1) prepares sodium hydroxide solution with deionized water, concentration 5-10%mol/L;
(2) take by weighing the Ni (OH) of 0.1～5mol/L
2Powder and press Ni (OH)
2High-purity oildag of 5～10% mass ratio mix, join in the sodium hydroxide solution, stir, keep solution temperature at 40～100 ℃;
(3) impose on electric field in the hybrid reaction groove, and feed direct current in reactive tank by the current density of every square centimeter of 0.05-0.5mA, stir simultaneously, the bath voltage at anode and cathode two ends is 1.5～1.85V;
(4) reaction soln is left standstill 40～80 ℃ of precipitations;
(5) feed ultrasonic wave to reaction soln concussion 2～5h, reaction particle is carried out emulsification, atomizing processing;
(6) reaction soln is left standstill, precipitation is filtered;
(7) filtering precipitate is washed until non-alkali liquor with 40～100 ℃ deionization;
(8) with the reaction precipitation thing 40～120 ℃ of vacuum-dryings.
Stirring velocity in step (3) is that per minute 500～1500 changes; With the nickel metal sheet as anode and cathode; Reaction times is 2～5h.
The precipitation time of shelving in step (4) is 12h～24h.。
Precipitation time of repose 2～10h in step (6).
Advantage of the present invention is:
1. the present invention is to the modification of ball-shape nickel hydroxide, employing is under alkaline condition, be aided with electric field, the nano carbon of the high conductivity of growing height orientation on the particle of ball-shape nickel hydroxide, replaced covering the method for cobalt at ball nickel surface, the present invention is in uniform liquid phase production, finishes under the prescription of the best and reasonable process conditions.
2. the present invention assists and gives electric field action when mixing stirring reaction, makes superfine graphite ion be adsorbed onto ball-shape nickel hydroxide particulate surface sooner, and anchoring strength of coating increases substantially; When mixing stirring reaction, auxilliaryly give proper temperature, make be heated between particle more even.
3. the present invention passes to ultrasonic oscillation in reaction soln, and the emulsification of generation, atomizing make the dispersivity of the height that ball-shape nickel hydroxide had that nano carbon modifies and a large amount of interfaces provide the short-range diffusion approach for atom.
4. have the characteristic of high discharge voltage plateau, low internal resistance with this material as the Edison battery of positive electrode material, be applicable to the Edison battery of high power discharge, reduced the usage quantity of nickel, cobalt, the more conventional Edison battery of cost has descended about 20%.
Embodiment
The present invention will be further described below in conjunction with example:
Embodiment 1:
A kind of preparation method of modifying spherical nickel hydroxide by nano carbon technique, take following steps: the high-purity oildag of superfine that takes by weighing 1000g ball-shape nickel hydroxide and 70g mixes, and the temperature that slowly evenly joins 1.4L concentration and be 8M/L (being mol/L) is in 70 ℃ the sodium hydroxide solution; Solution is under 70 ℃ of conditions, and the current density feeding direct current by every square centimeter of 0.5mA keeps bath voltage 1.8V, changes at the uniform velocity with per minute 1000 simultaneously and stirs reaction times 3h; Reaction is shelved 20h after finishing under 70 ℃ of conditions; Feed ultrasonic wave at ambient temperature reaction soln is shaken 3h, then reaction soln is left standstill 7h, after the filtration, filter with 75 ℃ washed with de-ionized water, throw out is till the non-alkali liquor, at last cleaned reaction precipitation thing is dried under 90 ℃ vacuum condition, make the ball-shape nickel hydroxide that nano carbon is modified.
Embodiment 2:
A kind of preparation method of modifying spherical nickel hydroxide by nano carbon technique, take following steps: the high-purity oildag of superfine that takes by weighing 1000g ball-shape nickel hydroxide and 50g mixes, and the temperature that slowly evenly joins 1.96L concentration and be 5.5M/L is in 50 ℃ the sodium hydroxide solution; Solution is under 95 ℃ of conditions, and the current density feeding direct current by every square centimeter of 0.45mA keeps bath voltage 1.8V, changes at the uniform velocity with per minute 600 simultaneously and stirs reaction times 2-5h; Reaction is shelved 15h after finishing under 45 ℃ of conditions; Feed ultrasonic wave at ambient temperature reaction soln is shaken 2.5h, then reaction soln is left standstill 3h, after the filtration, filter with 95 ℃ washed with de-ionized water, throw out is till the non-alkali liquor, at last cleaned reaction precipitation thing is dried under 100 ℃ vacuum condition, make the ball-shape nickel hydroxide that nano carbon is modified.
Embodiment 3:
A kind of preparation method of modifying spherical nickel hydroxide by nano carbon technique, take following steps: the high-purity oildag of superfine that takes by weighing 1000g ball-shape nickel hydroxide and 90g mixes, and the temperature that slowly evenly joins 1.14L concentration and be 5.5M/L is in 90 ℃ the sodium hydroxide solution; Solution is under 55 ℃ of conditions, and the current density feeding direct current by every square centimeter of 0.15mA keeps bath voltage 1.55V, changes at the uniform velocity with per minute 1400 simultaneously and stirs reaction times 4.5h; Reaction is shelved 22h after finishing under 75 ℃ of conditions; Feed ultrasonic wave at ambient temperature reaction soln is shaken 4h, then reaction soln is left standstill 8h, after the filtration, filter with 55 ℃ washed with de-ionized water, throw out is till the non-alkali liquor, at last cleaned reaction precipitation thing is dried under 70 ℃ vacuum condition, make the ball-shape nickel hydroxide that nano carbon is modified.
Make anode with the ball-shape nickel hydroxide that the nano carbon of the embodiment of the invention 1 preparation is modified, make negative pole with hydrogen storing alloy powder, and potassium hydroxide electrolyte, barrier film is assembled into D type high-capacity nickel-hydrogen battery.
Battery was with 9000mA charging 72 minutes, 9000mA only discharges into final voltage 1.0V/, battery discharge 1.2V platform voltage is at more than 95% of battery actual capacity, battery was with 9000mA charging 72 minutes, 90000mA only discharges into final voltage 0.7V/, discharge time〉5.5 minutes, loading capacity is 92% of an actual capacity.Battery high power discharge performance is good, and reduces cost about 20% than conventional nickel metal hydride battery.
Use without the ball-shape nickel hydroxide of modifying and make anode, make negative pole with hydrogen storing alloy powder, and potassium hydroxide electrolyte, barrier film is assembled into D type high-capacity nickel-hydrogen battery.
Battery was with 9000mA charging 72 minutes, 9000mA only discharges into final voltage 1.0V/, battery discharge 1.2V platform voltage is at more than 80% of battery actual capacity, battery was with 9000mA charging 72 minutes, 90000mA only discharges into final voltage 0.7V/, discharge time〉4.8 minutes, loading capacity is 80% of an actual capacity.
Claims (6)
1, a kind of nano carbon technique is modified the method for nickel hydroxide, it is characterized in that comprising the following steps:
(1) in the sodium hydroxide solution of 0.05～0.1mol/L, adds Ni (OH)
2, make Ni (OH)
2Concentration reach 0.1～5mol/L, and add Ni (OH)
25～10% graphite of quality makes mixed solution;
(2) with mixed solution 40～100 ℃ and stir under place electric field, feed direct current by the current density of every square centimeter of 0.05～0.5mA and react; Wherein the bath voltage at the anode and cathode two ends of electric field is 1.5～1.85V;
(3) will through the mixed solution of reaction after 40～80 ℃ down precipitation is shelved, feed ultrasonic wave to mixed solution concussion 2～5h;
(4) will staticly settle, filter, wash through the mixed solution of concussion, obtain the nickel hydroxide that nano carbon is modified after the drying.
2, nano carbon technique according to claim 1 is modified the method for nickel hydroxide, it is characterized in that the stirring velocity in the step (2) is that per minute 500～1500 changes.
3, nano carbon technique according to claim 1 is modified the method for nickel hydroxide, and the negative and positive that it is characterized in that electric field in the step (2) are the nickel metal sheet very.
4, nano carbon technique according to claim 1 is modified the method for nickel hydroxide, it is characterized in that the reaction times in the step (2) is 2～5h.
5, nano carbon technique according to claim 1 is modified the method for nickel hydroxide, it is characterized in that the precipitation time of shelving in the step (3) is 12～24h.
6, nano carbon technique according to claim 1 is modified the method for nickel hydroxide, it is characterized in that the time of staticly settling in the step (4) is 2～10h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200710024530XA CN100500578C (en) | 2007-06-21 | 2007-06-21 | Method for modifying spherical nickel hydroxide by nano carbon technique |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710024530XA CN100500578C (en) | 2007-06-21 | 2007-06-21 | Method for modifying spherical nickel hydroxide by nano carbon technique |
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| CN100500578C true CN100500578C (en) | 2009-06-17 |
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| CNB200710024530XA Expired - Fee Related CN100500578C (en) | 2007-06-21 | 2007-06-21 | Method for modifying spherical nickel hydroxide by nano carbon technique |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618895A (en) * | 2008-07-04 | 2010-01-06 | 中国科学院福建物质结构研究所 | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof |
| CN102826617B (en) * | 2012-09-21 | 2015-05-20 | 中国科学院过程工程研究所 | Spherical nickel hydroxide material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3817789A (en) * | 1971-05-13 | 1974-06-18 | Gates Rubber Co | Compressed powder electrode |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3817789A (en) * | 1971-05-13 | 1974-06-18 | Gates Rubber Co | Compressed powder electrode |
Non-Patent Citations (2)
| Title |
|---|
| Nickel hydroxide/activated carbon composite electrodesfor electrochemical capacitors. Huang QH, etc.Journal of Power Sources,Vol.164 . 2006 |
| Nickel hydroxide/activated carbon composite electrodesfor electrochemical capacitors. Huang QH, etc.Journal of Power Sources,Vol.164 . 2006 * |
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